WO2018181302A1 - 発光ディスプレイシステム及びヘッドアップディスプレイ - Google Patents
発光ディスプレイシステム及びヘッドアップディスプレイ Download PDFInfo
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- WO2018181302A1 WO2018181302A1 PCT/JP2018/012418 JP2018012418W WO2018181302A1 WO 2018181302 A1 WO2018181302 A1 WO 2018181302A1 JP 2018012418 W JP2018012418 W JP 2018012418W WO 2018181302 A1 WO2018181302 A1 WO 2018181302A1
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- WIPO (PCT)
- Prior art keywords
- light
- resin film
- light emitting
- preferable
- display system
- Prior art date
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Images
Classifications
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- G02B27/00—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00
- G02B27/01—Head-up displays
- G02B27/0149—Head-up displays characterised by mechanical features
- G02B2027/015—Head-up displays characterised by mechanical features involving arrangement aiming to get less bulky devices
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B27/00—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00
- G02B27/01—Head-up displays
- G02B2027/0192—Supplementary details
- G02B2027/0194—Supplementary details with combiner of laminated type, for optical or mechanical aspects
Definitions
- the present invention relates to a light emitting display system capable of displaying information of a predetermined luminance in a wide range safely and easily, and a head-up display using the light emitting display system.
- Laminated glass is safe because it does not scatter glass fragments even if it is damaged by an external impact, so it can be used as a windshield, side glass, rear glass for vehicles such as automobiles, and window glass for aircraft, buildings, etc. Widely used.
- the laminated glass include a laminated glass obtained by integrating an interlayer film for laminated glass including a liquid plasticizer and a polyvinyl acetal resin between at least a pair of glasses.
- HUD head-up display
- Patent Document 2 the applicant of the present application is for a laminated glass having a light emitting layer containing a binder resin and at least one light emitting material selected from the group consisting of a light emitting particle, a light emitting pigment, and a light emitting dye.
- An interlayer film has been disclosed.
- the light emitting material has a property of emitting light when irradiated with light of a specific wavelength.
- the amount of information desired to be displayed by HUD has been steadily expanding, and there is an increasing demand for displaying information over a wider range, preferably the entire surface of the windshield.
- the light emission luminance of the light emitting material greatly depends on the irradiation intensity of light from the light source and the distance between the light source and the display location. If information is to be displayed over a wide range, a light source with an extremely high irradiation intensity must be used, which is problematic in terms of safety. On the other hand, even if it is intended to irradiate from a short distance, it is difficult to arrange a light source so that information can be displayed in a wide range in a limited space.
- An object of the present invention is to provide a light emitting display system capable of displaying information of a predetermined luminance in a wide range safely and easily, and a head-up display using the light emitting display system.
- the present invention includes a light emitting resin film containing a thermoplastic resin and a light emitting material, and two or more light sources that emit light having an excitation wavelength of the light emitting material, and the light emitted from the light source is the light emitting resin film.
- the light-emitting resin film and two or more light sources are disposed so as to overlap at least partly.
- the present inventors have studied a light emitting display system that can display information of a predetermined luminance in a wide range safely and easily.
- two or more light sources are prepared, and the light emitted from the light sources is arranged so that at least part of the light emitted from the light sources overlaps the light emitting resin film.
- information of a predetermined luminance can be displayed in a wide range.
- information of a predetermined luminance can be displayed in a sufficiently wide range, so that the light source can be disposed even in a limited space. completed.
- FIG. 1 is a schematic diagram for explaining a method of displaying information by the light emitting display system of the present invention.
- the light emitting display system of FIG. 1 includes a light emitting resin film 1 and two light sources (light source 2 and light source 3). Information is displayed on the light emitting resin film 1 by irradiating the light emitting resin film 1 with light beams having an excitation wavelength from the light source 2 and the light source 3.
- the light source 2 and the light source 3 are arranged so that the irradiated light beam overlaps the light emitting resin film 1.
- information can be displayed with high luminance in a wide range even if the irradiation intensity of each light source is low.
- the individual light sources can obtain sufficient effects even if they are arranged at relatively remote locations, the degree of freedom of light source arrangement is high. Compared with the light emitting display system of FIG. 2 using only one light source 4, the difference in the effect is obvious.
- the two or more light sources are preferably arranged so that the light rays to be irradiated are completely overlapped on the light emitting resin film, but may be arranged to be partially overlapped.
- a part overlaps information is displayed at a particularly high luminance in the overlapping part, so that particularly important information can be displayed in the overlapping part.
- the overlapping rate of light rays emitted from two or more light sources is defined as follows.
- the irradiation area towards the light source area of the light beam is small to be irradiated on the light emitting resin film as S 1, it is different from the light sources the area is small
- the overlapping rate of at least one pair of light sources is preferably 10% or more, more preferably 30% or more, and even more preferably 50% or more.
- 70% or more is particularly preferable, and 100% is most preferable. Furthermore, since information can be displayed more safely and with high brightness, it is preferable that the overlapping rate of all sets of light sources is 10% or more, more preferably 30% or more, and even more preferably 50% or more. It is preferably 70% or more, and most preferably 100%.
- the light-emitting display system of the present invention has a light-emitting resin film containing a thermoplastic resin and a light-emitting material.
- the light emitting material By irradiating with a light beam having an excitation wavelength, the light emitting material emits light, and information can be displayed on the light emitting resin film. That is, the light emitting resin film serves as a screen for displaying information.
- thermoplastic resin is not particularly limited.
- polyvinyl acetal resin ethylene-vinyl acetate copolymer resin, ethylene-acrylic copolymer resin, polyurethane resin, polyurethane resin containing sulfur element, polyvinyl alcohol resin, vinyl chloride. Resin, polyethylene terephthalate resin, ionomer resin, and the like.
- polyvinyl acetal resin is suitable.
- the polyvinyl acetal resin is not particularly limited as long as it is a polyvinyl acetal resin obtained by acetalizing polyvinyl alcohol with an aldehyde, but polyvinyl butyral is preferable. Moreover, you may use together 2 or more types of polyvinyl acetal resin as needed.
- the preferable lower limit of the degree of acetalization of the polyvinyl acetal resin is 40 mol%, the preferable upper limit is 85 mol%, the more preferable lower limit is 60 mol%, and the more preferable upper limit is 75 mol%.
- the polyvinyl acetal resin has a preferred lower limit of the hydroxyl group content of 15 mol% and a preferred upper limit of 35 mol%.
- the amount of the hydroxyl group is 15 mol% or more, the light emitting resin film can be easily formed.
- the hydroxyl group amount is 35 mol% or less, the resulting light-emitting resin film can be easily handled.
- the degree of acetalization and the amount of hydroxyl groups can be measured in accordance with, for example, JIS K6728 “Testing method for polyvinyl butyral”.
- the polyvinyl acetal resin can be prepared by acetalizing polyvinyl alcohol with an aldehyde.
- the polyvinyl alcohol is usually obtained by saponifying polyvinyl acetate, and polyvinyl alcohol having a saponification degree of 70 to 99.8 mol% is generally used.
- the preferable lower limit of the polymerization degree of the polyvinyl alcohol is 500, and the preferable upper limit is 4000.
- the polymerization degree of the polyvinyl alcohol is 500 or more, the penetration resistance of the laminated glass manufactured using the light-emitting display system of the present invention as HUD becomes high. Molding is facilitated when the polymerization degree of the polyvinyl alcohol is 4000 or less.
- the minimum with a more preferable polymerization degree of the said polyvinyl alcohol is 1000, and a more preferable upper limit is 3600.
- the aldehyde is not particularly limited, but generally an aldehyde having 1 to 10 carbon atoms is preferably used.
- the aldehyde having 1 to 10 carbon atoms is not particularly limited.
- n-butyraldehyde, n-hexylaldehyde, and n-valeraldehyde are preferable, and n-butyraldehyde is more preferable.
- These aldehydes may be used alone or in combination of two or more.
- the light-emitting material include a lanthanoid complex having a ligand containing a halogen atom because it can exhibit high light-emitting properties.
- lanthanoid complexes lanthanoid complexes having a ligand containing a halogen atom emit light with high emission intensity when irradiated with light.
- the lanthanoid complex having a ligand containing a halogen atom include a lanthanoid complex having a monodentate ligand containing a halogen atom, a lanthanoid complex having a bidentate ligand containing a halogen atom, and a tridentate configuration containing a halogen atom.
- Halogens such as lanthanoid complexes having ligands, lanthanoid complexes having tetradentate ligands containing halogen atoms, lanthanoid complexes having pentadentate ligands containing halogen atoms, and lanthanoid complexes having hexadentate ligands containing halogen atoms
- a lanthanoid complex having a polydentate ligand containing an atom is exemplified.
