WO2016052478A1 - 合わせガラス用中間膜及び合わせガラス - Google Patents
合わせガラス用中間膜及び合わせガラス Download PDFInfo
- Publication number
- WO2016052478A1 WO2016052478A1 PCT/JP2015/077456 JP2015077456W WO2016052478A1 WO 2016052478 A1 WO2016052478 A1 WO 2016052478A1 JP 2015077456 W JP2015077456 W JP 2015077456W WO 2016052478 A1 WO2016052478 A1 WO 2016052478A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- laminated glass
- light emitting
- interlayer film
- emitting layer
- layer
- Prior art date
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- 239000005340 laminated glass Substances 0.000 title claims abstract description 164
- 239000011229 interlayer Substances 0.000 title claims abstract description 96
- 239000010410 layer Substances 0.000 claims abstract description 212
- 239000000463 material Substances 0.000 claims abstract description 54
- 239000004014 plasticizer Substances 0.000 claims abstract description 39
- 229920005989 resin Polymers 0.000 claims abstract description 32
- 239000011347 resin Substances 0.000 claims abstract description 32
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 19
- 239000011354 acetal resin Substances 0.000 claims description 32
- 229920006324 polyoxymethylene Polymers 0.000 claims description 32
- 229920002554 vinyl polymer Polymers 0.000 claims description 32
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 31
- 239000011521 glass Substances 0.000 claims description 23
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 23
- -1 polyethylene terephthalate Polymers 0.000 description 39
- 150000001875 compounds Chemical class 0.000 description 37
- 125000004432 carbon atom Chemical group C* 0.000 description 22
- 239000011342 resin composition Substances 0.000 description 19
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 16
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 15
- 239000004372 Polyvinyl alcohol Substances 0.000 description 15
- 229910052749 magnesium Inorganic materials 0.000 description 15
- 239000011777 magnesium Substances 0.000 description 15
- 239000002245 particle Substances 0.000 description 15
- 229920002451 polyvinyl alcohol Polymers 0.000 description 15
- 150000002430 hydrocarbons Chemical group 0.000 description 12
- FRQDZJMEHSJOPU-UHFFFAOYSA-N Triethylene glycol bis(2-ethylhexanoate) Chemical compound CCCCC(CC)C(=O)OCCOCCOCCOC(=O)C(CC)CCCC FRQDZJMEHSJOPU-UHFFFAOYSA-N 0.000 description 11
- 239000002270 dispersing agent Substances 0.000 description 11
- 239000003963 antioxidant agent Substances 0.000 description 10
- 230000003078 antioxidant effect Effects 0.000 description 10
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- 238000006116 polymerization reaction Methods 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 238000009413 insulation Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 150000007524 organic acids Chemical class 0.000 description 8
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- KKEYFWRCBNTPAC-UHFFFAOYSA-N benzene-dicarboxylic acid Natural products OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 7
- 125000000332 coumarinyl group Chemical group O1C(=O)C(=CC2=CC=CC=C12)* 0.000 description 7
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
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- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- 150000001299 aldehydes Chemical class 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 6
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
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- 159000000003 magnesium salts Chemical class 0.000 description 6
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 5
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 5
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 5
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- 235000011037 adipic acid Nutrition 0.000 description 5
- 125000003277 amino group Chemical group 0.000 description 5
- XJHABGPPCLHLLV-UHFFFAOYSA-N benzo[de]isoquinoline-1,3-dione Chemical group C1=CC(C(=O)NC2=O)=C3C2=CC=CC3=C1 XJHABGPPCLHLLV-UHFFFAOYSA-N 0.000 description 5
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 5
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- 239000011654 magnesium acetate Substances 0.000 description 5
- 229940069446 magnesium acetate Drugs 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
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- 125000000962 organic group Chemical group 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
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- 230000008901 benefit Effects 0.000 description 4
- UQOUOXLHXPHDHF-UHFFFAOYSA-N diethyl 2,5-dihydroxybenzene-1,4-dicarboxylate Chemical compound CCOC(=O)C1=CC(O)=C(C(=O)OCC)C=C1O UQOUOXLHXPHDHF-UHFFFAOYSA-N 0.000 description 4
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- 230000035515 penetration Effects 0.000 description 4
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N pentanal Chemical compound CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
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- 238000005096 rolling process Methods 0.000 description 4
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- 229910052693 Europium Inorganic materials 0.000 description 3
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- 238000006640 acetylation reaction Methods 0.000 description 3
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- 229910052748 manganese Inorganic materials 0.000 description 3
- 238000000034 method Methods 0.000 description 3
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- 229910052757 nitrogen Inorganic materials 0.000 description 3
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 description 2
- YJGHMLJGPSVSLF-UHFFFAOYSA-N 2-[2-(2-octanoyloxyethoxy)ethoxy]ethyl octanoate Chemical compound CCCCCCCC(=O)OCCOCCOCCOC(=O)CCCCCCC YJGHMLJGPSVSLF-UHFFFAOYSA-N 0.000 description 2
- GOLORTLGFDVFDW-UHFFFAOYSA-N 3-(1h-benzimidazol-2-yl)-7-(diethylamino)chromen-2-one Chemical compound C1=CC=C2NC(C3=CC4=CC=C(C=C4OC3=O)N(CC)CC)=NC2=C1 GOLORTLGFDVFDW-UHFFFAOYSA-N 0.000 description 2
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- HSHNITRMYYLLCV-UHFFFAOYSA-N 4-methylumbelliferone Chemical compound C1=C(O)C=CC2=C1OC(=O)C=C2C HSHNITRMYYLLCV-UHFFFAOYSA-N 0.000 description 2
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- VSSSHNJONFTXHS-UHFFFAOYSA-N coumarin 153 Chemical compound C12=C3CCCN2CCCC1=CC1=C3OC(=O)C=C1C(F)(F)F VSSSHNJONFTXHS-UHFFFAOYSA-N 0.000 description 2
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- 238000010030 laminating Methods 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
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- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 1
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- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- KZVBBTZJMSWGTK-UHFFFAOYSA-N 1-[2-(2-butoxyethoxy)ethoxy]butane Chemical compound CCCCOCCOCCOCCCC KZVBBTZJMSWGTK-UHFFFAOYSA-N 0.000 description 1
- DLZBUNUDESZERL-UHFFFAOYSA-N 1-o-heptyl 6-o-nonyl hexanedioate Chemical compound CCCCCCCCCOC(=O)CCCCC(=O)OCCCCCCC DLZBUNUDESZERL-UHFFFAOYSA-N 0.000 description 1
- XCTNDJAFNBCVOM-UHFFFAOYSA-N 1h-imidazo[4,5-b]pyridin-2-ylmethanamine Chemical compound C1=CC=C2NC(CN)=NC2=N1 XCTNDJAFNBCVOM-UHFFFAOYSA-N 0.000 description 1
- BVUXDWXKPROUDO-UHFFFAOYSA-N 2,6-di-tert-butyl-4-ethylphenol Chemical compound CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 BVUXDWXKPROUDO-UHFFFAOYSA-N 0.000 description 1
- BUUQZURCNBMDGS-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethyl 2,2-diethylhexanoate Chemical compound CCCCC(CC)(CC)C(=O)OCCOCCO BUUQZURCNBMDGS-UHFFFAOYSA-N 0.000 description 1
- UNNGUFMVYQJGTD-UHFFFAOYSA-N 2-Ethylbutanal Chemical compound CCC(CC)C=O UNNGUFMVYQJGTD-UHFFFAOYSA-N 0.000 description 1
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- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
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- 125000004174 2-benzimidazolyl group Chemical group [H]N1C(*)=NC2=C([H])C([H])=C([H])C([H])=C12 0.000 description 1
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- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- XVKWQENVLGYYFO-UHFFFAOYSA-N 3,3,3-triethoxypropylsilyl prop-2-enoate Chemical compound C(C)OC(CC[SiH2]OC(C=C)=O)(OCC)OCC XVKWQENVLGYYFO-UHFFFAOYSA-N 0.000 description 1
- VMUXSMXIQBNMGZ-UHFFFAOYSA-N 3,4-dihydrocoumarin Chemical compound C1=CC=C2OC(=O)CCC2=C1 VMUXSMXIQBNMGZ-UHFFFAOYSA-N 0.000 description 1
- QYBPUVGDDCVYPC-UHFFFAOYSA-N 3-[4,4-bis(5-tert-butyl-3-hydroxy-2-methylphenyl)butan-2-yl]-5-tert-butyl-2-methylphenol Chemical compound C=1C(C(C)(C)C)=CC(O)=C(C)C=1C(C)CC(C=1C(=C(O)C=C(C=1)C(C)(C)C)C)C1=CC(C(C)(C)C)=CC(O)=C1C QYBPUVGDDCVYPC-UHFFFAOYSA-N 0.000 description 1
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
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- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
- B32B17/10036—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheets
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- B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
- B32B17/10651—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer comprising colorants, e.g. dyes or pigments
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- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C27/00—Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing
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Definitions
- the present invention uses an interlayer film for laminated glass that is capable of displaying a high-contrast image with a certain range of brightness and that is not double-displayed in a specific region of the laminated glass, and the interlayer film for laminated glass. It relates to laminated glass.
