WO2014084046A1 - Glass with phase differentiation function, organic el display, and liquid crystal display - Google Patents
Glass with phase differentiation function, organic el display, and liquid crystal display Download PDFInfo
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- WO2014084046A1 WO2014084046A1 PCT/JP2013/080657 JP2013080657W WO2014084046A1 WO 2014084046 A1 WO2014084046 A1 WO 2014084046A1 JP 2013080657 W JP2013080657 W JP 2013080657W WO 2014084046 A1 WO2014084046 A1 WO 2014084046A1
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- glass
- retardation
- layer
- resin
- cellulose
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- WEUBQNJHVBMUMD-UHFFFAOYSA-N trichloro(3,3,3-trifluoropropyl)silane Chemical compound FC(F)(F)CC[Si](Cl)(Cl)Cl WEUBQNJHVBMUMD-UHFFFAOYSA-N 0.000 description 1
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- PGOAAUBOHVGLCX-UHFFFAOYSA-N trichloro-[3-(2,3,4,5,6-pentafluorophenyl)propyl]silane Chemical compound FC1=C(F)C(F)=C(CCC[Si](Cl)(Cl)Cl)C(F)=C1F PGOAAUBOHVGLCX-UHFFFAOYSA-N 0.000 description 1
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- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
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- MDDPTCUZZASZIQ-UHFFFAOYSA-N tris[(2-methylpropan-2-yl)oxy]alumane Chemical compound [Al+3].CC(C)(C)[O-].CC(C)(C)[O-].CC(C)(C)[O-] MDDPTCUZZASZIQ-UHFFFAOYSA-N 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
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- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 description 1
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- 150000003755 zirconium compounds Chemical class 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- 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
- B32B17/08—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 cellulosic plastic substance or gelatin
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3083—Birefringent or phase retarding elements
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
- H10K59/8791—Arrangements for improving contrast, e.g. preventing reflection of ambient light
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/13363—Birefringent elements, e.g. for optical compensation
- G02F1/133638—Waveplates, i.e. plates with a retardation value of lambda/n
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F2202/00—Materials and properties
- G02F2202/28—Adhesive materials or arrangements
Definitions
- the present invention relates to a glass with a retardation function in which a ⁇ / 4 retardation layer is provided on a thin film glass, and an organic EL (Electro-Luminescence) display device and a liquid crystal display device including the glass.
- a glass with a retardation function in which a ⁇ / 4 retardation layer is provided on a thin film glass, and an organic EL (Electro-Luminescence) display device and a liquid crystal display device including the glass.
- a glass substrate is generally used for the display device, and the display device can be made thin and light by thinning the glass substrate.
- the glass substrate is easily broken and the handling property is deteriorated.
- Patent Document 1 a resin film is bonded to a glass film having a thickness of 0.1 ⁇ m to 100 ⁇ m via an adhesive to reduce damage when the glass film is handled.
- Patent Document 2 also proposes a method of attaching a film to a thin film glass via an adhesive.
- Patent Document 3 an ultrathin glass with a thickness of 50 ⁇ m is sandwiched and laminated between PET (polyethylene terephthalate) films with an adhesive to increase the strength while giving flexibility to the entire film. I am doing so.
- Patent Document 1 mentions an acrylic pressure-sensitive adhesive
- Patent Document 2 mentions a thermosetting epoxy resin
- Patent Document 3 discloses a specific example thereof. It has not been.
- JP 2001-97733 A see claim 1, paragraphs [0017], [0059], etc.
- JP 2009-94050 A (refer to claim 1, paragraph [0008], FIG. 1, etc.)
- JP 2002-299041 A (refer to claim 1, paragraphs [0013] and [0016], FIG. 1, etc.)
- a glass with a retardation function is formed by laminating a ⁇ / 4 retardation film that gives an in-plane retardation of about 1 ⁇ 4 of a wavelength ⁇ (nm) to transmitted light on a thin film glass with a film.
- the film itself of the thin film glass with a film can be provided with a function as a ⁇ / 4 retardation film, the total number of layers can be reduced as compared with a configuration in which the ⁇ / 4 retardation film is separately bonded. Since it can be reduced by one, it is advantageous for thinning and cost reduction.
- ⁇ / 4 retardation layer a layer having a function as a ⁇ / 4 retardation film (hereinafter referred to as ⁇ / 4 retardation layer) is adhered to the thin film glass with a conventional adhesive (acrylic adhesive or epoxy resin).