- a lanthanoid complex having a bidentate ligand containing a halogen atom or a lanthanoid complex having a tridentate ligand containing a halogen atom has a wavelength of 580 to 780 nm when irradiated with light having a wavelength of 300 to 410 nm.
- Light with extremely high emission intensity Since this light emission has extremely high intensity, a light emitting display system having a light emitting resin film containing the light emission can emit light with relatively high luminance even when irradiated with a light beam with low output.
- the lanthanoid complex having a bidentate ligand containing a halogen atom or the lanthanoid complex having a tridentate ligand containing a halogen atom is also excellent in heat resistance.
- the light-emitting display system is used as an automobile roof glass or building window glass as a HUD, it is often used in a high temperature environment by being irradiated with infrared rays of sunlight. In such a high temperature environment, the luminescent material may be deteriorated, and the luminescent material may be deteriorated particularly at the end of the laminated glass.
- the lanthanoid complex having a bidentate ligand containing a halogen atom or the lanthanoid complex having a tridentate ligand containing a halogen atom as the light emitting material, deterioration can be prevented even in a high temperature environment.
- the lanthanoid includes lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium or lutetium. Since higher emission intensity can be obtained, the lanthanoid is preferably neodymium, europium or terbium, more preferably europium or terbium, and still more preferably europium.
- Examples of the bidentate ligand containing a halogen atom include a ligand having a structure represented by the following general formula (1), a ligand having a structure represented by the following general formula (2), and the like. Can be mentioned.
- R 1 and R 3 represents an organic group, at least one of R 1 and R 3 is an organic group containing a halogen atom, R 2 is the number 1 or more linear carbon Represents an organic group.
- R 1 and R 3 are preferably a hydrocarbon group, more preferably a hydrocarbon group having 1 to 10 carbon atoms, still more preferably a hydrocarbon group having 1 to 5 carbon atoms, Particularly preferred is a hydrocarbon group having 1 to 3 carbon atoms.
- a part of hydrogen atoms may be substituted with an atom other than a hydrogen atom and a functional group.
- hydrocarbon group having 1 to 3 carbon atoms examples include methyl, ethyl, and propyl groups in which hydrogen atoms are not substituted, and methyl, ethyl, and propyl groups in which some of the hydrogen atoms are substituted with halogen atoms. Group and the like.
- a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom can be used as a halogen atom of a methyl group, an ethyl group, or a propyl group in which a part of the hydrogen atom is substituted with a halogen atom.
- the hydrocarbon group having 1 to 3 carbon atoms is preferably a methyl group, an ethyl group or a propyl group in which a part of the hydrogen atoms are substituted with a halogen atom, since it emits light with high emission intensity. More preferably, it is a fluoromethyl group.
- R 2 is preferably an alkylene group having 1 or more carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, and most preferably a methylene group having 1 carbon atom. In the alkylene group having 1 or more carbon atoms, a part of hydrogen atoms may be substituted with an atom other than a hydrogen atom and a functional group.
- the lanthanoid complex having a ligand containing a halogen atom only needs to have at least one ligand containing a halogen atom, and may have a ligand not containing a halogen atom.
- the ligand that does not contain a halogen atom includes a ligand that is the same as the above general formula (1) except that it does not contain a halogen atom, and a structure represented by the following general formulas (2) to (8). And the like.
- two Ns may be anywhere in the bipyridine skeleton.
- two Ns may be anywhere in the bipyridine skeleton. Among them, it is preferable that there are two Ns at the 1 and 10 positions.
- two Ns may be anywhere in the bipyridine skeleton. Among them, it is preferable that there are two Ns at the 1 and 10 positions.
- the three Ns may be anywhere in the terpyridine skeleton.
- the central R 4 represents a linear organic group having 1 or more carbon atoms.
- two R 5 represents one or more linear organic group having a carbon number.
- n represents an integer of 1 or 2.
- Examples of the lanthanoid complex having a bidentate ligand containing a halogen atom include tris (trifluoroacetylacetone) phenanthroline europium (Eu (TFA) 3 phen), tris (trifluoroacetylacetone) diphenylphenanthroline europium (Eu (TFA) 3 dpphen), tris (hexafluoroacetylacetone) diphenylphenanthroline europium, tris (hexafluoroacetylacetone) bis (triphenylphosphine) europium, tris (trifluoroacetylacetone) 2,2′-bipyridine europium, tris (hexafluoroacetylacetone) 2,2 '-Bipyridine Europium, Tris (5,5,6,6,7,7,7-heptafluoro-2,4-pentandionate) 2 2'-bipyridine europium ([Eu (FPD
- lanthanoid complex having a bidentate ligand containing a halogen atom examples include tris (trifluoroacetylacetone) phenanthroline terbium (Tb (TFA) 3 phen), tris (trifluoroacetylacetone) diphenylphenanthroline terbium (Tb ( TFA) 3 dpphen), tris (hexafluoroacetylacetone) diphenylphenanthroline terbium, tris (hexafluoroacetylacetone) bis (triphenylphosphine) terbium, tris (trifluoroacetylacetone) 2,2′-bipyridineterbium, tris (hexafluoroacetylacetone) 2,2'-bipyridineterbium, tris (5,5,6,6,7,7,7-heptafluoro-2,4-pentanedionate) 2,2'- Bipyridine terbium ([
- halogen atom of the lanthanoid complex having a ligand containing a halogen atom a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom can be used.
- a fluorine atom is preferable because the structure of the ligand is stabilized.
- the lanthanoid complex having a halogen atom and an acetylacetone skeleton containing a halogen atom is particularly excellent.
- Lanthanoid complexes having a bidentate ligand are preferred.
- Examples of the lanthanoid complex having a bidentate ligand having an acetylacetone skeleton containing a halogen atom include Eu (TFA) 3 phen, Eu (TFA) 3 dpphen, Eu (HFA) 3 phen, and [Eu (FPD) 3 ]. bpy, [Eu (TFA) 3 ] tmphen, [Eu (FPD) 3 ] phen and the like. The structure of a lanthanoid complex having a bidentate ligand having an acetylacetone skeleton containing these halogen atoms is shown.
- Lanthanide complex having a bidentate ligand having acetylacetone skeleton containing the halogen atom Additional e.g., Tb (TFA) 3 phen, Tb (TFA) 3 dpphen, Tb (HFA) 3 phen, [Tb (FPD ) 3 ] bpy, [Tb (TFA) 3 ] tmphen, [Tb (FPD) 3 ] phen and the like.
- the lanthanoid complex having a ligand containing a halogen atom is preferably particulate. By being particulate, it becomes easier to finely disperse the lanthanoid complex having a ligand containing a halogen atom in a thermoplastic resin.
- the preferable lower limit of the average particle diameter of the lanthanoid complex is 0.01 ⁇ m
- the preferable upper limit is 10 ⁇ m
- the more preferable lower limit is 0.03 ⁇ m, more preferable.
- the upper limit is 1 ⁇ m.
- a light emitting material having a terephthalic acid ester structure can also be used.
- the light emitting material having the terephthalic acid ester structure emits light when irradiated with light.
- Examples of the light emitting material having the terephthalic acid ester structure include a compound having a structure represented by the following general formula (9) and a compound having a structure represented by the following general formula (10). These may be used alone or in combination of two or more.
- R 6 represents an organic group, and x is 1, 2, 3 or 4. Since the transparency of the light emitting display is further enhanced, x is preferably 1 or 2, more preferably a hydroxyl group at the 2-position or 5-position of the benzene ring, and at the 2-position and 5-position of the benzene ring. More preferably, it has a hydroxyl group.
- the organic group for R 6 is preferably a hydrocarbon group, more preferably a hydrocarbon group having 1 to 10 carbon atoms, still more preferably a hydrocarbon group having 1 to 5 carbon atoms, Particularly preferred is a hydrocarbon group having 1 to 3 carbon atoms. When the hydrocarbon group has 10 or less carbon atoms, the light-emitting material having the terephthalic acid ester structure can be easily dispersed in the thermoplastic resin.
- the hydrocarbon group is preferably an alkyl group.
- Examples of the compound having the structure represented by the general formula (9) include diethyl-2,5-dihydroxyterephthalate, dimethyl-2,5-dihydroxyterephthalate and the like. Among these, since an image can be displayed with higher brightness, the compound having the structure represented by the general formula (9) is diethyl-2,5-dihydroxyterephthalate (“2,5-dihydroxyterephthalic acid manufactured by Aldrich). Diethyl ”) is preferred.
- R 7 represents an organic group
- R 8 and R 9 represent a hydrogen atom or an organic group
- y is 1, 2, 3, or 4.