- an instrument display such as speed information as automobile driving data is displayed as a head-up display (HUD) in the same field of view as the windshield.
- HUD head-up display
- the HUD display part is not on the windshield surface, and the speed information transmitted from the control unit is reflected from the instrument panel display unit to the windshield, so that the driver can be in the same position as the windshield (i.e. There is a form of visual recognition within the same visual field.
- Such a reflection type HUD is safe because the displayed information is visually recognized as being present in the distance by appropriately adjusting the focal length, and it is not necessary to change the focus of the driver's eyes.
- Patent Document 1 discloses a laminated glass in which an intermediate layer containing hydroxyterephthalate as a light emitting material is laminated between two transparent plates.
- the laminated glass described in Patent Document 1 can display an image with high contrast when irradiated with light.
- the laminated glass described in Patent Document 1 because the laminated glass constituting the windshield is composed of two parallel glasses, the instrument display reflected in the driver's field of view may appear double. There was a problem.
- the present inventors studied to blend a light emitting material into a wedge-shaped interlayer film for laminated glass having a predetermined wedge angle.
- Laminated glass using an interlayer film for laminated glass having a wedge-shaped cross section allows the driver to display the instrument display reflected by one glass and the instrument display reflected by the other glass by adjusting the wedge angle. It is known that it can be connected to one point in the field of view, and the problem that the instrument display appears double can be solved.
- an interlayer film for laminated glass having a wedge-shaped cross section in which a light emitting material is actually blended is used, there arises a new problem that the brightness of an image displayed by the light emitting material varies depending on the portion of the laminated glass.
- the present invention provides an interlayer film for laminated glass that can display a high-contrast image with a certain range of brightness and is not double-displayed in a specific region of the laminated glass, and the laminated glass.
- An object of the present invention is to provide a laminated glass using an interlayer film for use.
- the present invention relates to a multilayer including a light emitting layer containing a thermoplastic resin, a plasticizer and a light emitting material, and a resin layer containing a thermoplastic resin and a plasticizer laminated on at least one surface of the light emitting layer.
- An interlayer film for laminated glass having a structure, in which the sectional shape of the interlayer film for laminated glass is wedge-shaped, and the difference between the maximum thickness and the minimum thickness of the light emitting layer is 100 ⁇ m or less. The present invention is described in detail below.
- the present inventors have examined the reason why the brightness of the displayed image is different in the laminated glass using the interlayer film for laminated glass having a wedge-shaped cross section in which the light emitting material is blended. As a result, it has been found that the cross-sectional shape in the thickness direction of the interlayer film for laminated glass is wedge-shaped, thereby causing the surface density of the fluorescent material to be higher in the thicker portion than in the thinner portion.
- the present inventors have made the difference between the maximum thickness and the minimum thickness of the light emitting layer containing the light emitting material to be 100 ⁇ m or less to keep the variation in the surface density of the fluorescent material below a certain level, and
- a laminated multilayer structure a laminated glass capable of displaying an image with a certain range of luminance while preventing the generation of a double image is obtained by making the cross-sectional shape of the entire interlayer film for laminated glass a wedge shape. The present invention has been completed.
- the interlayer film for laminated glass of the present invention has a wedge shape in cross section.
- the wedge angle ⁇ of the wedge shape is 0.1 mrad
- the more preferable lower limit is 0.2 mrad
- the still more preferable lower limit is 0.3 mrad
- the preferable upper limit is 1 mrad
- the more preferable upper limit is 0.9 mrad.
- an interlayer film for laminated glass having a wedge-shaped cross section is manufactured by a method of extruding a resin composition using an extruder, a slightly inner region (specifically, from one end on the thin side) , Where X is the distance between one end and the other end, and has a minimum thickness in the range from 0X to 0.2X inward from one end on the thin side, and one end on the thick side
- the maximum thickness in the region slightly inside specifically, when the distance between one end and the other end is X, the region from 0X to 0.2X inward from one end on the thick side
- It may become the shape which has. In the present specification, such a shape is also included in the wedge shape.
- the interlayer film for laminated glass of the present invention has a multilayer structure including a light emitting layer containing a light emitting material and a resin layer (hereinafter also referred to as “shape auxiliary layer”). While the thickness of the light emitting layer is set within a certain range, the shape auxiliary layer is laminated so that the cross-sectional shape of the entire interlayer film for laminated glass is adjusted to a wedge shape.
- the shape auxiliary layer may be laminated only on one surface of the light emitting layer, or may be laminated on both surfaces. Further, a plurality of shape auxiliary layers may be laminated.
- the light emitting layer may have a wedge-shaped cross section or a rectangular shape.
- the light emitting layer preferably has a wedge shape in cross section.
- the maximum thickness of the light emitting layer is set above the HUD so that the minimum thickness of the light emitting layer is located below the HUD.
- the reflective HUD light source is disposed in the vicinity of the lower portion of the HUD, and the light emitting HUD excitation light source is disposed in the vicinity of the upper portion of the HUD.
- the self-luminous layer is wedge-shaped so that the self-luminous layer near the reflective HUD light source is thinned so that the excitation light of the luminescent material is included in the reflective HUD light source. Unexpected emission of the luminescent material can be suppressed, and a reflection type HUD image can be clearly displayed. Furthermore, since the self-luminous layer is wedge-shaped, a sufficient amount of light-emitting material can be present in the upper part of the HUD near the excitation light source of the light-emitting HUD, to display a clear image, A light-emitting HUD image can be clearly displayed. The difference between the maximum thickness and the minimum thickness of the light emitting layer is 100 ⁇ m or less.
- the difference between the maximum thickness and the minimum thickness of the light emitting layer is preferably 95 ⁇ m or less, more preferably 90 ⁇ m or less, still more preferably 60 ⁇ m or less, and particularly preferably 50 ⁇ m or less.
- the lower limit of the difference between the maximum thickness and the minimum thickness of the light emitting layer is not particularly limited, but is preferably 0.
- the thickness of the said light emitting layer is not specifically limited, A preferable minimum is 50 micrometers and a preferable upper limit is 700 micrometers. When the thickness of the light emitting layer is within this range, a sufficiently high contrast image can be displayed.
- the more preferable lower limit of the thickness of the light emitting layer is 70 ⁇ m
- the more preferable upper limit is 400 ⁇ m
- the still more preferable lower limit is 80 ⁇ m
- the still more preferable upper limit is 150 ⁇ m.
- the lower limit of the thickness of the light emitting layer means the thickness of the minimum thickness portion of the light emitting layer
- the upper limit of the thickness of the light emitting layer means the thickness of the maximum thickness portion of the light emitting layer.
- the shape auxiliary layer has a role of being laminated on the light emitting layer and adjusting the cross-sectional shape of the entire interlayer film for laminated glass to be a wedge shape.
- the cross-sectional shape of the interlayer film for laminated glass as a whole is preferably a wedge shape having a constant wedge angle. If the cross-sectional shape of the interlayer film for laminated glass as a whole is a wedge shape, it may not have a certain wedge angle.
- the shape auxiliary layer preferably has a wedge shape, a triangle shape, or a trapezoidal shape in cross section. By laminating a wedge-shaped, triangular, or trapezoidal shape auxiliary layer, the sectional shape of the interlayer film for laminated glass as a whole can be adjusted to be wedge-shaped.
- the said shape auxiliary layer may have shapes, such as a pentagon, a hexagon, and an ellipse, for example.
- the thickness of the shape auxiliary layer is not particularly limited, but from the viewpoint of practical use and from the viewpoint of sufficiently increasing 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 further preferable lower limit is 300 ⁇ m.
- the lower limit of the thickness of the shape auxiliary layer means the thickness of the minimum thickness portion of the shape auxiliary layer, and the upper limit of the thickness of the shape auxiliary layer means the thickness of the maximum thickness portion of the shape auxiliary layer. To do. Further, when a plurality of shape auxiliary layers are used in combination, the total thickness is meant.
- the total thickness of the interlayer film for laminated glass of the present invention is not particularly limited, but a preferable lower limit is 100 ⁇ m, a preferable upper limit is 3000 ⁇ m, a more preferable lower limit is 250 ⁇ m, a more preferable upper limit is 2000 ⁇ m, and a further preferable lower limit is 500 ⁇ m.
- a preferable upper limit is 1500 ⁇ m, and a particularly preferable lower limit is 800 ⁇ m.