- a conventional adhesive acrylic adhesive or epoxy resin
- the above glass with retardation function can be applied to, for example, a sealing glass of an organic EL display device, but the ⁇ / 4 retardation layer is positioned on the organic EL element side with respect to the thin film glass. If a glass with a retardation function is placed on the surface, the heat generated in the organic EL element during use (heat of the light emitting layer) is confined to the inner side (on the organic EL element side) than the thin film glass. The dimensional change (resin expansion and contraction) of the four retardation layers is likely to occur, and uneven retardation is likely to occur.
- the glass with retardation function when the glass with retardation function is applied to the organic EL display device, the glass with retardation function is arranged so that the ⁇ / 4 retardation layer is located on the opposite side of the organic EL element with respect to the thin film glass. It is desirable to be in a usage form. However, in this case, since the ⁇ / 4 retardation layer is located outside the thin film glass, when the wet heat durability test is performed, the dimension of the ⁇ / 4 retardation layer is affected by environmental changes such as temperature change and humidity change. Changes are likely to occur and phase difference unevenness is likely to occur.
- the above-mentioned glass with retardation function can be applied to, for example, a glass substrate of a liquid crystal cell of a liquid crystal display device.
- a glass substrate of a liquid crystal cell of a liquid crystal display device since the ⁇ / 4 retardation layer is affected by environmental fluctuations during the durability test, the same problem as described above may occur.
- the object of the present invention is to provide a ⁇ / 4 retardation layer that has a structure in which a ⁇ / 4 retardation layer is laminated on a thin film glass via an adhesive.
- An object of the present invention is to provide a glass with a retardation function capable of suppressing dimensional changes and suppressing retardation unevenness, and an organic EL display device and a liquid crystal display device including the glass.
- a thin film glass and a ⁇ / 4 retardation layer are laminated via an adhesive layer,
- the adhesive layer contains a condensate of a reactive metal compound and a hydroxyl group-containing polymer compound.
- An organic EL display device comprising the glass with a retardation function according to any one of 1 to 7 on an organic EL element.
- a liquid crystal display device having a liquid crystal layer sandwiched between two substrates, 8.
- the metal component contained in the reactive metal compound can be covalently bonded to the glass component.
- the hydroxyl group-containing polymer compound contains a hydroxyl group and has high affinity with the resin.
- the adhesive layer that adheres the thin film glass and the ⁇ / 4 retardation layer is a condensate of the reactive metal compound and the hydroxyl group-containing polymer compound.
- the numerical value range includes the values of the lower limit A and the upper limit B.
- FIG. 1 is a cross-sectional view showing a schematic configuration of an organic EL display device 1 of the present embodiment.
- the organic EL display device 1 is configured by laminating an organic EL element 2, a glass 3 with a retardation function, and a polarizing plate 4 in this order.
- the organic EL element 2, the glass with phase difference function 3, and the polarizing plate 4 are shown separated from each other for the purpose of clearly distinguishing them.
- the organic EL element 2 is a display called OLED (Organic light-Emitting Diode), and on a substrate 21 made of glass, polyimide, or the like, in order, for example, a metal electrode 22 made of aluminum, a light emitting layer 23, and a transparent electrode ( For example, an ITO (Indium TinTOxide) 24 is included.
- a sealing glass for protecting the surface is provided on the transparent electrode 24, but in this embodiment, the glass 3 with a retardation function to which the polarizing plate 4 is bonded is used instead of the sealing glass. It is used as.
- the glass with phase difference function 3 has a function of imparting an in-plane phase difference of about 1 ⁇ 4 of the wavelength ⁇ (nm) to transmitted light, and the detailed configuration thereof will be described later.
- the polarizing plate 4 transmits predetermined linearly polarized light, and is configured by laminating a polarizing layer 41 (polarizer) and a protective layer 42.
- the polarizing layer 41 is obtained, for example, by dyeing a polyvinyl alcohol film with a dichroic dye and stretching the film at a high magnification.
- the thickness of the polarizing layer 41 is, for example, 10 ⁇ m or less.
- the protective layer 42 is composed of, for example, a cellulose resin or a hard coat layer, and is provided for the purpose of protecting the surface of the polarizing layer 41.
- the protective layer 42 is bonded to the polarizing layer 41 via an ultraviolet curable adhesive, or is bonded to the polarizing layer 41 using a polyvinyl alcohol aqueous solution as an adhesive (water glue).
- the protective layer 42 is formed only on one side of the polarizing layer 41 to constitute the polarizing plate 4. However, as shown in FIG. 2, the polarizing layer 41 is sandwiched between the protective layers 42 and 42 from both sides.
- the polarizing plate 4 may be configured as follows.
