DISPLAY DEVICE CAPABLE OF DISPLAYING GRADATION PATTERN, GLASS FOR AUTOMOBILE ROOF, AND WINDOW GLASS FOR BUILDING

Abstract

The present invention aims to provide a display device capable of displaying a gradation pattern in which the gradation pattern on a laminated glass can be changed at will and a display state can be switched to a transparent state, and an automobile roof glass and a building window glass each including the display device. Provided is a display device capable of displaying a gradation pattern, including: a laminated glass including a pair of glass plates and an interlayer film for a laminated glass that contains a thermoplastic resin and a luminescent material and is interposed between the pair of glass plates; and a light source configured to emit light of excitation wavelength for the luminescent material, the laminated glass and the light source being disposed such that the laminated glass is irradiated from its periphery toward the inside with the light emitted from the light source.

Claims

1. A display device capable of displaying a gradation pattern, comprising: a laminated glass comprising a pair of glass plates and an interlayer film for a laminated glass that contains a thermoplastic resin and a luminescent material and is interposed between the pair of glass plates; and a light source configured to emit light of excitation wavelength for the luminescent material, the laminated glass and the light source being disposed such that the laminated glass is irradiated from its periphery toward the inside with the light emitted from the light source.

2. The display device capable of displaying a gradation pattern according to claim 1, wherein a surface direction of the laminated glass and an optical axis of the light emitted from the light source form an angle of 30 or smaller.

3. The display device capable of displaying a gradation pattern according to claim 2, wherein the surface direction of the laminated glass and the optical axis of the light emitted from the light source form an angle of 0.1 or larger but 30 or smaller.

4. The display device capable of displaying a gradation pattern according to claim 1, wherein the luminescent material is contained in the interlayer film for a laminated glass in an amount of 0.01 parts by weight or more but 15 parts by weight or less relative to 100 parts by weight of the thermoplastic resin.

5. The display device capable of displaying a gradation pattern according to claim 1, wherein the light emitted from the light source has an intensity of 50 mW/cm.sup.2 or higher.

6. The display device capable of displaying a gradation pattern according to claim 1, wherein the light emitted from the light source has an irradiation diameter of 0.5 cm or larger.

7. An automobile roof glass comprising the display device according to claim 1.

8. A building window glass comprising the display device according to claim 1.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0149] FIG. 1 illustrates a schematic view of an exemplary embodiment of the interlayer film for a laminated glass of the present invention having a wedge-shaped cross section.

[0150] FIG. 2 illustrates a schematic view of an exemplary embodiment of the interlayer film for a laminated glass of the present invention having a wedge-shaped cross section.

[0151] FIG. 3 illustrates a schematic view of an exemplary embodiment of the interlayer film for a laminated glass of the present invention having a wedge-shaped cross section.

[0152] FIG. 4 includes schematic views each illustrating a positional relation between a laminated glass and a light source of the display device of the present invention.

DESCRIPTION OF EMBODIMENTS

[0153] The present invention is more specifically described in the following with reference to, but not limited to, examples.

(Luminescent Material)

[0154] The following luminescent materials are used in the examples. [0155] Eu(TFA).sub.3phen [0156] Eu(HFA).sub.3phen [0157] Tb(HFA).sub.3phen [0158] Tb(TFA).sub.3phen [0159] Diethyl-2,5-dihydroxylterephthalate (Diethyl 2,5-dihydroxyterephthalate available from Sigma-Aldrich)

[0160] Four luminescent materials other than diethyl-2,5-dihydroxylterephthalate that is a commercial product were prepared as follows.