- the lower limit of the thickness of the entire interlayer film for laminated glass means the thickness of the minimum thickness portion of the entire interlayer film for laminated glass
- the upper limit of the thickness of the entire interlayer film for laminated glass is the middle for laminated glass It means the thickness of the maximum thickness portion of the entire film.
- FIGS. 1 to 3 are schematic views for explaining an example of the embodiment of the interlayer film for laminated glass of the present invention.
- FIGS. 1 to 3 for convenience of illustration, the thickness and wedge angle ⁇ of the interlayer film for laminated glass and each layer constituting the interlayer film for laminated glass are shown to be different from the actual thickness and wedge angle. Yes.
- FIG. 1 shows a cross section in the thickness direction of the interlayer film 1 for laminated glass.
- the interlayer film 1 for laminated glass has a two-layer structure in which a shape auxiliary layer 12 is laminated on one surface of a light emitting layer 11 containing a light emitting material.
- the shape auxiliary layer 12 is formed in a wedge shape, a triangle shape, or a trapezoidal shape, so that the wedge film angle ⁇ of the laminated glass interlayer 1 as a whole is 0.1 to 1 mrad. It has a wedge shape.
- FIG. 2 shows a cross section in the thickness direction of the interlayer film 2 for laminated glass.
- the interlayer film 2 for laminated glass has a three-layer structure in which a shape auxiliary layer 22 and a shape auxiliary layer 23 are laminated on both surfaces of a light emitting layer 21 containing a light emitting material.
- the shape of the shape auxiliary layer 22 is a wedge shape, a triangle shape, or a trapezoidal shape so that the entire interlayer film 2 for laminated glass is formed.
- a wedge shape with a wedge angle ⁇ of 0.1 to 1 mrad As a wedge shape with a wedge angle ⁇ of 0.1 to 1 mrad.
- FIG. 3 shows a cross section in the thickness direction of the interlayer film 3 for laminated glass.
- the interlayer film 3 for laminated glass has a three-layer structure in which a shape auxiliary layer 32 and a shape auxiliary layer 33 are laminated on both surfaces of a light emitting layer 31 containing a light emitting material.
- the light emitting layer 31 has a gentle wedge shape with a difference between the maximum thickness and the minimum thickness of 100 ⁇ m or less.
- the wedge angle ⁇ of the laminated glass intermediate film 3 as a whole is increased. It has a wedge shape of 0.1 to 1 mrad.
- the light emitting layer contains a thermoplastic resin, a plasticizer, and a light emitting material.
- 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.
- thermoplastic resins such as resin and polyethylene terephthalate resin.
- 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 a polyvinyl butyral resin 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 said polyvinyl acetal resin has a preferable minimum of the amount of hydroxyl groups of 10 mol%, and a preferable upper limit of 32 mol%. When the amount of hydroxyl groups of the polyvinyl acetal resin contained in the light emitting layer is within this range, the light emitting layer can be easily molded, and the obtained interlayer film for laminated glass has high penetration resistance.
- the more preferable lower limit of the hydroxyl group amount of the polyvinyl acetal resin is 15 mol%, the more preferable upper limit is 30 mol%, the still more preferable lower limit is 18 mol%, the still more preferable upper limit is 28 mol%, and the particularly preferable lower limit is 20 mol%, particularly preferable.
- the upper limit is 25 mol%.
- 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 saponification degree of the polyvinyl alcohol is preferably 80 to 99.8 mol%.
- the preferable lower limit of the polymerization degree of the polyvinyl alcohol is 500, and the preferable upper limit is 4000. When the polymerization degree of the polyvinyl alcohol is 500 or more, the penetration resistance of the obtained laminated glass is increased.
- the interlayer film for laminated glass can be easily molded.
- 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 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 monobasic organic acid ester is not particularly limited.
- glycol such as triethylene glycol, tetraethylene glycol, tripropylene glycol, butyric acid, isobutyric acid, caproic acid, 2-ethylbutyric acid, heptylic acid, n-octyl
- glycol esters obtained by reaction with monobasic organic acids such as acid, 2-ethylhexyl acid, pelargonic acid (n-nonyl acid), and decyl acid.
- 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.
- the content of the plasticizer in the light emitting layer is not particularly limited, a preferable lower limit with respect to 100 parts by weight of the polyvinyl acetal resin is 30 parts by weight, and a preferable upper limit is 100 parts by weight.
- a preferable lower limit with respect to 100 parts by weight of the polyvinyl acetal resin is 30 parts by weight
- a preferable upper limit is 100 parts by weight.
- the content of the plasticizer is 30 parts by weight or more, the melt viscosity of the laminated glass interlayer film is lowered, and the degassing property when the laminated glass is produced using this laminated glass interlayer film is increased.
- the content of the plasticizer is 100 parts by weight or less, the transparency of the interlayer film for laminated glass increases.
- 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 luminescent material is at least one selected from the group consisting of luminescent particles, luminescent pigments and luminescent dyes.
- the luminescent particles and the luminescent pigment are, for example, Y 2 O 2 S: Eu, BaMg 2 Al 16 O 27 : Eu, Mn, (SrCaBaMg) 5 (PO 4 ) 3 Cl: Eu, BaMg 2 Al 16 O 27 : Eu, BaMg 2 Al 16 O 27 : Eu, Mn, Sr 5 (PO 4) 3 Cl: Eu, LaPO 4: Ce, Tb, MgAl 11 O 19: Ce, Tb, Y 2 O 3: Eu, Y (PV ) O 4 : Eu, 3.5MgO ⁇ 0.5MgF 2 ⁇ GeO 2 : Mn, Ca 10 (PO 4 ) 6 FCl: Sb, Mn, Sr 10 (PO 4 ) 6 FCl: Sb, Mn, (SrMg) 2 P 2 O 7 : Eu, Sr 2
- luminescent dye examples include (carbazole-naphthalimide) dye, (acetonitrile-triphenyleneamine) dye, aryl sulfonate cyanine dye, perylene dye, coumarin dye, tris (4,4,4-trifluoro-1- (2- Thienyl) -1,3-butanedionate-O, O ′) bis (triphenylphosphine oxide-O—) europium and the like.
- a compound having a naphthalimide skeleton or a compound having a coumarin skeleton is preferable.
- a compound having a naphthalimide skeleton and a compound having a coumarin skeleton have a high affinity for a thermoplastic resin used as a binder resin, so that it can be uniformly dispersed in the binder resin, and has high transparency and low haze.
- An interlayer film for glass can be obtained.
- a compound having a naphthalimide skeleton and a compound having a coumarin skeleton are extremely excellent in durability against ultraviolet rays, an interlayer film for laminated glass using the same can exhibit excellent light resistance.
- the compound having a naphthalimide skeleton include 4-bromo-1,8-naphthalimide, 4-amino-1,8-naphthalimide, 4-methoxy-N-methylnaphthalimide, naphthalimide, 4-aminonaphthalimide, N-methyl-4-aminonaphthalimide, N-ethyl-4-aminonaphthalimide, N-propyl-4-aminonaphthalimide, Nn-butyl-4-aminonaphthalimide, 4- Acetylaminonaphthalimide, N-methyl-4-acetylaminonaphthalimide, N-ethyl-4-acetylaminonaphthalimide, N-propyl-4-acetylaminonaphthalimide, Nn-butyl-4-acetylaminonaphthalimide N-methyl-4-methoxynaphthalimide, N-ethyl-4-methoxynaphtha Imido, N
- the compound having a coumarin skeleton include derivatives having an electron-donating substituent at the 7-position of the coumarin ring. More specifically, 3- (2′-benzothiazolyl) -7-diethylaminocoumarin (coumarin 6), 3- (2′-benzoimidazolyl)-, which is a derivative characterized by having an amino group at the 7-position of the coumarin ring.
- a light emitting material having a terephthalic acid ester structure is preferably used as the light emitting material.
- the light emitting material having the terephthalic acid ester structure include a compound having a structure represented by the following general formula (1) and a compound having a structure represented by the following general formula (2). These may be used alone or in combination of two or more.
- R 1 represents an organic group, and x is 1, 2, 3 or 4. Since the transparency of the interlayer film for laminated glass is further increased, x is preferably 1 or 2, more preferably a hydroxyl group at the 2-position or 5-position of the benzene ring, More preferably, it has a hydroxyl group at the 5-position.
- the organic group for R 1 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 terephthalate structure can be easily dispersed in the interlayer film for laminated glass.
- the hydrocarbon group is preferably an alkyl group.
- Examples of the compound having the structure represented by the general formula (1) include diethyl-2,5-dihydroxyterephthalate, dimethyl-2,5-dihydroxyterephthalate and the like. Among them, since a higher-contrast image can be displayed, the compound having the structure represented by the general formula (1) is diethyl-2,5-dihydroxyterephthalate (manufactured by Aldrich, “2,5-dihydroxyterephthalic acid”). Diethyl ”) is preferred. For example, the compound having the structure represented by the general formula (1) can be easily excited by light having a wavelength of 405 nm.