- the organic group for R 7 is preferably a hydrocarbon group, more preferably a hydrocarbon group having 1 to 10 carbon atoms, still more preferably a hydrocarbon group having 1 to 5 carbon atoms, Particularly preferred is a hydrocarbon group having 1 to 3 carbon atoms.
- the hydrocarbon group is preferably an alkyl group.
- NR 8 R 9 is an amino group.
- R 8 and R 9 are preferably hydrogen atoms.
- one hydrogen atom may be the amino group, and two hydrogen atoms may be the amino group.
- the three hydrogen atoms may be the amino group, and the four hydrogen atoms may be the amino group.
- diethyl-2,5-diaminoterephthalate (manufactured by Aldrich) is preferable because an image can be displayed with higher luminance.
- the content of the light emitting material in the light emitting resin film is preferably 0.001 part by weight with respect to 100 parts by weight of the thermoplastic resin, and 15 parts by weight with respect to the preferable upper limit.
- the more preferable lower limit of the content of the light emitting material is 0.01 parts by weight, the more preferable upper limit is 10 parts by weight, the still more preferable lower limit is 0.05 parts by weight, the still more preferable upper limit is 8 parts by weight, and the particularly preferable lower limit is 0.1 parts by weight.
- Part by weight, particularly preferred upper limit is 5 parts by weight, and the most preferred upper limit is 1 part by weight.
- the light emitting resin film preferably further contains a dispersant.
- a dispersant is, for example, a compound having a sulfonic acid structure such as a linear alkylbenzene sulfonate, or an ester structure such as a diester compound, a ricinoleic acid alkyl ester, a phthalic acid ester, an adipic acid ester, a sebacic acid ester, or a phosphoric acid ester.
- Compounds having an ether structure such as polyoxyethylene glycol, polyoxypropylene glycol and alkylphenyl-polyoxyethylene-ether, compounds having a carboxylic acid structure such as polycarboxylic acid, laurylamine, dimethyllauryl
- Compounds having an amine structure such as amines, oleylpropylenediamine, secondary amines of polyoxyethylene, tertiary amines of polyoxyethylene, and diamines of polyoxyethylene
- polyalkylenepolyaminealkyleneoxy Dispersants such as compounds having a polyamine structure such as amides, compounds having an amide structure such as oleic acid diethanolamide and alkanol fatty acid amide, and compounds having a high molecular weight amide structure such as polyvinylpyrrolidone and polyester acid amide amine salts Can be used.
- high molecular weight dispersing agents such as polyoxyethylene alkyl ether phosphoric acid (salt), high molecular polycarboxylic acid, and condensed ricinoleic acid ester.
- the high molecular weight dispersant is defined as a dispersant having a molecular weight of 10,000 or more.
- the preferred lower limit of the content of the dispersant relative to the luminescent material in the luminescent resin film is 1 part by weight, and the preferred upper limit is 50 parts by weight.
- the content of the dispersant is within this range, the light emitting material can be uniformly dispersed in the thermoplastic resin.
- the more preferable lower limit of the content of the dispersant is 3 parts by weight, the more preferable upper limit is 30 parts by weight, the still more preferable lower limit is 5 parts by weight, and the still more preferable upper limit is 25 parts by weight.
- the light emitting resin film may further contain an ultraviolet absorber.
- the content of the ultraviolet absorber in the light emitting resin film is preferably 1 part by weight, more preferably 0.5 part by weight with respect to 100 parts by weight of the thermoplastic resin.
- a more preferred upper limit is 0.2 parts by weight, and a particularly preferred upper limit is 0.1 parts by weight.
- Examples of the ultraviolet absorber include a compound having a malonic ester structure, a compound having an oxalic acid anilide structure, a compound having a benzotriazole structure, a compound having a benzophenone structure, a compound having a triazine structure, a compound having a benzoate structure, and a hindered amine
- Examples include ultraviolet absorbers such as compounds having a structure.
- the light emitting resin film may further contain a plasticizer.
- the plasticizer is not particularly limited, and examples thereof include organic ester plasticizers such as monobasic organic acid esters and polybasic organic acid esters, phosphoric acid plasticizers such as organic phosphoric acid plasticizers and organic phosphorous acid plasticizers, and the like. Is mentioned.
- the plasticizer is preferably a liquid plasticizer.
- the said monobasic organic acid ester is not specifically limited,
- the glycol ester obtained by reaction of glycol and a monobasic organic acid etc. are mentioned.
- the glycol include triethylene glycol, tetraethylene glycol, and tripropylene glycol.
- the monobasic organic acid include butyric acid, isobutyric acid, caproic acid, 2-ethylbutyric acid, heptylic acid, n-octylic acid, 2-ethylhexylic acid, pelargonic acid (n-nonylic acid), decylic acid and the like. It is done.
- triethylene glycol dicaproate, triethylene glycol di-2-ethylbutyrate, triethylene glycol di-n-octylate, triethylene glycol di-2-ethylhexylate and the like are preferable.
- the polybasic organic acid ester is not particularly limited.
- an ester compound of a polybasic organic acid such as adipic acid, sebacic acid or azelaic acid and an alcohol having a linear or branched structure having 4 to 8 carbon atoms.
- dibutyl sebacic acid ester, dioctyl azelaic acid ester, dibutyl carbitol adipic acid ester and the like are preferable.
- the organic ester plasticizer is not particularly limited, and triethylene glycol di-2-ethylbutyrate, triethylene glycol di-2-ethylhexanoate, triethylene glycol dicaprylate, triethylene glycol di-n-octanoate, Triethylene glycol di-n-heptanoate, tetraethylene glycol di-n-heptanoate, tetraethylene glycol di-2-ethylhexanoate, dibutyl sebacate, dioctyl azelate, dibutyl carbitol adipate, ethylene glycol di-2-ethyl Butyrate, 1,3-propylene glycol di-2-ethyl butyrate, 1,4-butylene glycol di-2-ethyl butyrate, diethylene glycol di-2-ethyl butyrate, diethylene glycol di- -Ethylhexanoate, dipropylene glycol di-2-ethylbutyrate,
- the organophosphate plasticizer is not particularly limited, and examples thereof include tributoxyethyl phosphate, isodecylphenyl phosphate, triisopropyl phosphate, and the like.
- dihexyl adipate DHA
- triethylene glycol di-2-ethylhexanoate 3GO
- tetraethylene glycol di-2-ethylhexanoate 4GO
- content of the said plasticizer in the said light emitting resin film is not specifically limited,
- the preferable minimum with respect to 100 weight part of the said thermoplastic resins is 30 weight part, and a preferable upper limit is 100 weight part.
- the content of the plasticizer is 30 parts by weight or more, the light-emitting resin film has a low melt viscosity, and thus can be easily molded.
- the transparency of a light emitting resin film becomes it high that content of the said plasticizer is 100 weight part or less.
- a more preferred lower limit of the plasticizer content is 35 parts by weight, a more preferred upper limit is 80 parts by weight, a still more preferred lower limit is 45 parts by weight, a still more preferred upper limit is 70 parts by weight, a particularly preferred lower limit is 50 parts by weight, and a particularly preferred upper limit. Is 63 parts by weight.
- the antioxidant is not particularly limited, and examples thereof include an antioxidant having a phenol structure, an antioxidant containing sulfur, and an antioxidant containing phosphorus.
- the antioxidant having the phenol structure is an antioxidant having a phenol skeleton.
- antioxidant having a phenol structure examples include 2,6-di-t-butyl-p-cresol (BHT), butylated hydroxyanisole (BHA), 2,6-di-t-butyl-4- Ethylphenol, stearyl- ⁇ - (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,2′-methylenebis- (4-methyl-6-butylphenol), 2,2′-methylenebis- ( 4-ethyl-6-t-butylphenol), 4,4'-butylidene-bis- (3-methyl-6-t-butylphenol), 1,1,3-tris- (2-methyl-hydroxy-5-t -Butylphenyl) butane, tetrakis [methylene-3- (3 ', 5'-butyl-4-hydroxyphenyl) propionate] methane, 1,3,3-tris- (2-methyl) 4-hydroxy-5-tert-butylphenol) butane, 1,3,5-trimethyl-2
- the light emitting resin film may contain an adhesive strength adjusting agent in order to adjust the adhesive strength to glass.
- an adhesive force regulator at least 1 sort (s) selected from the group which consists of an alkali metal salt, alkaline-earth metal salt, and magnesium salt, for example is used suitably.
- salts such as potassium, sodium, magnesium, are mentioned, for example.
- the acid constituting the salt include organic acids of carboxylic acids such as octylic acid, hexyl acid, 2-ethylbutyric acid, butyric acid, acetic acid and formic acid, or inorganic acids such as hydrochloric acid and nitric acid.
- the light emitting resin film may contain additives such as a light stabilizer, an antistatic agent, a blue pigment, a blue dye, a green pigment, and a green dye as necessary.