(1) Preparation of Eu(TFA).SUB.3.phen

[0161] Europium acetate (Eu(CH.sub.3COO).sub.3) in an amount of 12.5 mmol was dissolved in 50 mL of distilled water. To the solution was added 33.6 mmol of trifluoroacetylacetone (TFA, CH.sub.3COCH.sub.2COCF.sub.3), and the mixture was stirred at room temperature for 3 hours. The precipitated solid was filtered, washed with water, and recrystallized using methanol and distilled water to give Eu(TFA).sub.3(H.sub.2O).sub.2. Then, 5.77 g of the resulting complex (Eu(TFA).sub.3(H.sub.2O).sub.2) and 2.5 g of 1,10-phenanthroline(phen) were dissolved in 100 mL of methanol, followed by heating under reflux for 12 hours. After 12 hours, methanol was distilled off under reduced pressure, thereby obtaining a white product. The white product powder was washed with toluene so that unreacted materials were removed by suction filtration. Subsequently, toluene was distilled off under reduced pressure, thereby preparing a powder. Through recrystallization using a solvent mixture of toluene and hexane, Eu(TFA).sub.3phen was obtained.

(2) Preparation of Eu(HFA).SUB.3.phen

[0162] Europium acetate (Eu(CH.sub.3COO).sub.3) in an amount of 12.5 mmol was dissolved in 50 mL of distilled water. To the solution was added 33.6 mmol of hexafluoroacetylacetone (HFA), and the mixture was stirred at room temperature for 3 hours. The precipitated solid was filtered, washed with water, and recrystallized using methanol and distilled water to give Eu(HFA).sub.3(H.sub.2O).sub.2. Then, 7.20 g of the obtained complex (Eu(HFA).sub.3(H.sub.2O).sub.2) and 2.5 g of 1,10-phenanthroline(phen) were added to 100 mL of methanol, followed by heating under reflux for 12 hours. After 12 hours, methanol was distilled off under reduced pressure, thereby obtaining a white product. The white product powder was washed with toluene so that unreacted materials were removed by suction filtration. Subsequently, toluene was distilled off under reduced pressure, thereby preparing a powder. Through recrystallization using a solvent mixture of toluene and hexane, Eu(HFA).sub.3phen was obtained.

(3) Preparation of Tb(HFA).SUB.3.phen

[0163] Terbium acetate (Tb(CH.sub.3COO).sub.3) in an amount of 12.5 mmol was dissolved in 50 mL of distilled water. To the solution was added 33.6 mmol of hexafluoroacetylacetone (HFA, CF.sub.3COCH.sub.2COCF.sub.3), and the mixture was stirred at room temperature for 3 hours. The precipitated solid was filtered, washed with water, and recrystallized using methanol and distilled water to give Tb(HFA).sub.3(H.sub.2O).sub.2. Then, 7.26 g of the obtained complex (Tb(HFA).sub.3(H.sub.2O).sub.2) and 2.5 g of 1,10-phenanthroline(phen) were dissolved in 100 mL of methanol, followed by heating under reflux for 12 hours. After 12 hours, methanol was distilled off under reduced pressure, thereby obtaining a white product. The white product powder was washed with toluene so that unreacted materials were removed by suction filtration. Subsequently, toluene was distilled off under reduced pressure, thereby preparing a powder. Through recrystallization using a solvent mixture of toluene and hexane, Tb(HFA).sub.3phen was obtained.

(4) Preparation of Tb(TFA).SUB.3.phen

[0164] Tb(TFA).sub.3phen was obtained in the same manner as in the case of Tb(HFA).sub.3phen, except that trifluoroacetylacetone was used instead of hexafluoroacetylacetone.

(Thermoplastic Resin)

[0165] In examples, polyvinyl butyral prepared by the following procedure was used as a thermoplastic resin.

[0166] To a 2 m.sup.3 reactor equipped with a stirrer were charged 1,700 kg of a 7.5% by mass aqueous solution of PVA (degree of polymerization: 1,700, degree of saponification: 99 mol %), 74.6 kg of n-butyraldehyde, and 0.13 kg of 2,6-di-t-butyl-4-methyl phenol, and the entire mixture was cooled to 14 C. Subsequently, 99.44 L of 30% by mass nitric acid was added to the mixture to initiate the butyralization of PVA. Ten minutes after the end of the addition, the temperature was raised to 65 C. over 90 minutes, followed by further reaction for 120 minutes. Thereafter, the temperature was lowered to room temperature, and the precipitated solid was filtered. The solid was washed ten times with a 10-fold amount (by mass) of ion exchange water. The washed solid was sufficiently neutralized using a 0.3% by mass sodium hydrogen carbonate aqueous solution and was then washed ten times with a 10-fold amount (by mass) of ion exchange water. The resulting solid was dehydrated and dried, thereby obtaining polyvinyl butyral (PVB).