- R 2 represents an organic group
- R 3 and R 4 represent a hydrogen atom or an organic group
- y is 1, 2, 3, or 4.
- the organic group for R 2 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 3 R 4 is an amino group.
- R 3 and R 4 are preferably hydrogen atoms.
- one hydrogen atom may be the amino group, and two hydrogen atoms may be the amino, Three hydrogen atoms may be the amino group, and four hydrogen atoms may be the amino group.
- diethyl-2,5-diaminoterephthalate (manufactured by Aldrich) is preferable because an image with higher contrast can be displayed.
- the content of the light emitting material in the light emitting layer is preferably 0.005 parts by weight with respect to 100 parts by weight of the thermoplastic resin, and 5 parts by weight with respect to the preferred upper limit.
- the light emitting property may be lowered. This is thought to be due to the concentration quenching phenomenon in which the energy absorbed is shifted to a non-radiation process in which light is not emitted due to the interaction of the excited light emitting material, and the light emission intensity is reduced.
- the content of the light emitting material is within this range, light emission with sufficiently high contrast can be obtained when light having a specific wavelength is irradiated.
- 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 3 parts by weight, the still more preferable lower limit is 0.05 parts by weight, and the still more preferable upper limit is 1 part by weight.
- a preferable lower limit is 0.005% by weight and a preferable upper limit is 5% by weight in 100% by weight of the light emitting layer.
- the content of the light emitting material is 0.005% by weight or more, an interlayer film for laminated glass capable of displaying an image with higher contrast can be obtained.
- the content of the light emitting material is 5% by weight or less, an interlayer film for laminated glass having much higher transparency can be obtained.
- the more preferable lower limit of the content of the light emitting material is 0.01% by weight, the more preferable upper limit is 3% by weight, the still more preferable lower limit is 0.02% by weight, and the still more preferable upper limit is 1% by weight.
- the light emitting layer 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.
- compound may be a conventionally known dispersing agent such as a compound having an isocyanurate group such as isocyanurate.
- compound having an isocyanurate group such as isocyanurate.
- 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 preferable lower limit of the content of the dispersant with respect to 100 parts by weight of the light emitting material in the light emitting layer is 1 part by weight, and the preferable 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 light emitting layer.
- 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 layer may further contain an ultraviolet absorber.
- an ultraviolet absorber When the light emitting layer contains an ultraviolet absorber, the light resistance of the light emitting layer is increased.
- 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
- ultraviolet absorbers such as compounds having a structure.
- the preferable upper limit of the content of the ultraviolet absorber with respect to 100 parts by weight of the polyvinyl acetal resin in the light emitting layer is 1 part by weight, and the more preferable upper limit is 0.5 part by weight.
- the upper limit is 0.2 parts by weight, and a particularly preferred upper limit is 0.1 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 said light emitting layer may contain a heat ray absorber, when the heat shielding property is requested
- 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 light emitting layer may further contain additives such as a light stabilizer and an antistatic agent as necessary. Further, when providing a colored band in a partial region of the interlayer film for laminated glass of the present invention, a colorant such as a blue pigment, a blue dye, a green pigment, or a green dye is blended in a part of the light emitting layer. Also good.
- the magnesium element concentration in the light emitting layer is preferably 80 ppm or less.
- the light emitting material is a light emitting material having a terephthalic acid ester structure
- discoloration of the interlayer film for laminated glass is likely to occur particularly when the light emitting material having the terephthalic acid ester structure and a magnesium element form a complex.
- the magnesium element concentration of the light emitting layer is 80 ppm or less, discoloration of the interlayer film for laminated glass can be suppressed.
- the magnesium element concentration in the light emitting layer is preferably 75 ppm or less, more preferably 60 ppm or less, still more preferably 50 ppm or less, and 40 ppm. It is particularly preferred that it is below, most preferably 30 ppm or less, and most preferably 25 ppm or less.
- the magnesium element concentration in the light emitting layer may be 0 ppm.
- the magnesium element may be contained in the light emitting layer as, for example, metallic magnesium or a magnesium salt.
- discoloration means that the YI value of the laminated glass in which the interlayer film for laminated glass is laminated between two clear glasses (thickness 2.5 mm) exceeds 20.
- the YI value can be measured according to JIS Z 8722 using a spectrophotometer (manufactured by Hitachi High-Technologies Corporation, “U-4100”).
- the YI value is preferably 20 or less, more preferably 15 or less, and still more preferably 10 or less.
- the YI value is preferably 0 or more.
- the concentration of lithium element in the light emitting layer is preferably 25 ppm or less.
- the reason why the interlayer film for laminated glass is discolored is considered to be that the light emitting material having the terephthalic acid ester structure and the lithium element form a complex.
- concentration of the lithium element in the light emitting layer is 25 ppm or less, discoloration of the interlayer film for laminated glass can be further suppressed.
- a more preferable upper limit of the concentration of lithium element in the light emitting layer is 20 ppm, a further preferable upper limit is 10 ppm or less, a preferable lower limit is 0 ppm, and a more preferable lower limit is 1 ppm.
- the shape auxiliary layer contains a thermoplastic resin and a plasticizer.
- the thermoplastic resin and plasticizer contained in the shape auxiliary layer the same thermoplastic resin and plasticizer contained in the light emitting layer can be used. Since a higher contrast image can be displayed with a certain range of brightness, the shape auxiliary layer does not contain a light emitting material, or the concentration (wt%) of the light emitting material in the shape auxiliary layer is The concentration is preferably lower than the concentration (% by weight) of the light emitting material in the light emitting layer.
- the thermoplastic resin of the shape auxiliary layer is preferably a polyvinyl acetal resin.
- the shape auxiliary layer further contains an adhesive strength adjusting agent.
- the adhesive strength modifier is not particularly limited, and is preferably a metal salt, and is preferably at least one metal salt selected from the group consisting of alkali metal salts, alkaline earth metal salts, and magnesium salts.
- the metal salt preferably contains at least one metal selected from potassium and magnesium.
- the metal salt is more preferably an alkali metal salt of an organic acid having 1 to 16 carbon atoms, an alkaline earth metal salt of an organic acid having 1 to 16 carbon atoms, or a magnesium salt of an organic acid having 1 to 16 carbon atoms.
- an alkali metal salt of an organic acid having 2 to 16 carbon atoms More preferably, an alkali metal salt of an organic acid having 2 to 16 carbon atoms, an alkaline earth metal salt of an organic acid having 2 to 16 carbon atoms, or a magnesium salt having 2 to 16 carbon atoms.
- a magnesium salt of carboxylic acid or a potassium salt of carboxylic acid having 2 to 16 carbon atoms is particularly preferable.
- the magnesium salt of the carboxylic acid having 2 to 16 carbon atoms and the potassium salt of the carboxylic acid having 2 to 16 carbon atoms are not particularly limited, and examples thereof include magnesium acetate, potassium acetate, magnesium propionate, potassium propionate, 2- Examples thereof include magnesium ethyl butanoate, potassium 2-ethylbutanoate, magnesium 2-ethylhexanoate, potassium 2-ethylhexanoate and the like.
- the preferable lower limit of the carbon number of the organic acid is 1, the preferable upper limit is 10, the more preferable lower limit is 2, and the more preferable upper limit is 8.
- the content of the adhesive strength adjusting agent in the shape auxiliary layer is not particularly limited, but a preferable lower limit with respect to 100 parts by weight of the thermoplastic resin is 0.0005 parts by weight, and a preferable upper limit is 0.05 parts by weight.
- the penetration resistance of laminated glass becomes high as content of the said adhesive force regulator is 0.0005 weight part or more.
- the content of the adhesion adjusting agent is 0.05 parts by weight or less, the transparency of the interlayer film for laminated glass is increased.
- the minimum with more preferable content of the said adhesive force regulator is 0.002 weight part, and a more preferable upper limit is 0.02 weight part.
- the total content of alkali metal, alkaline earth metal and magnesium in the shape auxiliary layer is preferably 300 ppm or less.
- the alkali metal, alkaline earth metal, and magnesium may be included as a metal derived from the adhesive strength adjusting agent, or may be included as a metal derived from a neutralizing agent used when a polyvinyl acetal resin is synthesized.
- the total content of alkali metal, alkaline earth metal and magnesium in the shape auxiliary layer is more preferably 200 ppm or less, further preferably 150 ppm or less, and particularly preferably 100 ppm or less.
- the concentration of magnesium element contained in the shape auxiliary layer is preferably 150 ppm or less, more preferably 100 ppm or less, and further preferably 50 ppm or less. It is preferably 30 ppm or less.