- the glass with phase difference function 3 and the polarizing plate 4 are arranged on the outside light incident side of the organic EL element 2, these prevent the reflection of the outside light incident on the organic EL element 2.
- Functions as a polarizing plate That is, out of the external light incident on the polarizing plate 4, the light transmitted through the polarizing layer 41 (linearly polarized light) is converted to circularly polarized light by the glass 3 with a retardation function, and reflected by the metal electrode 22 of the organic EL element 2. In this case, the phase is inverted by 180 ° and reflected as a reverse circularly polarized light. The reflected light again enters the glass with phase difference function 3, is converted into linearly polarized light perpendicular to the transmission axis of the polarizing layer 41, and is completely absorbed by the polarizing layer 41.
- the glass 3 with retardation function is formed by laminating an adhesive layer 32 (first adhesive layer) and a ⁇ / 4 retardation layer 33 in this order on one surface side of the thin film glass 31. On the other surface side, an adhesive layer 34 (second adhesive layer) and a resin layer 35 are laminated in this order.
- the glass 3 with a retardation function is disposed so that the ⁇ / 4 retardation layer 33 is located on the opposite side of the organic EL element 2 with respect to the thin film glass 31, and the ⁇ / 4 retardation is obtained.
- the polarizing layer 41 is bonded to the layer 33.
- the glass with phase difference function 3 may have a configuration in which the adhesive layer 34 and the resin layer 35 are omitted. That is, as shown in FIG. 3, even if the adhesive layer 32 and the ⁇ / 4 retardation layer 33 are laminated on one surface side of the thin film glass 31, and the resin layer is not provided on the other surface side. Good.
- the adhesive layers 32 and 34 are not clearly present as layers is also included in the scope of the present invention. That is, the component contained in the adhesive layer 32 permeates into the ⁇ / 4 retardation layer 33 or the polarizing layer 41 and reacts, so that the integrated state or the component contained in the adhesive layer 34 penetrates into the resin layer 35. The integrated state by reacting is also included in the scope of the present invention.
- the ⁇ / 4 retardation layer 33 is a layer that imparts an in-plane retardation of about 1 ⁇ 4 of the wavelength to the transmitted light.
- the angle formed between the slow axis of the ⁇ / 4 retardation layer 33 and the absorption axis of the polarizing layer 41 is set to 30 to 60 °. Thereby, it becomes possible to switch the polarization state of incident light between linearly polarized light and circularly polarized light (or elliptically polarized light) by the combination of the ⁇ / 4 retardation layer 33 and the polarizing layer 41.
- the ⁇ / 4 retardation layer 33 includes a cellulose resin or a polycarbonate resin (PC). From the viewpoint of heat resistance during a durability test, the ⁇ / 4 retardation layer 33 may include a cellulose resin having heat resistance. desirable. As such a cellulose resin, for example, diacetyl cellulose (DAC) or cellulose acetate propionate (CAP) can be used.
- DAC diacetyl cellulose
- CAP cellulose acetate propionate
- the adhesive layer 32 that bonds the thin film glass 31 and the ⁇ / 4 retardation layer 33 is an organic material containing a condensate of a reactive metal compound (inorganic compound) and a hydroxyl group-containing polymer compound (organic compound). -An inorganic hybrid adhesive layer (HB glue).
- the condensate of a reactive metal compound and a hydroxyl group-containing polymer compound means that it includes a structure in which a hydroxyl group generated from the reactive metal compound and a hydroxyl group in the hydroxyl group-containing polymer compound are condensed.
- the reactive metal compound for example, silicon alkoxide such as tetraethoxysilane (TEOS) or tetramethoxysilane (TMOS) can be used.
- TEOS tetraethoxysilane
- TMOS tetramethoxysilane
- the hydroxyl group-containing polymer compound for example, diacetyl cellulose (DAC) or cellulose acetate propionate (CAP) can be used. Details of the reactive metal compound and the hydroxyl group-containing polymer compound will be described later.
- the metal component contained in the reactive metal compound is likely to be strongly bonded to the glass material component by a chemical bond such as a covalent bond.
- the hydroxyl group-containing polymer compound contains a hydroxyl group, it has high affinity with the resin and can improve adhesiveness. Therefore, by using the organic-inorganic hybrid adhesive layer 32, the adhesion between the thin film glass 31 and the ⁇ / 4 retardation layer 33 can be improved through the adhesive layer 32. Thereby, the dimensional change (resin expansion and contraction) of the ⁇ / 4 retardation layer 33 due to the environmental change (temperature change, humidity change) during the durability test can be suppressed, and the slow axis of the ⁇ / 4 retardation layer 33 can be suppressed.