- the thickness of the said light emitting resin film is not specifically limited, A preferable minimum is 100 micrometers and a preferable upper limit is 2000 micrometers. When the thickness of the light emitting resin film is within this range, information can be displayed with high luminance.
- the more preferable lower limit of the thickness of the light emitting resin film is 300 ⁇ m, the further preferable lower limit is 740 ⁇ m, the particularly preferable lower limit is 760 ⁇ m, the more preferable upper limit is 1600 ⁇ m, the still more preferable upper limit is 1400 ⁇ m, and the particularly preferable upper limit is 880 ⁇ m.
- the light emitting resin film may be used as a single layer or as a multilayer resin film in which other resin films are laminated (hereinafter also simply referred to as “multilayer resin film”).
- the light emitting resin film may be disposed on the entire surface of the multilayer resin film, or may be disposed only on a part thereof, and is perpendicular to the thickness direction of the multilayer resin film. It may be arranged on the entire surface in the surface direction, or may be arranged only in part.
- the light emitting resin film is disposed only in a part, information can be displayed only in the light emitting area, with the part as a light emitting area and the other part as a non-light emitting area.
- the plasticizer content (hereinafter also referred to as content X) with respect to 100 parts by weight of the thermoplastic resin in the light emitting resin film is used as the heat in other resin films.
- content Y The content of the plasticizer relative to 100 parts by weight of the plastic resin
- the content X is preferably 5 parts by weight or more, more preferably 10 parts by weight or more, and still more preferably 15 parts by weight or more than the content Y. Since the penetration resistance of the multilayer resin film is further enhanced, the difference between the content X and the content Y is preferably 50 parts by weight or less, and more preferably 40 parts by weight or less. More preferably, it is 35 parts by weight or less.
- the preferred lower limit of the content X is 45 parts by weight, the preferred upper limit is 80 parts by weight, the more preferred lower limit is 50 parts by weight, the more preferred upper limit is 75 parts by weight, and the still more preferred lower limit is 55 parts by weight. Is 70 parts by weight.
- the preferred lower limit of the content Y is 20 parts by weight, the preferred upper limit is 45 parts by weight, the more preferred lower limit is 30 parts by weight, the more preferred upper limit is 43 parts by weight, and the still more preferred lower limit is 35 parts by weight. Is 41 parts by weight.
- the thermoplastic resin in the light emitting resin film is preferably polyvinyl acetal X.
- the polyvinyl acetal X can be prepared by acetalizing polyvinyl alcohol with an aldehyde.
- the polyvinyl alcohol is usually obtained by saponifying polyvinyl acetate.
- a preferable lower limit of the average degree of polymerization of the polyvinyl alcohol is 200, and a preferable upper limit is 5000.
- the more preferable lower limit of the average degree of polymerization of the polyvinyl alcohol is 500, and the more preferable upper limit is 4000.
- the average degree of polymerization of the polyvinyl alcohol is determined by a method based on JIS K6726 “Testing method for polyvinyl alcohol”.
- the preferable lower limit of the carbon number of the aldehyde for acetalizing the polyvinyl alcohol is 4, and the preferable upper limit is 6.
- the aldehyde having 4 to 6 carbon atoms may be a linear aldehyde or a branched aldehyde, and examples thereof include n-butyraldehyde and n-valeraldehyde. .
- the upper limit with the preferable amount of hydroxyl groups of the said polyvinyl acetal X is 30 mol%.
- the upper limit of the amount of hydroxyl groups in the polyvinyl acetal X is more preferably 28 mol%, more preferably 26 mol%, and particularly preferably 24 mol%, the preferable lower limit is 10 mol%, and the more preferable lower limit is 15 mol%.
- a preferred lower limit is 20 mol%.
- the amount of hydroxyl groups in the polyvinyl acetal X is a value obtained by dividing the amount of ethylene groups to which the hydroxyl groups are bonded by the total amount of ethylene groups in the main chain, as a percentage (mol%).
- the amount of ethylene group to which the hydroxyl group is bonded can be determined, for example, by measuring the amount of ethylene group to which the hydroxyl group of polyvinyl acetal X is bonded by a method based on JIS K6728 “Testing method for polyvinyl butyral”. it can.
- the minimum with the preferable amount of acetal groups of the said polyvinyl acetal X is 60 mol%, and a preferable upper limit is 85 mol%.
- a preferable upper limit is 85 mol%.
- the lower limit of the amount of acetal group of the polyvinyl acetal X is more preferably 65 mol%, still more preferably 68 mol% or more.
- the amount of the acetal group can be determined by measuring the amount of ethylene group to which the acetal group of the polyvinyl acetal X is bonded by a method based on JIS K6728 “Testing method for polyvinyl butyral”.
- the minimum with the preferable amount of acetyl groups of the said polyvinyl acetal X is 0.1 mol%, and a preferable upper limit is 30 mol%.
- a preferable upper limit is 30 mol%.
- the more preferable lower limit of the acetyl group amount of the polyvinyl acetal X is 1 mol%, the more preferable lower limit is 5 mol%, the particularly preferable lower limit is 8 mol%, the more preferable upper limit is 25 mol%, and the more preferable upper limit is 20 mol%. It is.
- the amount of acetyl groups is the value obtained by subtracting the amount of ethylene groups to which acetal groups are bonded and the amount of ethylene groups to which hydroxyl groups are bonded from the total amount of ethylene groups in the main chain. This is a value expressed as a percentage (mol%) of the mole fraction obtained by dividing by.
- the polyvinyl acetal X is a polyvinyl acetal having an acetyl group content of 8 mol% or more, or The polyvinyl acetal having an acetyl group content of less than 8 mol% and an acetal group content of 65 mol% or more is preferred.
- the polyvinyl acetal X is a polyvinyl acetal having an acetyl group amount of 8 mol% or more, or a polyvinyl acetal having an acetyl group amount of less than 8 mol% and an acetal group amount of 68 mol% or more. More preferable.
- the thermoplastic resin in the other resin film is preferably polyvinyl acetal Y.
- the polyvinyl acetal Y preferably has a larger amount of hydroxyl groups than the polyvinyl acetal X.
- the polyvinyl acetal Y can be prepared by acetalizing polyvinyl alcohol with an aldehyde.
- the polyvinyl alcohol is usually obtained by saponifying polyvinyl acetate.
- the preferable minimum of the average degree of polymerization of the said polyvinyl alcohol is 200, and a preferable upper limit is 5000.
- the more preferable lower limit of the average degree of polymerization of the polyvinyl alcohol is 500, and the more preferable upper limit is 4000.
- the preferable lower limit of the carbon number of the aldehyde for acetalizing the polyvinyl alcohol is 3, and the preferable upper limit is 4.
- the carbon number of the aldehyde is 3 or more, the penetration resistance of the multilayer resin film is increased.
- the aldehyde having 3 to 4 carbon atoms may be a linear aldehyde or a branched aldehyde, and examples thereof include n-butyraldehyde.
- the upper limit with the preferable amount of hydroxyl groups of the said polyvinyl acetal Y is 33 mol%, and a preferable minimum is 28 mol%.
- a preferable minimum is 28 mol%.
- the minimum with the preferable amount of acetal groups of the said polyvinyl acetal Y is 60 mol%, and a preferable upper limit is 80 mol%.
- a preferable upper limit is 80 mol%.
- the upper limit with the preferable amount of acetyl groups of the said polyvinyl acetal Y is 7 mol%.
- the upper limit with the more preferable amount of acetyl groups of the said polyvinyl acetal Y is 2 mol%, and a preferable minimum is 0.1 mol%.
- the amount of hydroxyl groups, the amount of acetal groups, and the amount of acetyl groups of polyvinyl acetal Y can be measured by the same method as for polyvinyl acetal X.
- any one layer, any two layers, or all layers of the light emitting resin film and other resin films are allowed to contain a heat ray absorbent. be able to.
- the heat ray absorber is not particularly limited as long as it has the ability to shield infrared rays, but is tin-doped indium oxide (ITO) particles, antimony-doped tin oxide (ATO) particles, aluminum-doped zinc oxide (AZO) particles, indium-doped oxide. At least one selected from the group consisting of zinc (IZO) particles, tin-doped zinc oxide particles, silicon-doped zinc oxide particles, lanthanum hexaboride particles and cerium hexaboride particles is preferred.
- the thickness of the multilayer resin film is not particularly limited, but a preferred lower limit is 50 ⁇ m, a preferred upper limit is 1700 ⁇ m, a more preferred lower limit is 100 ⁇ m, a more preferred upper limit is 1000 ⁇ m, and a further preferred upper limit is 900 ⁇ m.