- the magnesium concentration contained in the shape auxiliary layer may be 0 ppm or may exceed 0 ppm.
- the shape auxiliary layer may further contain additives such as an ultraviolet absorber, an antioxidant, a heat ray absorber, a light stabilizer, and an antistatic agent as necessary. Further, when a colored band is provided in a partial region of the interlayer film for laminated glass of the present invention, a colorant such as a blue pigment, a blue dye, a green pigment, or a green dye is blended in a part of the shape auxiliary layer. May be.
- the amount of hydroxyl groups of the polyvinyl acetal resin contained in the light emitting layer is as described above. It is preferable to select a combination of polyvinyl acetal resins in each layer so that the amount of hydroxyl groups in the polyvinyl acetal resin contained in the shape auxiliary layer is lower. Thereby, it can prevent that a luminescent material transfers to a shape auxiliary layer from a light emitting layer.
- the difference between the amount of hydroxyl groups of the polyvinyl acetal resin contained in the light emitting layer and the amount of hydroxyl groups of the polyvinyl acetal resin contained in the shape auxiliary layer. Is preferably less than 6.5 mol%.
- the difference in the amount of hydroxyl groups is more preferably 6.4 mol% or less, still more preferably 6.2 mol% or less, particularly preferably 6.0 mol% or less, and 5.8 mol%. % Is most preferred.
- the difference in the amount of hydroxyl groups is preferably 1 mol% or more, more preferably 2 mol% or more, and further preferably 3 mol% or more.
- thermoplastic resin and a plasticizer contained in the light emitting layer and the shape auxiliary layer various performances can be imparted to the resulting interlayer film for laminated glass.
- the content of the plasticizer contained in the light emitting layer larger than the content of the plasticizer contained in the shape auxiliary layer, it is possible to impart sound insulation performance to the interlayer film for laminated glass of the present invention. it can.
- high sound insulation can be imparted by setting the difference in the plasticizer content to preferably 5 parts by weight or more, more preferably 10 parts by weight or more, and even more preferably 15 parts by weight or more. it can.
- the difference in content of the plasticizer is preferably 50 parts by weight or less, more preferably 40 parts by weight or less, and still more preferably 35 parts by weight or less.
- the degree of acetylation of the polyvinyl acetal resin contained in the light emitting layer is higher than the degree of acetylation of the polyvinyl acetal resin contained in the shape auxiliary layer.
- the difference in the degree of acetylation of the polyvinyl acetal resin is preferably 0.1 mol% or less, more preferably 1 mol% or more, and even more preferably 5 mol% or more. It is particularly preferable that the amount be 10 mol% or more.
- the amount of hydroxyl groups of the polyvinyl acetal resin contained in the light emitting layer is lower than the amount of hydroxyl groups of the polyvinyl acetal resin contained in the shape auxiliary layer.
- the difference in the amount of hydroxyl groups is preferably 1 mol% or more, more preferably 3 mol% or more, and even more preferably 5 mol% or more.
- the degree of acetalization of the polyvinyl acetal resin contained in the light emitting layer is preferably higher than the degree of acetalization of the polyvinyl acetal resin contained in the shape auxiliary layer.
- the method for producing the interlayer film for laminated glass of the present invention is not particularly limited.
- a plasticizer solution containing a plasticizer and a light emitting material and a polyvinyl acetal resin are sufficiently mixed to produce a resin composition for forming the light emitting layer.
- a plasticizer solution containing an adhesive force adjusting agent and a plasticizer and a polyvinyl acetal resin are sufficiently mixed to prepare a resin composition for forming the shape auxiliary layer.
- the resin composition for forming the said light emitting layer and the resin composition for forming the said shape auxiliary layer are coextruded using a co-extruder, and the laminated glass by which the light emitting layer and the shape auxiliary layer were laminated
- the interlayer film for laminated glass of the present invention has the light emitting layer, it emits light when irradiated with light having a specific wavelength. By utilizing this property, information can be displayed with high contrast.
- a spot light source manufactured by Hamamatsu Photonics, “LC-8”
- a xenon flash lamp manufactured by Heraeus, “CW lamp”
- a black light Inai) Seieido Co., Ltd., “Carry Hand”.
- the laminated glass in which the interlayer film for laminated glass of the present invention is laminated between a pair of glass plates is also one aspect of the present invention.
- 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 plate glass, lined plate glass, colored plate glass, heat ray absorbing glass, heat ray reflective 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.
- glass plate Two or more types of glass plates may be used as the glass plate.
- stacked the intermediate film for laminated glasses of this invention between transparent float plate glass and colored glass plates like green glass is mentioned.
- the intermediate film for laminated glasses which can display an image with a high contrast with the brightness
- Example 1 Preparation of resin composition for light emitting layer Diethyl which is a compound having a structure represented by the above general formula (1) as a light emitting material in 60 parts by weight of triethylene glycol di-2-ethylhexanoate (3GO) 1.5 parts by weight of -2,5-dihydroxyterephthalate (manufactured by Aldrich, “diethyl 2,5-dihydroxyterephthalate”) was added to prepare a luminescent plasticizer solution.
- 3GO triethylene glycol di-2-ethylhexanoate
- -2,5-dihydroxyterephthalate manufactured by Aldrich, “diethyl 2,5-dihydroxyterephthalate”
- the total amount of the obtained plasticizer solution and polyvinyl butyral obtained by acetalizing polyvinyl alcohol having a polymerization degree of 2300 with n-butyraldehyde (acetyl group amount 12.5 mol%, hydroxyl group amount 23.6 mol) %, Butyralization degree 63.9 mol%) was sufficiently kneaded with a mixing roll to prepare a light emitting layer resin composition.
- the light emitting layer in the obtained interlayer film for laminated glass has a wedge-shaped cross-sectional shape with a minimum thickness of 90 ⁇ m and a maximum thickness of 140 ⁇ m
- the entire interlayer film for laminated glass has a wedge-shaped cross-sectional shape with a minimum thickness of 800 ⁇ m and a maximum thickness of 1200 ⁇ m.
- One end of the interlayer film for laminated glass has a minimum thickness and the other end has a maximum thickness, and the minimum thickness and the maximum thickness were measured by observation with an optical microscope.
- the obtained interlayer film was sandwiched between two transparent float glasses (length 1000 mm x width 300 mm x thickness 2.5 mm) to obtain a laminate.
- the obtained laminated body was temporarily press-bonded using a 230 ° C. heating roll. Then, the laminated body temporarily pressure-bonded by the heating roll method using an autoclave for 20 minutes under the conditions of 135 ° C. and a pressure of 1.2 MPa to produce a laminated glass (length 1000 mm ⁇ width 300 mm).
- the laminated body temporarily bonded was pressure-bonded for 20 minutes under the conditions of 135 ° C. and a pressure of 1.2 MPa using an autoclave by a heating roll method to produce a laminated glass for luminance measurement (length 100 mm ⁇ width 100 mm). .
- Example 2 An interlayer film for laminated glass and a laminated glass were obtained in the same manner as in Example 1 except that the type of the luminescent material and the maximum thickness and the minimum thickness in the thickness direction of the luminescent layer were as shown in Table 1.
- Examples 4 to 8, Comparative Examples 3 and 4 In the same manner as in Example 1, except that the maximum thickness and the minimum thickness in the thickness direction of the light emitting layer and the minimum thickness, the maximum thickness and the wedge angle of the intermediate film were changed as shown in Table 2, an intermediate for laminated glass A film and laminated glass were obtained.
- Example 9 to 12 Comparative Examples 5 and 6 Except for changing the composition of polyvinyl butyral to be used, the plasticizer content, the maximum thickness and the minimum thickness in the thickness direction of the light emitting layer, and the minimum thickness, the maximum thickness and the wedge angle of the intermediate film as shown in Table 3, In the same manner as in Example 1, an interlayer film for laminated glass and a laminated glass were obtained.
- Polyvinyl butyral obtained by acetalizing polyvinyl alcohol having a polymerization degree of 1700 with n-butyraldehyde (acetyl group content 0.9 mol%, hydroxyl group content 30.0 mol) %, Butyralization degree 69.1 mol%) was sufficiently kneaded with a mixing roll to prepare a light emitting layer resin composition.
- the first resin layer and the second resin layer resin composition and the sound insulation layer resin composition are co-extruded using a co-extruder to produce the first resin.
- a laminate having a three-layer structure in which a layer, a sound insulating layer and a second resin layer were laminated in this order was obtained as a shape auxiliary layer.
- the light emitting layer was obtained by extruding the obtained resin composition for light emitting layers as a single layer.
- the shape auxiliary layer and the light emitting layer were laminated in the order of the first resin layer, the sound insulating layer, the second resin layer, and the light emitting layer to obtain an interlayer film for laminated glass having a four-layer structure.