Examples 1 to 6

(1) Production of Interlayer Film for a Laminated Glass and Laminated Glass

[0167] A luminescent plasticizer solution was prepared by adding 0.2 parts by weight of Eu(TFA).sub.3phen to 40 parts by weight of triethylene glycol di-2-ethylhexanoate (3GO). The entire amount of the obtained plasticizer solution was mixed and sufficiently kneaded with 100 parts by weight of polyvinyl butyral using a mixing roll to give a resin composition.

[0168] The obtained resin composition was extruded using an extruder to provide an interlayer film for a laminated glass (thickness: 760 m).

[0169] The total amount of sodium, potassium, and magnesium in the obtained interlayer film for a laminated glass measured with an ICP emission analyzer (ICPE-9000 available from Shimadzu Corporation) was 5 ppm.

[0170] The resulting interlayer film for a laminated glass was sandwiched between a pair of clear glass plates (thickness: 2.5 mm, 5 cm in length x 5 cm in width) to prepare a laminate. The laminate was pressed under vacuum at 90 C. for 30 minutes to be press-bonded using a vacuum laminator. The press-bonded laminate was subjected to further 20-minute press-bonding under 14 MPa at 140 C. using an autoclave, thereby obtaining a laminated glass.

(2) Production of Display Device

[0171] A display device was obtained by combining the obtained laminated glass and a mercury light source (REX-250 available from Asahi Spectra Co., Ltd.) in which the output power or wavelength of the light was adjustable by adjusting the output power of the light source and using a band-pass filter (LX0405 available from Asahi Spectra Co., Ltd.), a rod lens (Asahi Spectra Co., Ltd.), and a fiber (Asahi Spectra Co., Ltd.). In the obtained display device, the optical axis was positioned at the center in the thickness direction of the interlayer film for a laminated glass in the laminated glass and the light source was positioned at a position of 1 cm distant from an end portion of the laminated glass.

(3) Display of Gradation Pattern

[0172] The obtained display device was placed in a dark room and subjected to irradiation with light in which the output power of the light source and the angle formed between the surface direction of the laminated glass and the optical axis of the light emitted from the light source were set as shown in Table 1.

[0173] Luminance meters (SR-3AR available from Topcon Technohouse Corporation) were set orthogonally to the surface direction of the laminated glass and at positions at 0 mm, 10 mm, 30 mm, and 50 mm from the end portion of the laminated glass on the light source side for measurement of the luminance of the laminated glass.

[0174] As a result, in Examples 1 to 5, a very beautiful gradation pattern in which the luminance was changed according to the distance from the end portion was displayed. In Example 6 in which the irradiation with light was not carried out, the laminated glass was transparent.

TABLE-US-00001 TABLE 1 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Interlayer Thermoplastic resin PVB phr 100 film Luminescent material Type Eu(TFA).sub.3phen Amount phr 0.2 Plasticizer 3GO phr 40 Light Wavelength nm 405 405 405 405 405 Not source Intensity mW/cm.sup.2 100 50 300 100 100 irradiated Angle 5 5 5 15 30 Evaluation Luminance (0 mm from end cd/m.sup.2 1000 500 3000 1000 1000 0 portion) Luminance (10 mm from end cd/m.sup.2 850 400 2500 900 950 0 portion) Luminance (30 mm from end cd/m.sup.2 550 200 1800 700 850 0 portion) Luminance (50 mm from end cd/m.sup.2 250 100 1200 500 750 0 portion)

Examples 7 to 22

[0175] An interlayer film for a laminated glass, a laminated glass, and a display device were produced in the same manner as in Example 1, except that the type and amount of the luminescent material, the intensity and irradiation diameter of the light, and the angle formed between the surface direction of the laminated glass and the optical axis of the light emitted from the light source were changed as shown in Tables 2 to 4.

[0176] As a result of the confirmation of display of the gradation pattern in the same manner as in Examples 1 to 5, display of a very beautiful gradation pattern in which the luminance was changed according to the distance from the end portion was confirmed.