- the lower limit of the thickness of the multilayer resin film means the thickness of the minimum thickness portion of the multilayer resin film
- the upper limit of the thickness of the multilayer resin film is the thickness of the maximum thickness portion of the multilayer resin film. Means.
- a preferable minimum is 50 micrometers and a preferable upper limit is 1000 micrometers.
- the thickness of the light emitting resin film is within this range, light emission with sufficiently high contrast can be obtained when irradiated with light having a specific wavelength.
- the more preferable lower limit of the thickness of the multilayer resin film is 80 ⁇ m, the more preferable upper limit is 500 ⁇ m, the still more preferable lower limit is 90 ⁇ m, and the still more preferable upper limit is 300 ⁇ m.
- the light emitting resin film or the multilayer resin film may have a wedge-shaped cross section.
- the cross-sectional shape is a wedge shape, it is possible to prevent the generation of a double image when used as a HUD, for example.
- the upper limit of the wedge angle ⁇ of the wedge shape is preferably 1 mrad.
- a film having a wedge-shaped cross-section is manufactured by a method of extruding a resin composition using an extruder, a region slightly inside from one end on the thin side (specifically, one end and the other)
- the shape may have a minimum thickness in the range from 0X to 0.2X inward from one end on the thin side.
- a region slightly inside from one end portion on the thick side may have a maximum thickness.
- such a shape is also included in the wedge shape.
- the cross-sectional shape of the multilayer resin film is wedge-shaped, while making the thickness of the light-emitting resin film a certain range, the cross-sectional shape of the multilayer resin film as a whole is obtained by laminating the other resin film as a shape auxiliary layer. It can be adjusted to have a wedge shape with a constant wedge angle. Alternatively, by making at least one of the light emitting resin film and the other resin film into a wedge shape, the cross-sectional shape of the entire multilayer resin film can be adjusted to be a wedge shape having a constant wedge angle.
- the other resin film may be laminated only on one surface of the light emitting resin film, or may be laminated on both surfaces. Further, a plurality of other resin films may be laminated.
- the light emitting resin film may have a wedge shape or a rectangular cross section.
- the difference between the maximum thickness and the minimum thickness of the light emitting resin film is preferably 100 ⁇ m or less. Thereby, it can suppress that a big difference arises in the brightness
- the difference between the maximum thickness and the minimum thickness of the light emitting resin film is more preferably 95 ⁇ m or less, and still more preferably 90 ⁇ m or less.
- the thickness of the light emitting resin film is not particularly limited, but a preferable lower limit is 50 ⁇ m and a preferable upper limit is 700 ⁇ m. When the thickness of the light emitting resin film is within this range, uniform information can be displayed.
- a more preferable lower limit of the thickness of the light emitting resin film is 70 ⁇ m, a more preferable upper limit is 400 ⁇ m, a still more preferable lower limit is 80 ⁇ m, and a still more preferable upper limit is 150 ⁇ m.
- the lower limit of the thickness of the light emitting resin film means the thickness of the minimum thickness portion of the light emitting resin film, and the upper limit of the thickness of the light emitting resin film means the thickness of the maximum thickness portion of the light emitting resin film. To do.
- the other resin film has a role of being laminated on the light emitting resin film and adjusting so that the cross-sectional shape of the entire multilayer resin film becomes a wedge shape having a constant wedge angle.
- the other resin film preferably has a wedge shape, a triangle shape, a trapezoidal shape or a rectangular shape in cross section.
- the thickness of the other resin film is not particularly limited, but from the viewpoint of practical use and from the viewpoint of sufficiently enhancing the adhesive strength and penetration resistance, the preferred lower limit is 10 ⁇ m, the preferred upper limit is 1000 ⁇ m, and the more preferred lower limit is 200 ⁇ m. A more preferable upper limit is 800 ⁇ m, and a still more preferable lower limit is 300 ⁇ m.
- the lower limit of the thickness of the other resin film means the thickness of the minimum thickness portion of the other resin film, and the upper limit of the thickness of the other resin film is a portion of the maximum thickness of the other resin film. Means the thickness of Moreover, when using combining several other resin films, the total thickness is meant.
- the light emitting resin film and the multilayer resin film are preferably reinforced with at least one glass plate.
- the light emitting resin film and the multilayer resin film may be used as laminated glass laminated between a pair of glass plates.
- the said glass plate can use the transparent plate glass generally used. Examples thereof include inorganic glass such as float plate glass, polished plate glass, template glass, netted glass, wire-containing plate glass, colored plate glass, heat ray absorbing glass, heat ray reflecting glass, and green glass.
- the ultraviolet shielding glass in which the ultraviolet shielding coating layer was formed in the glass surface can be used, it is preferable to use as a glass plate opposite to the side irradiated with the light ray of a specific wavelength.
- organic plastics plates such as polyethylene terephthalate, polycarbonate, and polyacrylate can be used as the glass plate.
- Two or more types of glass plates may be used as the glass plate.
- stacked the said light emitting resin film and the said multilayer resin film between transparent float plate glass and colored glass plates like green glass is mentioned.
- the light emitting display system of the present invention has a light source.
- the light source irradiates light having an excitation wavelength of the light emitting material in the light emitting resin film. It serves to display information on the light emitting resin film by irradiating the light.
- the irradiated light includes the excitation wavelength of the luminescent material and is selected according to the type of the luminescent material.
- the light-emitting display system of the present invention two or more light sources are used, and the light rays emitted from the light sources are arranged so that at least a part thereof overlaps the light-emitting resin film.
- the degree of freedom of light source arrangement is high.
- a larger number of light sources can display information with higher luminance in a wider range, but considering the arrangement in a limited space, the upper limit is practically about 10 units. .
- the irradiation intensity of the light having the excitation wavelength irradiated from the light source is 200 mW / cm 2 or less. If the irradiation intensity is 200 mW / cm 2 or less, sufficient safety can be ensured. In addition, if the irradiation intensity is 200 mW / cm 2 or less, it is not difficult to dispose the apparatus with a large size. Irradiation intensity of light of the excitation wavelength emitted from the light source is more preferably more preferably 150 mW / cm 2 or less, 100 mW / cm 2 or less.
- the lower limit of the irradiation intensity of the light of the excitation wavelength irradiated from the light source is not particularly limited, but in order to display information with sufficient luminance, it is preferably 10 mW / cm 2 or more, and 50 mW / cm 2 or more. More preferably.
- the output of the light beam to be irradiated is measured by irradiation intensity measurement using a laser power meter (for example, “Beam Track Power Measurement Sensor 3A-QUAD” manufactured by OFIEL JAPAN Co., Ltd.) disposed at a position 10 cm away from the light source. Can be measured.
- a laser power meter for example, “Beam Track Power Measurement Sensor 3A-QUAD” manufactured by OFIEL JAPAN Co., Ltd.
- Examples of the light source include spot light sources (manufactured by Hamamatsu Photonics, “LC-8”, etc.), xenon flash lamps (manufactured by Heraeus, “CW lamp”, etc.), black lights (manufactured by Inoue Seieido, “carry hand” ]) And the like.
- the light emitting display system of the present invention By using the light emitting display system of the present invention, it is possible to display information of a predetermined luminance in a wide range safely and easily.
- the light emitting display system of the present invention can be widely used as a windshield, side glass, rear glass of a vehicle such as an automobile, and a window glass of an aircraft, a building, or the like.
- the light emitting display system of this invention which has arrange
- the light emission display system which can display the information of predetermined
- Example 1 (1) the 2m 3 reactor fitted with a preparation stirrer polyvinyl butyral, PVA (polymerization degree 1700, saponification degree 99 mol%) 7.5 wt% aqueous solution of 1700kg and n- butyraldehyde 74.6kg of 2,6 Di-t-butyl-4-methylphenol (0.13 kg) was charged and the whole was cooled to 14 ° C. To this, 99.44 L of nitric acid having a concentration of 30% by mass was added, and butyralization of PVA was started. After 10 minutes from the end of the addition, the temperature was started to rise, the temperature was raised to 65 ° C. over 90 minutes, and the reaction was further carried out for 120 minutes.
- PVA polymerization degree 1700, saponification degree 99 mol% aqueous solution of 1700kg and n- butyraldehyde 74.6kg of 2,6 Di-t-butyl-4-methylphenol (0.13 kg) was charged and the whole was cooled to 14
- the obtained light-emitting resin film was laminated as an interlayer film for laminated glass between a pair of clear glass (thickness 2.5 mm) measuring 5 cm in length and 5 cm in width to obtain a laminate.
- the obtained laminate was vacuum-pressed while being held at 90 ° C. for 30 minutes with a vacuum laminator to be pressure-bonded. After the pressure bonding, pressure bonding was performed for 20 minutes using an autoclave under conditions of 140 ° C. and 14 MPa to obtain a laminated glass.