- the shortest distance between one end and the other end in the direction perpendicular to the extrusion direction of the obtained intermediate film was 1 m.
- the light emitting layer in the obtained interlayer film for laminated glass has a wedge-shaped cross-sectional shape with a minimum thickness of 90 ⁇ m and a maximum thickness of 140 ⁇ m
- the entire interlayer film for laminated glass has a wedge-shaped cross-sectional shape with a minimum thickness of 800 ⁇ m and a maximum thickness of 1200 ⁇ m. Had.
- the first resin layer has a wedge-shaped cross-sectional shape with a minimum thickness of 305 ⁇ m and a maximum thickness of 480 ⁇ m
- the sound insulating layer has a rectangular cross-sectional shape with an average thickness of 100 ⁇ m
- the resin layer had a wedge-shaped cross-sectional shape with a minimum thickness of 305 ⁇ m and a maximum thickness of 480 ⁇ m.
- One end of the interlayer film for laminated glass has a minimum thickness and the other end has a maximum thickness, and the minimum thickness and the maximum thickness were measured by observation with an optical microscope.
- the laminated body temporarily bonded was pressure-bonded for 20 minutes under the conditions of 135 ° C. and a pressure of 1.2 MPa using an autoclave by a heating roll method to produce a laminated glass for luminance measurement (length 100 mm ⁇ width 100 mm). .
- Example 14 Comparative Examples 7 and 8
- Example 13 except that the minimum thickness and maximum thickness of the light emitting layer, the minimum thickness and maximum thickness of the first resin layer, and the minimum thickness and maximum thickness of the second resin layer were changed as shown in Table 4.
- an interlayer film for laminated glass and a laminated glass were obtained.
- the intermediate film for laminated glasses which can display an image with a high contrast with the brightness
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Abstract
Description
HUDの機構としては、これまで種々の形態のものが開発されている。例えば、HUD表示部がフロントガラス表面にはなく、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にフロントガラスと同じ位置(すなわち、同一視野内)で視認させる形態のものがある。このような反射型のHUDには、焦点距離を適切に調節することで、表示される情報が遠方に存在するように視認され、運転者の眼の焦点を変更する必要が無く安全であるという利点がある。
しかしながら、実際に発光材料を配合した断面形状が楔形の合わせガラス用中間膜を用いると、発光材料により表示される画像の輝度が合わせガラスの部位によって異なってしまうという新たな問題が生じた。
以下に本発明を詳述する。
本発明者らは、更に鋭意検討の結果、発光材料を含む発光層の厚みを最大厚さと最小厚さの差を100μm以下として蛍光材料の面密度の変動を一定以下にするとともに、樹脂層を積層した多層構造として、合わせガラス用中間膜全体としての断面形状を楔形とすることにより、二重像の発生を防止しながら、一定範囲の輝度で画像を表示することができる合わせガラスを得ることができることを見出し、本発明を完成した。
本発明の合わせガラス用中間膜は、断面形状が楔形である。合わせガラスの取り付け角度に応じて、楔形の楔角θを調整することにより、二重像の発生を防止した画像表示が可能となる。二重像をより一層抑制する観点から、上記楔角θの好ましい下限は0.1mrad、より好ましい下限は0.2mrad、更に好ましい下限は0.3mradであり、好ましい上限は1mrad、より好ましい上限は0.9mradである。
なお、例えば押出機を用いて樹脂組成物を押出し成形する方法により断面形状が楔形の合わせガラス用中間膜を製造した場合、薄い側の一方の端部からわずかに内側の領域(具体的には、一端と他端との間の距離をXとしたときに、薄い側の一端から内側に向かって0X~0.2Xの距離の領域)に最小厚みを有し、厚い側の一方の端部からわずかに内側の領域(具体的には、一端と他端との間の距離をXとしたときに、厚い側の一端から内側に向かって0X~0.2Xの距離の領域)に最大厚みを有する形状となることがある。本明細書においては、このような形状も楔形に含まれる。
上記形状補助層は、上記発光層の一方の面にのみ積層されていてもよく、両方の面に積層されていてもよい。更に、複数の形状補助層を積層してもよい。
上記発光層の最大厚さと最小厚さの差は100μm以下である。これにより、一定範囲の輝度で画像を表示することができる。上記発光層の最大厚さと最小厚さの差は95μm以下であることが好ましく、90μm以下であることがより好ましく、60μm以下であることが更に好ましく、50μm以下であることが特に好ましい。上記発光層の最大厚さと最小厚さの差の下限は特に限定されないが、0であることが好ましい。
上記形状補助層は、断面形状が楔形、三角形、又は、台形であることが好ましい。断面形状が楔形、三角形、又は、台形の形状補助層を積層することにより、合わせガラス用中間膜全体としての断面形状を楔形となるように調整することができる。なお、上記形状補助層としての役割を果たせるのであれば、上記形状補助層は、例えば、五角形、六角形、楕円形等の形状をしていてもよい。また、複数の形状補助層を組み合わせて、合わせガラス用中間膜全体としての断面形状を整えてもよい。この場合、全ての形状補助層の断面形状が同一である必要はなく、異なっていてもよい。
なお、上記形状補助層の厚みの下限は、形状補助層の最小厚さの部分の厚みを意味し、上記形状補助層の厚みの上限は、形状補助層の最大厚さの部分の厚みを意味する。また、複数の形状補助層を組み合わせて用いる場合は、その合計の厚みを意味する。
なお、上記合わせガラス用中間膜全体の厚みの下限は、合わせガラス用中間膜全体の最小厚さの部分の厚みを意味し、上記合わせガラス用中間膜全体の厚みの上限は、合わせガラス用中間膜全体の最大厚さの部分の厚みを意味する。
合わせガラス用中間膜1は、発光材料を含有する発光層11の一方の面に形状補助層12が積層された2層構造を有する。
ここで発光層11は矩形であるのに対して、形状補助層12の形状を楔形、三角形、又は、台形とすることにより、合わせガラス用中間膜1全体として楔角θが0.1~1mradである楔形となっている。
合わせガラス用中間膜2は、発光材料を含有する発光層21の両面に形状補助層22と形状補助層23とが積層された3層構造を有する。
ここで発光層21と形状補助層23とが厚みが一定の矩形であるのに対して、形状補助層22の形状を楔形、三角形、又は、台形とすることにより、合わせガラス用中間膜2全体として楔角θが0.1~1mradである楔形となっている。
合わせガラス用中間膜3は、発光材料を含有する発光層31の両面に形状補助層32と形状補助層33とが積層された3層構造を有する。
ここで発光層31は最大厚さと最小厚さの差が100μm以下の緩やかな楔形であり、楔形の形状補助層32、33を積層することにより、合わせガラス用中間膜3全体として楔角θが0.1~1mradである楔形となっている。
上記発光層は、熱可塑性樹脂と可塑剤と発光材料とを含有する。発光材料を含有する発光層を有することにより、本発明の合わせガラス用中間膜は、光線を照射することにより、コントラストが高い画像を表示することができる。
上記ポリビニルアセタール樹脂は、水酸基量の好ましい下限が10モル%、好ましい上限が32モル%である。上記発光層に含まれるポリビニルアセタール樹脂の水酸基量がこの範囲内であると、発光層の成形が容易であり、かつ、得られる合わせガラス用中間膜の耐貫通性が高くなる。上記ポリビニルアセタール樹脂の水酸基量のより好ましい下限は15モル%、より好ましい上限は30モル%、更に好ましい下限は18モル%、更に好ましい上限は28モル%、特に好ましい下限は20モル%、特に好ましい上限は25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は、通常、ポリ酢酸ビニルを鹸化することにより得られ、鹸化度70~99.8モル%のポリビニルアルコールが一般的に用いられる。上記ポリビニルアルコールの鹸化度は、80~99.8モル%であることが好ましい。