- the resin layer 35 is laminated on the thin film glass 31 on the opposite side to the ⁇ / 4 retardation layer 33 with an adhesive layer 34 for the purpose of further improving the strength of the glass 3 with retardation function. That is, by providing the resin layer 35, the thin film glass 31 is sandwiched between the resin layers ( ⁇ / 4 retardation layer 33, resin layer 35) from both sides, and therefore the resin layer ( ⁇ / 4 position) only on one surface of the thin film glass 31. Compared with the configuration in which the phase difference layer 33) is provided, the strength of the entire glass 3 with a phase difference function can be further improved. As a result, the handling property of the glass 3 with a retardation function is improved, and it is difficult to break during handling.
- the light emitting layer 23 of the organic EL element 2 described above is configured to emit white light, for example, R (red), G (green), and B (blue) in order to support color display.
- Color filters are required.
- heating is required for fixing the latent pigment. Therefore, from the viewpoint of heat resistance against heating, it is desirable to use a cellulose resin having heat resistance such as triacetyl cellulose (TAC) as the resin layer 35.
- TAC triacetyl cellulose
- the resin layer 35 other than a cellulose resin is used.
- Resin for example, polycarbonate resin
- the adhesive layer 34 that bonds the thin film glass 31 and the resin layer 35 may be made of any material as long as the thin film glass 31 and the resin layer 35 can be bonded to each other, and a known acrylic pressure-sensitive adhesive (for example, PSA (Pressure Sensitive (Adhesive), pressure-sensitive adhesive) or thermosetting epoxy resin can be used.
- a known acrylic pressure-sensitive adhesive for example, PSA (Pressure Sensitive (Adhesive), pressure-sensitive adhesive) or thermosetting epoxy resin
- PSA Pressure Sensitive (Adhesive), pressure-sensitive adhesive
- thermosetting epoxy resin thermosetting epoxy resin
- the metal component contained in the reactive metal compound is likely to be firmly bonded to the glass material component, and the hydroxyl group-containing polymer compound has a high affinity with the resin, so that the thin film glass 31 and the resin layer 35 are bonded.
- an organic-inorganic hybrid adhesive layer similar to the adhesive layer 32 as the layer 34 the adhesion between the thin film glass 31 and the resin layer 35 can be improved. Thereby, it can suppress that the resin layer 35 deteriorates with the heat
- the hydroxyl group-containing polymer compound is desirably a cellulose ester (for example, DAC or CAP) having a total acyl group substitution degree of 1.0 to 2.6.
- a cellulose ester contains a hydroxyl group and improves the affinity with the ⁇ / 4 retardation layer 33 or the resin layer 35 made of a resin. Therefore, the adhesion between the thin film glass 31 and the ⁇ / 4 retardation layer 33 is improved.
- it is very effective as a material for improving the adhesion between the thin film glass 31 and the resin layer 35.
- the organic EL display device including the glass 3 with phase difference function on the organic EL element 2.
- the polarizing plate 4 is arranged on the outside light incident side, leakage of reflected light of outside light can be uniformly reduced regardless of the use environment.
- FIG. 4 is a cross-sectional view showing a schematic configuration of the liquid crystal display device 51 of the present embodiment.
- the above-described glass 3 with a retardation function can also be applied to the liquid crystal display device 51.
- the liquid crystal display device 51 includes a liquid crystal panel 52 and a backlight 53 that illuminates the liquid crystal panel 52.
- the liquid crystal panel 52 is configured by sandwiching a liquid crystal layer 63 between two substrates 61 and 62.
- the liquid crystal layer 63 is sealed between the two substrates 61 and 62 by a sealing material 64.
- a polarizing plate (not shown) is disposed in a crossed Nicols state on the outside of the substrates 61 and 62 (on the side opposite to the liquid crystal layer 63).
- the two substrates 61 and 62 are each composed of the glass 3 with a retardation function.
- the glass 3 with a retardation function has the ⁇ / 4 retardation layer 33. It arrange
- the slow axes of the ⁇ / 4 retardation layer 33 are perpendicular to each other, and the transmission axes of the two outer polarizing plates are also perpendicular to each other.
- a pixel electrode corresponding to each pixel On the liquid crystal layer 63 side of the substrate 62, a pixel electrode corresponding to each pixel, a TFT (Thin Film Transistor) that is a switching element for controlling ON / OFF of display in each pixel, and various types of devices connected to the TFT Wiring (including scanning lines and signal lines) and an alignment film for aligning liquid crystal molecules are formed.