- Example 3 12.5 mmol of terbium acetate (Tb (CH 3 COO) 3 ) was dissolved in 50 mL of distilled water, 33.6 mmol of trifluoroacetylacetone (TFA, CH 3 COCH 2 COCF 3 ) was added, and the mixture was stirred at room temperature for 3 hours. The precipitated solid was filtered, washed with water, and recrystallized with methanol and distilled water to obtain Tb (TFA) 3 (H 2 O) 2 . The obtained complex Tb (TFA) 3 (H 2 O) 2 (5.77 g) and 1,10-phenanthroline (phen) (2.5 g) were dissolved in 100 mL of methanol and heated under reflux for 12 hours.
- Tb (TFA) 3 (H 2 O) 2 5.77 g
- 1,10-phenanthroline (phen) 2.5 g
- Tb (TFA) 3 phene was obtained by recrystallization from a mixed solvent of toluene and hexane.
- Tb (TFA) 3 phen 0.4 obtained by replacing 0.54 parts by weight of diethyl-2,5-dihydroxyterephthalate (manufactured by Aldrich, “diethyl 2,5-dihydroxyterephthalate”) with respect to 40 parts by weight of 3GO
- a light emitting resin film and a laminated glass were produced in the same manner as in Example 1 except that parts by weight were used. Then, two or three light sources were arranged to construct a light emitting display system.
- the light emission display system which can display the information of predetermined
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Abstract
Description
HUDとしては、これまでに数々の形態が開発されている。最も一般的なHUDとしてコントロールユニットから送信される速度情報等をインストゥルメンタル・パネルの表示ユニットからフロントガラスに反射させることにより、運転者がフロントガラスと同じ位置、すなわち、同一視野内で速度情報等を視認できるHUDがある。
HUD用の合わせガラス用中間膜として、例えば、特許文献1には、所定の楔角を有する楔形合わせガラス用中間膜等が提案されており、合わせガラスにおいて計器表示が二重に見えるというHUDの欠点を解決することが提案されている。
特許文献1に記載された合わせガラスは、合わせガラスの面内の一部の領域であれば、計器表示が二重に見えるというHUDの欠点を解決することができる。即ち、合わせガラスの面内の全面において、計器表示が二重に見えるという問題は解決されていない。
以下に本発明を詳述する。
ここで光源2と光源3とは、照射される光線が発光樹脂フィルム1上に重複するように配置される。2台の光源から照射される光線が発光樹脂フィルム1上で重複することにより、たとえ個々の光源の照射強度が低くとも、広い範囲において高い輝度で情報を表示することができる。また、個々の光源は、比較的離れた場所に配置しても充分な効果を得られることから、光源配置の自由度も高い。1台の光源4のみを用いた図2の発光ディスプレイシステムと比べると、その効果の差は歴然である。
本明細書では、2台以上の光源から照射される光線の重複率を、以下のように定義する。2台以上の光源から照射される光線が重複している際に、発光樹脂フィルム上に照射される光線の面積が小さい方の光源の照射面積をS1とし、該面積が小さい光源とは異なる他方の光源と重複している面積をS2とした場合に、「重複率(%)=S2/S1×100」と定義する。3台以上の光源から光線が照射される場合には、2台を1組とし、組合せ毎に重複率を求めることが好ましい。
より一層安全かつ高い輝度で情報を表示できることから、少なくとも1組の光源の重複率が10%以上であることが好ましく、30%以上であることがより好ましく、50%以上であることが更に好ましく、70%以上であることが特に好ましく、100%であることが最も好ましい。更により一層安全かつ高い輝度で情報を表示できることから、全ての組の光源の重複率が10%以上であることが好ましく、30%以上であることがより好ましく、50%以上であることが更に好ましく、70%以上であることが特に好ましく、100%であることが最も好ましい。
上記ポリビニルアセタール樹脂のアセタール化度の好ましい下限は40モル%、好ましい上限は85モル%であり、より好ましい下限は60モル%、より好ましい上限は75モル%である。
なお、上記アセタール化度及び水酸基量は、例えば、JIS K6728「ポリビニルブチラール試験方法」に準拠して測定できる。
上記ポリビニルアルコールの重合度の好ましい下限は500、好ましい上限は4000である。上記ポリビニルアルコールの重合度が500以上であると、本発明の発光ディスプレイシステムをHUDとして用いて製造した合わせガラスの耐貫通性が高くなる。上記ポリビニルアルコールの重合度が4000以下であると、成形が容易になる。上記ポリビニルアルコールの重合度のより好ましい下限は1000、より好ましい上限は3600である。
ランタノイド錯体のなかでも、ハロゲン原子を含む配位子を有するランタノイド錯体は光線を照射することにより高い発光強度で発光する。上記ハロゲン原子を含む配位子を有するランタノイド錯体としては、ハロゲン原子を含む単座配位子を有するランタノイド錯体や、ハロゲン原子を含む二座配位子を有するランタノイド錯体、ハロゲン原子を含む三座配位子を有するランタノイド錯体、ハロゲン原子を含む四座配位子を有するランタノイド錯体、ハロゲン原子を含む五座配位子を有するランタノイド錯体、ハロゲン原子を含む六座配位子を有するランタノイド錯体等のハロゲン原子を含む多座配位子を有するランタノイド錯体が挙げられる。
しかも、上記ハロゲン原子を含む二座配位子を有するランタノイド錯体又はハロゲン原子を含む三座配位子を有するランタノイド錯体は、耐熱性にも優れる。発光ディスプレイシステムをHUDとして自動車ルーフ用ガラスや建築物用窓ガラスに用いた場合、太陽光の赤外線が照射されることにより、高温環境下で使用されることが多い。このような高温環境下では発光材料が劣化して、特に合わせガラスの端部において発光材料が劣化してしまうことがある。発光材料として上記ハロゲン原子を含む二座配位子を有するランタノイド錯体又はハロゲン原子を含む三座配位子を有するランタノイド錯体を用いることにより、高温環境下においても劣化を防止することができる。
上記R2は、炭素数1以上のアルキレン基であることが好ましく、炭素数1~5のアルキレン基であることがより好ましく、炭素数1のメチレン基であることが最も好ましい。上記炭素数1以上のアルキレン基は水素原子の一部が、水素原子以外の原子及び官能基と置換されていても良い。
上記ハロゲン原子を含むアセチルアセトン骨格を有する二座配位子を有するランタノイド錯体は、例えば、Eu(TFA)3phen、Eu(TFA)3dpphen、Eu(HFA)3phen、[Eu(FPD)3]bpy、[Eu(TFA)3]tmphen、[Eu(FPD)3]phen等が挙げられる。これらのハロゲン原子を含むアセチルアセトン骨格を有する二座配位子を有するランタノイド錯体の構造を示す。
上記ハロゲン原子を含む配位子を有するランタノイド錯体が粒子状である場合、ランタノイド錯体の平均粒子径の好ましい下限は0.01μm、好ましい上限は10μmであり、より好ましい下限は0.03μm、より好ましい上限は1μmである。
これらは単独で用いてもよく、2種以上を用いてもよい。
発光ディスプレイの透明性がより一層高くなることから、xは1又は2であることが好ましく、ベンゼン環の2位又は5位に水酸基を有することがより好ましく、ベンゼン環の2位及び5位に水酸基を有することが更に好ましい。
上記R6の有機基は炭化水素基であることが好ましく、炭素数が1~10の炭化水素基であることがより好ましく、炭素数が1~5の炭化水素基であることが更に好ましく、炭素数が1~3の炭化水素基であることが特に好ましい。