TABLE-US-00002 TABLE 2 Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- ple 7 ple 8 ple 9 ple 10 ple 11 ple 12 ple 13 ple 14 ple 15 Interlayer Thermoplastic resin PVB phr 100 100 100 film Luminescent material Type Eu(TFA).sub.3phen Eu(TFA).sub.3phen Eu(TFA).sub.3phen Amount phr 0.2 0.05 0.4 Plasticizer 3GO phr 40 40 40 Light Wavelength nm 405 405 405 405 405 405 405 405 405 source Intensity mW/cm.sup.2 100 100 50 300 100 100 100 100 100 Irradiation diameter cm 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 Angle 0.5 5 5 5 15 30 0.5 5 30 Evaluation Luminance (0 mm from end cd/m.sup.2 1000 240 120 750 240 240 240 2000 2000 portion) Luminance (10 mm from end cd/m.sup.2 580 210 110 670 220 230 170 1600 1800 portion) Luminance (30 mm from end cd/m.sup.2 70 140 70 520 180 210 30 800 1400 portion) Luminance (50 mm from end cd/m.sup.2 0 80 40 350 140 190 0 200 1000 portion)

TABLE-US-00003 TABLE 3 Example 16 Example 17 Example 18 Example 19 Interlayer Thermoplastic resin PVB phr 100 100 100 100 film Luminescent material Type Eu(HFA).sub.3phen Tb(TFA).sub.3phen Tb(HFA).sub.3phen Diethyl-2,5- dihydroxyterephthalate Amount phr 0.2 0.2 0.2 0.05 Plasticizer 3GO phr 40 40 40 40 Light Wavelength nm 405 405 405 405 source Intensity mW/cm.sup.2 100 100 100 100 Irradiation diameter cm 3.0 3.0 3.0 3.0 Angle .sup. 5 5 5 5 Evaluation Luminance (0 mm from end cd/m.sup.2 1050 2000 2100 2500 portion) Luminance (10 mm from end cd/m.sup.2 900 1700 1800 2180 portion) Luminance (30 mm from end cd/m.sup.2 600 1100 1200 1540 portion) Luminance (50 mm from end cd/m.sup.2 300 500 600 900 portion)

TABLE-US-00004 TABLE 4 Example 20 Example 21 Example 22 Interlayer Thermoplastic resin PVB phr 100 100 100 film Luminescent material Type Eu(TFA).sub.3phen Eu(TFA).sub.3phen Eu(TFA).sub.3phen Amount phr 0.4 0.4 0.4 Plasticizer 3GO phr 40 40 40 Light Wavelength nm 405 405 405 source Intensity mW/cm.sup.2 100 100 100 Irradiation diameter cm 0.5 1.0 5.0 Angle 5 5 5 Evaluation Luminance (0 mm from end cd/m.sup.2 2000 2000 2000 portion) Luminance (10 mm from end cd/m.sup.2 1300 1400 1800 portion) Luminance (30 mm from end cd/m.sup.2 50 200 1400 portion) Luminance (50 mm from end cd/m.sup.2 0 0 800 portion)

INDUSTRIAL APPLICABILITY

[0177] The present invention can provide a display device capable of displaying a gradation pattern in which the gradation pattern displayed on a laminated glass can be changed at will and a display state can be switched to a transparent state, and an automobile roof glass and a building window glass each including the display device.

REFERENCE SIGNS LIST

[0178] 1 Interlayer film for a laminated glass [0179] 11 Luminescent layer [0180] 12 Shape-adjusting layer [0181] 2 Interlayer film for a laminated glass [0182] 21 Luminescent layer [0183] 22 Shape-adjusting layer [0184] 23 Shape-adjusting layer [0185] 3 Interlayer film for a laminated glass [0186] 31 Luminescent layer [0187] 32 Shape-adjusting layer [0188] 33 Shape-adjusting layer [0189] 4 Laminated glass [0190] 41 Interlayer film for a laminated glass [0191] 42 Glass plate [0192] 5 Light source [0193] 6 Angle formed between surface direction of laminated glass 4 and optical axis of light emitted from light source 5