- TFT Thin Film Transistor
- a common electrode, a color filter for performing color display, and an alignment film are formed on the liquid crystal layer 63 side of the substrate 61.
- the light (linearly polarized light) transmitted through the polarizing plate outside the substrate 62 enters the liquid crystal layer 63 through the substrate 62, and the thickness of the liquid crystal layer 63 is increased. While propagating in the direction, the polarization state changes according to the refractive index anisotropy (birefringence) of the liquid crystal.
- the polarization state changes according to the refractive index anisotropy (birefringence) of the liquid crystal.
- the light incident on the substrate 61 via the liquid crystal layer 63 only the light of the polarization component in a specific direction passes through the polarizing plate outside the substrate 61 and is emitted to the viewer side as display light. Therefore, an image can be displayed by changing the orientation of the liquid crystal molecules by changing the voltage applied to the liquid crystal layer 63 for each pixel by ON / OFF control of the TFT.
- the substrates 61 and 62 are composed of the phase difference function glass 3 (the other substrate is a ⁇ / 4 retardation layer by a conventional adhesive such as PSA). Even if the substrates 61 and 62 are made of the glass 3 with a phase difference function, the effect can be obtained to the maximum.
- the ⁇ / 4 retardation layer 33 of the glass 3 with retardation function is made of a cellulose resin having heat resistance such as TAC. It is desirable that This is because when a color filter is formed on the substrate 61 (the glass 3 with retardation function) by using an inkjet method using a latent pigment, heat resistance against heating at the time of fixing the latent pigment is required.
- the ⁇ / 4 phase difference of the phase difference function glass 3 used as the substrate 61 is used. Since the layer 33 does not need heat resistance when forming the color filter, the ⁇ / 4 retardation layer 33 can be made of a resin other than the cellulose resin.
- the phase difference function glass 3 of this embodiment includes TN (Twisted Nematic), IPS (In-Plane Switching), FLC (Ferroelectric Liquid Crystal), AFLC (Anti-ferroelectric Liquid Crystal), OCB (Optically Compensatory Bend), STN. (Supper Twisted Nematic), VA (Vertical Alignment), HAN (Hybrid Aligned Nematic) can be used as a cell substrate for liquid crystal display devices in various display modes.
- the glass 3 with the retardation function (with the resin layer 35) of the present embodiment is used as the cell substrate of the IPS method.
- the phase difference in the resin layer 35 is almost zero (the visibility is improved when the phase difference is close to zero). Therefore, it is desirable that the in-plane retardation Ro of the resin layer 35 is 0 to 5 nm and the thickness direction retardation Rt is ⁇ 10 to 10 nm.
- Thin glass As thin film glass which comprises glass with a phase difference function, what was shape
- the shape of the thin film glass is not particularly limited and may be a chip cut shape, but is preferably a roll shape from the viewpoint of suitability for production on a roll-to-roll basis.
- the average thickness of the thin film glass is preferably 5 to 200 ⁇ m, and more preferably 5 to 100 ⁇ m. When the thickness is less than 5 ⁇ m, handling such as conveyance is difficult, and when the thickness exceeds 200 ⁇ m, the value of the thin film is diminished.
- the thin film glass is not particularly limited as long as it is a multi-component oxide glass.
- alkali-free glass, borosilicate glass, aluminosilicate glass and the like are particularly suitable as the thin film glass, and among them, alkali-free glass is most preferred.
- the surface of the thin film glass is preferably washed appropriately. If organic substances such as sebum and dust are attached, the adhesiveness with the adhesive layer is lowered.
- the cleaning method follows a known glass cleaning method. For example, alkali cleaning, acid cleaning, detergent cleaning, solvent cleaning, liquid jet cleaning, UV cleaning, excimer cleaning, plasma cleaning, ion cleaning, sputter cleaning, heat cleaning, dry ice jet Cleaning or the like is suitable as a cleaning method, and among them, alkali cleaning, UV cleaning, and excimer cleaning are preferable.
- surface treatment may be performed in advance on the thin film glass. For example, it is preferable that the surface treatment is performed with a silicon alkoxide such as TEOS or TMOS, or a silane coupling agent.
- the polarizing layer is an element (polarizer) that passes only light having a plane of polarization in a certain direction.
- polarizer an element that passes only light having a plane of polarization in a certain direction.
- a typical element currently used as a polarizing layer there is a polarizer using a polyvinyl alcohol-based resin, which includes a polyvinyl alcohol-based resin dyed with iodine and a dichroic dye. There is something.
- a polyvinyl alcohol aqueous solution is formed into a film, and this is uniaxially stretched and dyed as a raw fabric, or is uniaxially stretched after being dyed, and preferably subjected to a durability treatment with a boron compound. Can be used.