上記炭化水素基の炭素数が10以下であると、上記テレフタル酸エステル構造を有する発光材料を熱可塑性樹脂中に容易に分散させることができる。
上記炭化水素基はアルキル基であることが好ましい。
上記R7の有機基は炭化水素基であることが好ましく、炭素数が1~10の炭化水素基であることがより好ましく、炭素数が1~5の炭化水素基であることが更に好ましく、炭素数が1~3の炭化水素基であることが特に好ましい。
上記炭化水素基の炭素数が上記上限以下であると、上記テレフタル酸エステル構造を有する発光材料を熱可塑性樹脂中に容易に分散させることができる。
上記炭化水素基はアルキル基であることが好ましい。
上記一般式(10)中、NR8R9はアミノ基である。R8及びR9は、水素原子であることが好ましい。
上記一般式(10)で表される構造を有する化合物のベンゼン環の水素原子のうち、一つの水素原子が上記アミノ基であってもよく、二つの水素原子が上記アミノ基であってもよく、三つの水素原子が上記アミノ基であってもよく、四つの水素原子が上記アミノ基であってもよい。
上記分散剤は、例えば、直鎖アルキルベンゼンスルホン酸塩等のスルホン酸構造を有する化合物や、ジエステル化合物、リシノール酸アルキルエステル、フタル酸エステル、アジピン酸エステル、セバシン酸エステル、リン酸エステル等のエステル構造を有する化合物や、ポリオキシエチレングリコール、ポリオキシプロピレングリコールやアルキルフェニル-ポリオキシエチレン-エーテル等のエーテル構造を有する化合物や、ポリカルボン酸等のカルボン酸構造を有する化合物や、ラウリルアミン、ジメチルラウリルアミン、オレイルプロピレンジアミン、ポリオキシエチレンの2級アミン、ポリオキシエチレンの3級アミン、ポリオキシエチレンのジアミン等のアミン構造を有する化合物や、ポリアルキレンポリアミンアルキレンオキシド等のポリアミン構造を有する化合物や、オレイン酸ジエタノールアミド、アルカノール脂肪酸アミド等のアミド構造を有する化合物や、ポリビニルピロリドン、ポリエステル酸アマイドアミン塩等の高分子量型アミド構造を有する化合物等の分散剤を用いることができる。また、ポリオキシエチレンアルキルエーテルリン酸(塩)や高分子ポリカルボン酸、縮合リシノール酸エステル等の高分子量分散剤を用いてもよい。なお、高分子量分散剤とは、その分子量が1万以上である分散剤と定義される。
より一層高い輝度で画像を表示できることから、上記発光樹脂フィルム中における上記紫外線吸収剤の含有量は、上記熱可塑性樹脂100重量部に対する好ましい上限は1重量部、より好ましい上限は0.5重量部、更に好ましい上限は0.2重量部、特に好ましい上限は0.1重量部である。
上記可塑剤は特に限定されず、例えば、一塩基性有機酸エステル、多塩基性有機酸エステル等の有機エステル可塑剤、有機リン酸可塑剤、有機亜リン酸可塑剤等のリン酸可塑剤等が挙げられる。上記可塑剤は液状可塑剤であることが好ましい。
上記酸化防止剤は特に限定されず、フェノール構造を有する酸化防止剤、硫黄を含む酸化防止剤、リンを含む酸化防止剤等が挙げられる。
上記フェノール構造を有する酸化防止剤はフェノール骨格を有する酸化防止剤である。上記フェノール構造を有する酸化防止剤としては、例えば、2,6-ジ-t-ブチル-p-クレゾール(BHT)、ブチル化ヒドロキシアニソール(BHA)、2,6-ジ-t-ブチル-4-エチルフェノール、ステアリル-β-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート、2,2’-メチレンビス-(4-メチル-6-ブチルフェノール)、2,2’-メチレンビス-(4-エチル-6-t-ブチルフェノール)、4,4’-ブチリデン-ビス-(3-メチル-6-t-ブチルフェノール)、1,1,3-トリス-(2-メチル-ヒドロキシ-5-t-ブチルフェニル)ブタン、テトラキス[メチレン-3-(3’,5’-ブチル-4-ヒドロキシフェニル)プロピオネート]メタン、1,3,3-トリス-(2-メチル-4-ヒドロキシ-5-t-ブチルフェノール)ブタン、1,3,5-トリメチル-2,4,6-トリス(3,5-ジ-t-ブチル-4-ヒドロキシベンジル)ベンゼン、ビス(3,3’-t-ブチルフェノール)ブチリックアシッドグリコールエステル、ペンタエリスリトールテトラキス[3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオナート]等が挙げられる。上記酸化防止剤は、単独で用いてもよいし、2種以上を併用してもよい。
上記接着力調整剤としては、例えば、アルカリ金属塩、アルカリ土類金属塩及びマグネシウム塩からなる群より選択される少なくとも1種が好適に用いられる。上記接着力調整剤として、例えば、カリウム、ナトリウム、マグネシウム等の塩が挙げられる。
上記塩を構成する酸としては、例えば、オクチル酸、ヘキシル酸、2-エチル酪酸、酪酸、酢酸、蟻酸等のカルボン酸の有機酸、又は、塩酸、硝酸等の無機酸が挙げられる。
上記発光樹脂フィルムを多層樹脂フィルムとして用いる場合、上記発光樹脂フィルムは多層樹脂フィルムの全面に配置されていてもよく、一部にのみ配置されていてもよく、多層樹脂フィルムの厚み方向とは垂直の面方向の全面に配置されていてもよく、一部にのみ配置されていてもよい。上記発光樹脂フィルムが一部にのみ配置されている場合には、該一部を発光エリア、他の部分を非発光エリアとして、発光エリアにおいてのみ情報を表示できるようにすることができる。
例えば、上記多層樹脂フィルムに遮音性能を付与するために、上記発光樹脂フィルムにおける熱可塑性樹脂100重量部に対する可塑剤の含有量(以下、含有量Xともいう。)を、他の樹脂フィルムにおける熱可塑性樹脂100重量部に対する可塑剤の含有量(以下、含有量Yともいう。)よりも多くすることができる。この場合、上記含有量Xは上記含有量Yよりも5重量部以上多いことが好ましく、10重量部以上多いことがより好ましく、15重量部以上多いことが更に好ましい。上記多層樹脂フィルムの耐貫通性がより一層高くなることから、上記含有量Xと上記含有量Yとの差は、50重量部以下であることが好ましく、40重量部以下であることがより好ましく、35重量部以下であることが更に好ましい。なお、上記含有量Xと上記含有量Yとの差は、(上記含有量Xと上記含有量Yとの差)=(上記含有量X-上記含有量Y)により算出される。
上記含有量Yの好ましい下限は20重量部、好ましい上限は45重量部であり、より好ましい下限は30重量部、より好ましい上限は43重量部であり、更に好ましい下限は35重量部、更に好ましい上限は41重量部である。上記含有量Yを上記好ましい下限以上とすることにより、高い耐貫通性を発揮することができる。上記含有量Yを上記好ましい上限以下とすることにより、可塑剤のブリードアウトの発生を抑止し、上記多層樹脂フィルムの透明性や接着性の低下を防止することができる。
上記ポリビニルアセタールXの水酸基量は、水酸基が結合しているエチレン基量を、主鎖の全エチレン基量で除算して求めたモル分率を百分率(モル%)で表した値である。上記水酸基が結合しているエチレン基量は、例えば、JIS K6728「ポリビニルブチラール試験方法」に準拠した方法により、上記ポリビニルアセタールXの水酸基が結合しているエチレン基量を測定することにより求めることができる。
上記アセタール基量は、JIS K6728「ポリビニルブチラール試験方法」に準拠した方法により、上記ポリビニルアセタールXのアセタール基が結合しているエチレン基量を測定することにより求めることができる。
上記アセチル基量は、主鎖の全エチレン基量から、アセタール基が結合しているエチレン基量と、水酸基が結合しているエチレン基量とを差し引いた値を、主鎖の全エチレン基量で除算して求めたモル分率を百分率(モル%)で表した値である。
なお、ポリビニルアセタールYの水酸基量、アセタール基量、及び、アセチル基量は、ポリビニルアセタールXと同様の方法で測定できる。
上記熱線吸収剤は、赤外線を遮蔽する性能を有すれば特に限定されないが、錫ドープ酸化インジウム(ITO)粒子、アンチモンドープ酸化錫(ATO)粒子、アルミニウムドープ酸化亜鉛(AZO)粒子、インジウムドープ酸化亜鉛(IZO)粒子、錫ドープ酸化亜鉛粒子、珪素ドープ酸化亜鉛粒子、6ホウ化ランタン粒子及び6ホウ化セリウム粒子からなる群より選択される少なくとも1種が好適である。
上記多層樹脂フィルムにおける上記発光樹脂フィルムの厚さは特に限定されないが、好ましい下限は50μm、好ましい上限は1000μmである。上記発光樹脂フィルムの厚さがこの範囲内であると、特定の波長の光線を照射したときに充分にコントラストの高い発光が得られる。上記多層樹脂フィルムの厚さのより好ましい下限は80μm、より好ましい上限は500μm、更に好ましい下限は90μm、更に好ましい上限は300μmである。
上記ガラス板は、一般に使用されている透明板ガラスを使用することができる。例えば、フロート板ガラス、磨き板ガラス、型板ガラス、網入りガラス、線入り板ガラス、着色された板ガラス、熱線吸収ガラス、熱線反射ガラス、グリーンガラス等の無機ガラスが挙げられる。また、ガラスの表面に紫外線遮蔽コート層が形成された紫外線遮蔽ガラスも用いることができるが、特定の波長の光線を照射する側とは反対のガラス板として用いることが好ましい。更に、上記ガラス板としてポリエチレンテレフタレート、ポリカーボネート、ポリアクリレート等の有機プラスチックス板を用いることもできる。