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、得られる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、合わせガラス用中間膜の成形が容易になる。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。
上記発光粒子及び上記発光顔料は、例えば、Y2O2S:Eu、BaMg2Al16O27:Eu,Mn、(SrCaBaMg)5(PO4)3Cl:Eu、BaMg2Al16O27:Eu、BaMg2Al16O27:Eu,Mn、Sr5(PO4)3Cl:Eu、LaPO4:Ce,Tb、MgAl11O19:Ce,Tb、Y2O3:Eu、Y(PV)O4:Eu、3.5MgO・0.5MgF2・GeO2:Mn、Ca10(PO4)6FCl:Sb,Mn、Sr10(PO4)6FCl:Sb,Mn、(SrMg)2P2O7:Eu、Sr2P2O7:Eu、CaWO4、CaWO4:Pb、MgWO4、(BaCa)5(PO4)3Cl:Eu、Sr4Al14O25:Eu、Zn2SiO4:Mn等で示される蛍光体やそれらからなる複合体や、ZnS粒子、GaSe粒子、SiC粒子、CdTe粒子等の粒子型等が挙げられる。
上記R1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合わせガラス用中間膜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R2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合わせガラス用中間膜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(2)中、NR3R4はアミノ基である。R3及びR4は、水素原子であることが好ましい。上記一般式(2)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や、トリエトキシプロピルイソシアネートシラン、トリエトキシブチルシラン等のアルキル基を有するシラン構造を有する化合物や、トリエトキシプロピルアクリロキシシラン等のアクリロキシ基を有するシラン構造を有する化合物や、トリエトキシプロピルビニルシラン等のビニル基を有するシラン構造を有する化合物や、エポキシ基やリン酸基、カルボキシル基、メルカプト基等の側鎖を有する高分子量体であるポリシロキサン構造を有する化合物や、イソシアネート等のイソシアネート基を有する化合物や、イソシアヌレート等のイソシアヌレート基を有する化合物等の従来公知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。
上記紫外線吸収剤は、例えば、マロン酸エステル構造を有する化合物、シュウ酸アニリド構造を有する化合物、ベンゾトリアゾール構造を有する化合物、ベンゾフェノン構造を有する化合物、トリアジン構造を有する化合物、ベンゾエート構造を有する化合物、ヒンダードアミン構造を有する化合物等の紫外線吸収剤が挙げられる。
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)ブチリックアッシ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。
上記マグネシウム元素は、例えば、金属マグネシウムやマグネシウム塩として、上記発光層に含まれていてもよい。
なお、変色とは、合わせガラス用中間膜が2枚のクリアガラス(厚み2.5mm)の間に積層された合わせガラスのYI値が20を超えることを意味する。YI値は、分光光度計(日立ハイテクノロジーズ社製、「U-4100」)を使用して、JIS Z 8722に準拠して、測定することができる。上記YI値は、20以下であることが好ましく、15以下であることがより好ましく、10以下であることが更に好ましい。また、上記YI値は、0以上であることが好ましい。
上記接着力調整剤は特に限定されず、金属塩であることが好ましく、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から選択された少なくとも1種の金属塩であることが好ましい。上記金属塩は、カリウム及びマグネシウムの内の少なくとも1種の金属を含むことが好ましい。上記金属塩は、炭素数1~16の有機酸のアルカリ金属塩、炭素数1~16の有機酸のアルカリ土類金属塩又は炭素数1~16の有機酸のマグネシウム塩であることがより好ましく、炭素数2~16の有機酸のアルカリ金属塩、炭素数2~16の有機酸のアルカリ土類金属塩又は炭素数2~16のマグネシウム塩であることが更に好ましく、炭素数2~16のカルボン酸のマグネシウム塩又は炭素数2~16のカルボン酸のカリウム塩であることが特に好ましい。上記炭素数2~16のカルボン酸のマグネシウム塩及び上記炭素数2~16のカルボン酸のカリウム塩としては特に限定されないが、例えば、酢酸マグネシウム、酢酸カリウム、プロピオン酸マグネシウム、プロピオン酸カリウム、2-エチルブタン酸マグネシウム、2-エチルブタン酸カリウム、2-エチルヘキサン酸マグネシウム、2-エチルヘキサン酸カリウム等が挙げられる。上記有機酸の炭素数の好ましい下限は1、好ましい上限は10、より好ましい下限は2、より好ましい上限は8である。
合わせガラス用中間膜の変色をより一層防止できることから、上記形状補助層に含まれるマグネシウム元素の濃度は150ppm以下であることが好ましく、100ppm以下であることがより好ましく、50ppm以下であることが更に好ましく、30ppm以下であることが特に好ましい。上記形状補助層に含まれるマグネシウム濃度は0ppmであってもよく、0ppmを超えてもよい。
また、本発明の合わせガラス用中間膜の一部の領域に着色帯を設ける場合には、上記形状補助層の一部に青色顔料、青色染料、緑色顔料、緑色染料等の着色剤を配合してもよい。
発光材料が発光層から形状補助層へ移行することをより一層防止できることから、上記発光層に含まれるポリビニルアセタール樹脂の水酸基量と、上記形状補助層に含まれるポリビニルアセタール樹脂の水酸基量との差は、6.5モル%未満であることが好ましい。上記水酸基量の差は、6.4モル%以下であることがより好ましく、6.2モル%以下であることが更に好ましく、6.0モル%以下であることが特に好ましく、5.8モル%以下であることが最も好ましい。
また、上記水酸基量の差は、1モル%以上であることが好ましく、2モル%以上であることがより好ましく、3モル%以上であることが更に好ましい。
例えば、上記発光層に含まれる可塑剤の含有量を、上記形状補助層に含まれる可塑剤の含有量よりも多くすることにより、本発明の合わせガラス用中間膜に遮音性能を付与することができる。具体的には、上記可塑剤の含有量の差を、好ましくは5重量部以上、より好ましくは10重量部以上、更に好ましくは15重量部以上とすることにより、高い遮音性を付与することができる。上記可塑剤の含有量の差は、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。
遮音性をより一層高める観点から、上記発光層に含まれるポリビニルアセタール樹脂の水酸基量は、上記形状補助層に含まれるポリビニルアセタール樹脂の水酸基量よりも低いことが好ましい。具体的には、上記水酸基量の差を、1モル%以上とすることが好ましく、3モル%以上とすることがより好ましく、5モル%以上とすることが更に好ましい。
遮音性をより一層高める観点から、上記発光層に含まれるポリビニルアセタール樹脂のアセタール化度は、上記形状補助層に含まれるポリビニルアセタール樹脂のアセタール化度よりも高いことが好ましい。
上記特定の波長の光線を照射するための装置として、例えば、スポット光源(浜松ホトニクス社製、「LC-8」)、キセノン・フラッシュランプ(ヘレウス社製、「CWランプ」)、ブラックライト(井内盛栄堂社製、「キャリーハンド」)等が挙げられる。
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、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、本発明の合わせガラス用中間膜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。
(1)発光層用樹脂組成物の調製
トリエチレングリコールジ-2-エチルヘキサノエート(3GO)60重量部に、発光材料として上記一般式(1)で表される構造を有する化合物であるジエチル-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」)1.5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、重合度が2300であるポリビニルアルコールをn-ブチルアルデヒドでアセタール化することにより得られたポリビニルブチラール(アセチル基量12.5モル%、水酸基量23.6モル%、ブチラール化度63.9モル%)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、発光層用樹脂組成物を調製した。
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、接着力調整剤として酢酸マグネシウムを加え、可塑剤溶液を調製した。得られた可塑剤溶液の全量と、重合度が1700であるポリビニルアルコールをn-ブチルアルデヒドでアセタール化することにより得られたポリビニルブチラール(アセチル基量0.9モル%、水酸基量30.0モル%、ブチラール化度69.1モル%)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、形状補助層用樹脂組成物を調製した。
なお、形状補助層中のマグネシウム元素の濃度が70ppmとなるように、酢酸マグネシウムをトリエチレングリコールジ-2-エチルヘキサノエート(3GO)に添加した。
得られた発光層用樹脂組成物及び形状補助層用樹脂組成物を、押出機を用いて共押出することにより、形状補助層、発光層及び形状補助層がこの順に積層した、図3に記載された3層構造の合わせガラス用中間膜を得た。
なお、得られた中間膜の押出方向に対する垂直方向における一端と他端の最短距離を測定すると1mであった。
また、得られた合わせガラス用中間膜における発光層は最小厚み90μm、最大厚み140μmの楔形の断面形状を有し、合わせガラス用中間膜全体では最小厚み800μm、最大厚み1200μmの楔形の断面形状を有していた。なお、合わせガラス用中間膜の一端が最小厚みを有し、他端が最大厚みを有しており、光学顕微鏡で観察し、最小厚み及び最大厚みを測定した。