- a thin film polarizer can be obtained by reducing the thickness of the original film.
- a coating-type thin film polarizer obtained by stretching, dyeing, and crosslinking a laminate obtained by coating and drying a polyvinyl alcohol aqueous solution on a stretching film substrate can be used.
- a coating-type thin film polarizer can be obtained with reference to FIG.
- the stretching film substrate After transferring the polarizer produced on the stretching film substrate onto the ⁇ / 4 retardation layer, the stretching film substrate may be peeled off, or may be used as it is as a protective layer without peeling. Good.
- a coating-type thin film polarizer is preferably used because it can be made thinner than a polarizer using an original film.
- a protective layer may be separately formed on the surface of the polarizing layer opposite to the side bonded to the ⁇ / 4 retardation layer.
- the protective layer may be bonded to the polarizing layer using an adhesive such as an adhesive, water glue, or ultraviolet (UV) curable adhesive, or a surface treatment such as a hard coat (HC) on the surface of the polarizer.
- the protective layer may be formed by applying
- the thickness of the polarizing layer is preferably 2 to 10 ⁇ m. When the thickness is less than 2 ⁇ m, the glass strength is insufficient, and when the thickness exceeds 10 ⁇ m, the meaning of thinning is reduced.
- the ⁇ / 4 retardation layer refers to a film having an in-plane retardation of the film of about 1 ⁇ 4 with respect to a predetermined light wavelength (usually in the visible light region).
- the ⁇ / 4 retardation layer is a broadband ⁇ / 4 retardation film having a phase difference of approximately 1/4 of the wavelength in the visible light wavelength range in order to obtain almost perfect circularly polarized light in the visible light wavelength range. Preferably there is.
- the in-plane retardation Ro and the film thickness direction retardation Rt of the ⁇ / 4 retardation layer of the present embodiment are expressed by the following equations, respectively.
- the value of the phase difference can be calculated by measuring the birefringence at each wavelength in an environment of 23 ° C. and 55% RH using, for example, Axoscan manufactured by Axometrcs.
- nx, ny, and nz are refractive indexes at 550 nm measured in an environment of 23 ° C. and 55% RH, respectively, and nx is the maximum refractive index in the plane of the film (in the slow axis direction). Ny is the refractive index in the direction perpendicular to the slow axis in the film plane, nz is the refractive index in the thickness direction perpendicular to the film plane, and d is the film thickness (nm). ).
- the in-plane retardation Ro of the ⁇ / 4 retardation layer may be 115 to 160 nm, preferably 120 to 160 nm, more preferably 130 to 150 nm.
- Ro exceeds the range of 115 to 160 nm, the phase difference at a wavelength of 550 nm does not become a quarter wavelength, and a long circular polarizing plate is produced using such a film and applied to an organic EL display, for example.
- the reflection of indoor lighting is intense, and there is a tendency that black color cannot be expressed in a bright place.
- the retardation Rt in the film thickness direction of the ⁇ / 4 retardation layer is preferably in the range of 60 to 200 nm, more preferably in the range of 70 to 150 nm, and in the range of 70 to 100 nm. Is more preferable.
- Rt exceeds the range of 60 to 200 nm, there is a tendency that the hue when viewed obliquely on a large screen is deteriorated.
- the ⁇ / 4 retardation layer is not particularly limited as long as it is an optically transparent resin.
- acrylic resin polycarbonate resin, cycloolefin resin, polyester resin, polylactic acid resin, polyvinyl alcohol type Resins, cellulose resins, and the like can be used.
- the ⁇ / 4 retardation layer it is preferable to use a cellulose-based resin in consideration of heat resistance during a durability test.
- a resin layer is formed on the side opposite to the ⁇ / 4 retardation layer with respect to the thin film glass via an adhesive layer.
- the resin layer is not particularly limited as long as it is an optically transparent resin.
- a cellulose-based resin as the resin layer in consideration of heat resistance when forming the color filter.
- the resin layer preferably has a small in-plane direction retardation (retardation) Ro and a thickness direction retardation (retardation) Rt, and more preferably, Ro is in the range of 0 to 5 nm and Rt is ⁇ 10. It is in the range of ⁇ 10 nm.