上記ガラス板として、2種類以上のガラス板を用いてもよい。例えば、透明フロート板ガラスと、グリーンガラスのような着色されたガラス板との間に、上記発光樹脂フィルムや上記多層樹脂フィルムを積層した合わせガラスが挙げられる。また、上記ガラス板として、2種以上の厚さの異なるガラス板を用いてもよい。
上記光源は、上記発光樹脂フィルム中の発光材料の励起波長の光線を照射するものである。該光線を照射することにより発光樹脂フィルム上に情報を表示させる役割を果たす。上記照射される光線は、上記発光材料の励起波長を含むものであり、上記発光材料の種類によって選択される。
上記光源の数は、多い方がより広い範囲において高い輝度で情報を表示することができるが、限られたスペースのなかで配置することを考えれば、実質的には10台程度が上限である。
上記光源から照射される励起波長の光線の照射強度の下限は特に限定されないが、充分な輝度で情報を表示させるためには、10mW/cm2以上であることが好ましく、50mW/cm2以上であることがより好ましい。
なお、上記照射する光線の出力は、光源より10cm離れた位置に配置したレーザーパワーメーター(例えば、オフィールジャパン社製、「ビームトラックパワー測定センサー3A-QUAD」等)を用いた照射強度測定により測定することができる。
本発明の発光ディスプレイシステムは、自動車等の車両のフロントガラス、サイドガラス、リアガラスや、航空機、建築物等の窓ガラス等として広く使用することができる。なかでも、上記発光樹脂フィルムを合わせガラス用中間膜として用いた合わせガラスと、2以上の光源とを配置した本発明の発光ディスプレイシステムは、ヘッドアップディスプレイとして極めて有用である。
(1)ポリビニルブチラールの調製
攪拌機を取り付けた2m3反応器に、PVA(重合度1700、けん化度99モル%)の7.5質量%水溶液1700kgとn-ブチルアルデヒド74.6kg、2,6-ジ-t-ブチル-4-メチルフェノール0.13kgを仕込み、全体を14℃に冷却した。これに、濃度30質量%の硝酸99.44Lを添加して、PVAのブチラール化を開始した。添加終了後から10分後に昇温を開始し、90分かけて65℃まで昇温し、更に120分反応を行なった。その後、室温まで冷却して析出した固形分を濾過後、固形分に対して質量で10倍量のイオン交換水で10回洗浄した。その後、0.3質量%の炭酸水素ナトリウム水溶液を用いて十分に中和を行ない、更に固形分に対して質量で10倍量のイオン交換水で10回洗浄し、脱水した後、乾燥させ、ポリビニルブチラール樹脂(PVB)を得た。
トリエチレングリコールジ-2-エチルヘキサノエート(3GO)40重量部に、ジエチル-2,5-ジヒドロキシテレフタレート(Aldrich社製、「2,5-ジヒドロキシテレフタル酸ジエチル」)0.54重量部を加え、発光性の可塑剤溶液を調製した。得られた可塑剤溶液の全量と、得られたポリビニルブチラール100重量部とをミキシングロールで充分に混練することにより樹脂組成物を調製した。
得られた樹脂組成物を、押出機を用いて押出し、厚み760μmの発光樹脂フィルムを得た。
光源として、ピコプロジェクター(ソニー社製)、を2台又は3台準備し、各々の光源の波長405nmの光線の照射強度が200mW/cm2となるように調整した。
得られた合わせガラスに対して、照射される光線が合わせガラス上に重複するように、光源を配置した。
酢酸ユーロピウム(Eu(CH3COO)3)12.5mmolを50mLの蒸留水へ溶かし、トリフルオロアセチルアセトン(TFA、CH3COCH2COCF3)33.6mmolを加え、室温で3時間撹拌した。沈殿した固体を濾過、水洗後、メタノールと蒸留水で再結晶を行なってEu(TFA)3(H2O)2を得た。得られた錯体Eu(TFA)3(H2O)25.77gと1,10-フェナントロリン(phen)2.5gを100mLのメタノールに溶かし、12時間加熱還流を行なった。12時間後、メタノールを減圧留去により取り除き、白色生成物を得た。この粉末をトルエンで洗浄し、未反応の原料を吸引濾過により取り除いた後、トルエンを減圧留去し、紛体を得た。トルエン、ヘキサンの混合溶媒により再結晶を行なうことにより、Eu(TFA)3phenを得た。
3GO40重量部に対して、ジエチル-2,5-ジヒドロキシテレフタレート(Aldrich社製、「2,5-ジヒドロキシテレフタル酸ジエチル」)0.54重量部に代えて得られたEu(TFA)3phen0.4重量部を用いた以外は実施例1と同様にして発光樹脂フィルム及び合わせガラスを製造した。そして、2台又は3台の光源を配置して発光ディスプレイシステムを構築した。
酢酸テルビウム(Tb(CH3COO)3)12.5mmolを50mLの蒸留水へ溶かし、トリフルオロアセチルアセトン(TFA、CH3COCH2COCF3)33.6mmolを加え、室温で3時間撹拌した。沈殿した固体を濾過、水洗後、メタノールと蒸留水で再結晶を行なってTb(TFA)3(H2O)2を得た。得られた錯体Tb(TFA)3(H2O)25.77gと1,10-フェナントロリン(phen)2.5gを100mLのメタノールに溶かし、12時間加熱還流を行なった。12時間後、メタノールを減圧留去により取り除き、白色生成物を得た。この粉末をトルエンで洗浄し、未反応の原料を吸引濾過により取り除いた後、トルエンを減圧留去し、紛体を得た。トルエン、ヘキサンの混合溶媒により再結晶を行なうことにより、Tb(TFA)3phenを得た。
3GO40重量部に対して、ジエチル-2,5-ジヒドロキシテレフタレート(Aldrich社製、「2,5-ジヒドロキシテレフタル酸ジエチル」)0.54重量部に代えて得られたTb(TFA)3phen0.4重量部を用いた以外は実施例1と同様にして発光樹脂フィルム及び合わせガラスを製造した。そして、2台又は3台の光源を配置して発光ディスプレイシステムを構築した。
光源の台数及び照射強度を表2のようにした以外は実施例1~3と同様にして発光樹脂フィルム及び合わせガラスを製造し、2又は3の光源を配置して発光ディスプレイシステムを構築した。
実施例及び比較例で得られた発光ディスプレイシステムについて、以下の方法で評価した。
結果を表1、2に示した。
発光ディスプレイシステムの安全性について、光源の照射強度が200mW/cm2以下である場合を「○」と、200mW/cm2を超える場合を「×」と評価した。
光を照射した合わせガラスの面から45度の角度で、合わせガラスの面からの最短距離が35cmとなる位置であり、かつ光を照射した側に輝度計(トプコンテクノハウス社製、「SR-3AR」)を配置した。そして、光源から合わせガラスへと光を照射し、合わせガラス上に表示された情報の輝度を測定した。
なお、複数の光源を用いた場合には、全ての光源からの光線が重複した部位における輝度を測定した。
2 光源
3 光源
4 光源
Claims (6)
- 熱可塑性樹脂と発光材料とを含有する発光樹脂フィルムと、前記発光材料の励起波長の光線を照射する光源を2台以上有し、
前記光源から照射される光線が前記発光樹脂フィルム上に少なくとも一部が重複するように前記発光樹脂フィルムと2以上の光源とが配置されている
ことを特徴とする発光ディスプレイシステム。 - 発光樹脂フィルムは、他の樹脂フィルムを積層した多層樹脂フィルムとして配置されることを特徴とする請求項1記載の発光ディスプレイシステム。
- 発光樹脂フィルムは、少なくとも1枚のガラス板により補強されていることを特徴とする請求項1又は2記載の発光ディスプレイシステム。
- 発光樹脂フィルムは、一対のガラス板の間に積層された合わせガラスとして配置されることを特徴とする請求項1、2又は3記載の発光ディスプレイシステム。
- 光源から照射される励起波長の光線の照射強度が200mW/cm2以下であることを特徴とする請求項1、2、3又は4記載の発光ディスプレイシステム。
- 請求項1、2、3、4又は5記載の発光ディスプレイシステムを用いたヘッドアップディスプレイ。
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US20190351654A1 (en) | 2019-11-21 |
KR20190126045A (ko) | 2019-11-08 |
US10960647B2 (en) | 2021-03-30 |
EP3605190A4 (en) | 2020-12-09 |
MX2019010813A (es) | 2019-12-11 |
JP7164432B2 (ja) | 2022-11-01 |
CN109863444A (zh) | 2019-06-07 |
JPWO2018181302A1 (ja) | 2020-02-13 |
EP3605190A1 (en) | 2020-02-05 |
KR102516915B1 (ko) | 2023-03-31 |
EP3605190B1 (en) | 2023-05-03 |
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