得られた中間膜を、2枚の透明なフロートガラス(縦1000mm×横300mm×厚さ2.5mm)で挟み込んで、積層体を得た。230℃の加熱ロールを用いて、得られた積層体を仮圧着した。その後、仮圧着された積層体を、加熱ロール法により、オートクレーブを用いて、135℃、圧力1.2MPaの条件で20分間圧着し、合わせガラス(縦1000mm×横300mm)を作製した。
一端と他端の最短距離上における、一端から10cmの点を中心となるように、縦10cm×横10cmの中間膜(薄い部分)を切り抜いた。同様に、一端と他端の最短距離上における、他端から10cmの点を中心となるように、縦10cm×横10cmの中間膜(厚い部分)を切り抜いた。
得られた中間膜(薄い部分)及び中間膜(厚い部分)それぞれを、2枚の透明なフロートガラス(縦100mm×横100mm×厚さ2.5mm)で挟み込んで、積層体を得た。230℃の加熱ロールを用いて、得られた積層体を仮圧着した。その後、仮圧着された積層体を、加熱ロール法により、オートクレーブを用いて、135℃、圧力1.2MPaの条件で20分間圧着し、輝度測定用合わせガラス(縦100mm×横100mm)を作製した。
発光材料の種類、発光層の厚み方向の最大厚み及び最小厚みを表1に示すようにしたこと以外は、実施例1と同様にして、合わせガラス用中間膜及び合わせガラスを得た。
発光材料の種類、発光層の厚み方向の最大厚み及び最小厚みを表1に示すようにし、形状補助層を積層しなかったこと以外は、実施例1と同様にして、合わせガラス用中間膜及び合わせガラスを得た。
発光層の厚み方向の最大厚み及び最小厚み、並びに、中間膜の最小厚み、最大厚み及び楔角を表2に示すように変更したこと以外は、実施例1と同様にして、合わせガラス用中間膜及び合わせガラスを得た。
用いるポリビニルブチラールの組成、可塑剤の含有量、発光層の厚み方向の最大厚み及び最小厚み、並びに、中間膜の最小厚み、最大厚み及び楔角を表3に示すように変更したこと以外は、実施例1と同様にして、合わせガラス用中間膜及び合わせガラスを得た。
(1)発光層用樹脂組成物の調製
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、発光材料として上記一般式(1)で表される構造を有する化合物であるジエチル-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」)1.5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、重合度が1700であるポリビニルアルコールをn-ブチルアルデヒドでアセタール化することにより得られたポリビニルブチラール(アセチル基量0.9モル%、水酸基量30.0モル%、ブチラール化度69.1モル%)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、発光層用樹脂組成物を調製した。
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、接着力調整剤として酢酸マグネシウムを加え、可塑剤溶液を調製した。得られた可塑剤溶液の全量と、重合度が1700であるポリビニルアルコールをn-ブチルアルデヒドでアセタール化することにより得られたポリビニルブチラール(アセチル基量0.9モル%、水酸基量30.0モル%、ブチラール化度69.1モル%)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、第1の樹脂層及び第2の樹脂層用樹脂組成物を調製した。
なお、第1の樹脂層及び第2の樹脂層中のマグネシウム元素の濃度が70ppmとなるように、酢酸マグネシウムをトリエチレングリコールジ-2-エチルヘキサノエート(3GO)に添加した。
トリエチレングリコールジ-2-エチルヘキサノエート(3GO)60重量部と、重合度が2300であるポリビニルアルコールをn-ブチルアルデヒドでアセタール化することにより得られたポリビニルブチラール(アセチル基量12.5モル%、水酸基量23.6モル%、ブチラール化度63.9モル%)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、遮音層用樹脂組成物を調製した。
第1の樹脂層及び第2の樹脂層用樹脂組成物と、遮音層用樹脂組成物とを、共押出機を用いて共押出することにより、第1の樹脂層、遮音層及び第2の樹脂層がこの順に積層した、3層構造の積層体を形状補助層として得た。
得られた発光層用樹脂組成物を、単層で押し出すことにより発光層を得た。形状補助層及び発光層を、第1の樹脂層、遮音層、第2の樹脂層、発光層の順に積層することで4層構造の合わせガラス用中間膜を得た。
なお、得られた中間膜の押出方向に対する垂直方向における一端と他端の最短距離を測定すると1mであった。
また、得られた合わせガラス用中間膜における発光層は最小厚み90μm、最大厚み140μmの楔形の断面形状を有し、合わせガラス用中間膜全体では最小厚み800μm、最大厚み1200μmの楔形の断面形状を有していた。更に、得られた合わせガラス用中間膜における第1の樹脂層は最小厚み305μm、最大厚み480μmの楔形の断面形状を有し、遮音層は平均厚み100μmの矩形の断面形状を有し、第2の樹脂層は最小厚み305μm、最大厚み480μmの楔形の断面形状を有していた。なお、合わせガラス用中間膜の一端が最小厚みを有し、他端が最大厚みを有しており、光学顕微鏡で観察し、最小厚み及び最大厚みを測定した。
得られた中間膜を、2枚の透明なフロートガラス(縦1000mm×横300mm×厚さ2.5mm)で挟み込んで、積層体を得た。230℃の加熱ロールを用いて、得られた積層体を仮圧着した。その後、仮圧着された積層体を、加熱ロール法により、オートクレーブを用いて、135℃、圧力1.2MPaの条件で20分間圧着し、合わせガラス(縦1000mm×横300mm)を作製した。
一端と他端の最短距離上における、一端から10cmの点を中心となるように、縦10cm×横10cmの中間膜(薄い部分)を切り抜いた。同様に、一端と他端の最短距離上における、他端から10cmの点を中心となるように、縦10cm×横10cmの中間膜(厚い部分)を切り抜いた。
得られた中間膜(薄い部分)及び中間膜(厚い部分)それぞれを、2枚の透明なフロートガラス(縦100mm×横100mm×厚さ2.5mm)で挟み込んで、積層体を得た。230℃の加熱ロールを用いて、得られた積層体を仮圧着した。その後、仮圧着された積層体を、加熱ロール法により、オートクレーブを用いて、135℃、圧力1.2MPaの条件で20分間圧着し、輝度測定用合わせガラス(縦100mm×横100mm)を作製した。
発光層の最小厚み及び最大厚み、第1の樹脂層の最小厚み及び最大厚み、並びに、第2の樹脂層の最小厚み及び最大厚みを表4に示すように変更したこと以外は、実施例13と同様にして、合わせガラス用中間膜及び合わせガラスを得た。
実施例及び比較例で得られた合わせガラスについて、以下の方法で評価を行った。
結果を表1~4に示した。
得られた合わせガラス(縦1000mm×横300mm)をフロントガラスの位置に設置した。合わせガラスの下方に設置した表示ユニットから表示情報を合わせガラスに反射させ、所定の位置で二重像の有無を目視で確認した。二重像が確認されない場合を「○」、二重像が確認される場合を「×」として評価した。
得られた輝度測定用合わせガラスを、暗室下にて、合わせガラスの面に対して垂直方向に10cm離れた位置に配置したHigh Powerキセノン光源(朝日分光社製、「REX-250」、照射波長405nm)から合わせガラスの全面へ光を照射し、光を照射した合わせガラスの面から45度の角度で、合わせガラス面からの最短距離として、35cm離れた位置に配置した輝度計(トプコンテクノハウス社製、「SR-3AR」)によって輝度を測定した。
中間膜(薄い部分)及び中間膜(厚い部分)における輝度の差の絶対値が200以下である場合を「○」、200を超える場合を「×」と評価した。
11 発光層
12 形状補助層
2 合わせガラス用中間膜
21 発光層
22 形状補助層
23 形状補助層
3 合わせガラス用中間膜
31 発光層
32 形状補助層
33 形状補助層
Claims (5)
- 熱可塑性樹脂と可塑剤と発光材料とを含有する発光層と、前記発光層の少なくとも一方の面に積層された、熱可塑性樹脂と可塑剤とを含有する樹脂層とを含む多層構造の合わせガラス用中間膜であって、
合わせガラス用中間膜の断面形状が楔形であり、前記発光層の最大厚さと最小厚さの差が100μm以下である
ことを特徴とする合わせガラス用中間膜。 - 合わせガラス用中間膜の断面形状が、楔角θが0.1~1mradである楔形であることを特徴とする請求項1記載の合わせガラス用中間膜。
- 発光層及び樹脂層に含まれる熱可塑性樹脂が、ポリビニルアセタール樹脂であることを特徴とする請求項1又は2記載の合わせガラス用中間膜。
- 発光層に含まれるポリビニルアセタール樹脂の水酸基量が、樹脂層に含まれるポリビニルアセタール樹脂の水酸基量よりも低いことを特徴とする請求項3記載の合わせガラス用中間膜。
- 請求項1、2、3又は4記載の合わせガラス用中間膜が、一対のガラス板の間に積層されていることを特徴とする合わせガラス。
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CN106132891B (zh) | 2021-05-04 |
MX2017001152A (es) | 2017-05-03 |
RU2017114974A3 (ja) | 2019-02-21 |
EP3202737A1 (en) | 2017-08-09 |
JPWO2016052478A1 (ja) | 2017-07-06 |
RU2017114974A (ru) | 2018-11-05 |
US10562276B2 (en) | 2020-02-18 |
JP6978185B2 (ja) | 2021-12-08 |
KR102391050B1 (ko) | 2022-04-26 |
EP3202737A4 (en) | 2018-04-18 |
KR20170063435A (ko) | 2017-06-08 |
RU2700354C2 (ru) | 2019-09-16 |
US20170136742A1 (en) | 2017-05-18 |
EP3202737B1 (en) | 2020-12-09 |
CN106132891A (zh) | 2016-11-16 |
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