- the above Ro and Rt can also be obtained by the following method. 1) The obtained resin layer is conditioned at 23 ° C. and 55% RH. The average refractive index of the resin layer after humidity adjustment is measured with an Abbe refractometer. 2) Ro is measured with KOBRA 21ADH (manufactured by Oji Scientific Instruments) when light having a measurement wavelength of 590 nm is incident on the resin layer after humidity adjustment from the normal direction of the resin layer. 3) Retardation value R ( ⁇ ) when light having a measurement wavelength of 590 nm is incident from the angle ⁇ (incident angle ( ⁇ )) with respect to the normal direction of the resin layer by KOBRA 21ADH (manufactured by Oji Scientific Instruments). ).
- ⁇ can be preferably 30 ° to 50 °. 4) nx, ny, and nz are calculated by KOBRA 21ADH (manufactured by Oji Scientific Instruments) from the measured Ro and R ( ⁇ ) and the above-described average refractive index and film thickness, and the measurement wavelength is 590 nm. Rt at is calculated. The retardation can be measured after tempering for about 12 hours, for example, at 23 ° C. and 55% RH.
- the resin layer prepared in advance in the form of a film may be adhered to the glass via the adhesive layer, or the adhesive layer is formed on the glass, and the resin layer is directly applied or cast. May be formed.
- Cellulosic resins used in the resin layer of the present embodiment include cellulose ethers such as methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, cyanoethyl cellulose, triacetyl cellulose (TAC), diacetyl cellulose (DAC), cellulose acetate pro Examples include cellulose esters such as pionate (CAP), cellulose acetate butyrate (CAB), cellulose acetate phthalate, cellulose acetate trimellitate, and cellulose nitrate, and cellulose esters are preferred.
- aromatic carboxylic acid esters described in paragraph numbers [0010] to [0027] of JP-A No. 2002-179701 are used, and in particular, celluloses of paragraph numbers [0028] to [0036] of JP-A No. 2002-17979. Acylate is preferably used.
- the raw material cellulose of the cellulose resin used in the resin layer of the present embodiment is not particularly limited, and examples thereof include cotton linter, wood pulp, and kenaf. Moreover, although the cellulose resin obtained from these can be used individually or in mixture of arbitrary ratios, it is preferable to use 50 mass% or more of cotton linters.
- the molecular weight of the cellulose ester is preferably 70000-200000 in terms of number average molecular weight, more preferably 100000-200000.
- the cellulose ester used in the present embodiment preferably has a weight average molecular weight of Mw, a number average molecular weight of Mn, and a Mw / Mn ratio of 1.4 to 3.0, more preferably 1.4 to 2. 3.
- the average molecular weight and molecular weight distribution of cellulose ester can be measured using high performance liquid chromatography, the number average molecular weight (Mn) and the weight average molecular weight (Mw) are calculated using this, and the ratio is calculated. be able to. Measurement conditions are as follows.
- the total acyl group substitution degree of the cellulose ester used in the resin layer of this embodiment is preferably 1.0 to 2.9, and more preferably 1.5 to 2.9.
- the total degree of acyl group substitution can be measured according to ASTM-D817-96.
- the resin film of the present embodiment includes a plasticizer that imparts processability, flexibility, and moisture resistance to the film, an ultraviolet absorber that imparts an ultraviolet absorbing function, fine particles (matting agent) that impart slipperiness to the film, You may contain the antioxidant which prevents deterioration, the retardation adjusting agent which adjusts the retardation of a film, etc.
- Plasticizer There is no particular limitation on the plasticizer used, but it has a functional group capable of interacting with the adhesive layer so as not to cause haze or bleed out or volatilization from the film. preferable.
- Examples of such functional groups include hydroxyl groups, ether groups, carbonyl groups, ester groups, carboxylic acid residues, amino groups, imino groups, amide groups, imide groups, cyano groups, nitro groups, sulfonyl groups, sulfonic acid residues, Examples thereof include a phosphonyl group and a phosphonic acid residue, and a carbonyl group, an ester group and a phosphonyl group are preferred.
- plasticizers examples include phosphate ester plasticizers, phthalate ester plasticizers, trimellitic acid ester plasticizers, pyromellitic acid plasticizers, polyhydric alcohol ester plasticizers, glycolate plasticizers. Agents, citrate plasticizers, fatty acid ester plasticizers, carboxylic acid ester plasticizers, polyester plasticizers, and the like can be preferably used. Particularly preferred are non-phosphate ester plasticizers such as polyhydric alcohol ester plasticizers, glycolate plasticizers, and polycarboxylic acid ester plasticizers.
- the polyhydric alcohol ester is composed of an ester of a dihydric or higher aliphatic polyhydric alcohol and a monocarboxylic acid, and preferably has an aromatic ring or a cycloalkyl ring in the molecule.
- the resin film preferably contains an ultraviolet absorber from the viewpoint of preventing deterioration of the liquid crystal.
- a layer having an ultraviolet absorbing function may be formed on the resin film.
- the ultraviolet absorber having an ultraviolet absorbing function those having an excellent ability to absorb ultraviolet rays having a wavelength of 370 nm or less and little absorption of visible light having a wavelength of 400 nm or more are preferably used.
- Specific examples of preferably used ultraviolet absorbers include triazine compounds, oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, nickel complex compounds, and the like. However, it is not limited to these. Further, a polymeric ultraviolet absorber described in JP-A-6-148430 is also preferably used.
- fine particles such as a matting agent can be added in order to impart slipperiness.
- the fine particles include fine particles of an inorganic compound or fine particles of an organic compound.
- inorganic compounds include fine particles such as silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, and tin oxide. In this, it is preferable that it is a compound containing a silicon atom, and especially a silicon dioxide fine particle is preferable.
- silicon dioxide fine particles include AEROSIL 200, 200V, 300, R972, R972V, R974, R202, R812, R805, OX50, and TT600 manufactured by Aerosil Co., Ltd.
- organic compounds examples include acrylic resins, silicone resins, fluorine compound resins, and urethane resins.
- Antioxidant are also referred to as deterioration inhibitors.
- the optical film When the liquid crystal display device is placed in a high humidity and high temperature state, the optical film may be deteriorated.
- Antioxidants have the role of delaying or preventing the optical film from being decomposed by, for example, the residual solvent amount of halogen in the optical film or phosphoric acid of the phosphoric acid plasticizer, so it is contained in the optical film. It is preferable to do so.
- a hindered phenol compound is preferably used, and in particular, 2,6-di-t-butyl-p-cresol, pentaerythrityl-tetrakis [3- (3,5-di- -T-butyl-4-hydroxyphenyl) propionate] and triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] are preferred.
- hydrazine-based metal deactivators such as N, N′-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine and tris (2,4-di- A phosphorus processing stabilizer such as t-butylphenyl) phosphite may be used in combination.
- Adhesive layer As the adhesive layer, a condensate of an inorganic reactive metal compound and an organic hydroxyl group-containing polymer compound is used.
- the adhesive layer by containing a metallic hydroxyl group that can be covalently bonded to the thin film glass, and an organic hydroxyl group-containing polymer compound having high compatibility and affinity with the organic component in the polarizing layer / ⁇ / 4 retardation layer.
- the thin film glass and the polarizing layer, and the thin film glass and the ⁇ / 4 retardation layer can be bonded.
- the condensation reaction may be performed by a generally known method, may be hydrolytic condensation by addition of a catalyst, or may be dehydration condensation by heating.
- the reactive polycondensable reactive metal compound that is an inorganic compound can use an acid such as hydrochloric acid, acetic acid, or citric acid as a hydrolysis catalyst, but a solid catalyst is preferably used. Further, water and another catalyst as required may be added to cause hydrolysis to accelerate the condensation reaction.
- the hydrolysis may be complete hydrolysis in which all hydrolyzable groups are hydrolyzed, but is particularly preferably partial hydrolysis in which only a part is hydrolyzed.
- the water added for hydrolysis is preferably used in the range of 0.5 to 10 mol per 1 mol of the reactive metal compound, and hydrolyzed with the solid catalyst. If the amount of water used for the hydrolysis is small, the hydrolysis of the alkoxy group becomes insufficient, resulting in a problem that only a few hydroxyl groups are generated. Preferably, the amount of water used is 0.5-4 moles per mole of reactive metal compound.
- Ion exchange water is preferable for hydrolyzing the reactive metal compound, and ion exchange water having an electric conductivity of 10 10 M ⁇ or more is preferably used. If the electrical conductivity is lower than this, the ions contained in the ion exchange resin and the hydrolyzed water will undergo ion exchange, the pH of the hydrolyzed water will fluctuate greatly, and the hydrolyzed polycondensate generated will be present with great stability. This is not preferable.
- the electric conductivity of the ion exchange water is more preferably 10 12 M ⁇ or more, and further preferably 10 15 M ⁇ or more.
- a hydrophobic hydrolytic polycondensable reactive metal compound when water is added to a hydrophobic hydrolytic polycondensable reactive metal compound, methanol, ethanol, acetonitrile, etc. are used so that the hydrolytic polycondensable reactive metal compound and water can be easily mixed. It is preferable that a hydrophilic organic solvent is also added.
- a hydroxyl group-containing polymer compound for example, a cellulose derivative
- a reactive metal compound capable of hydrolysis polycondensation are mixed, a good solvent for the cellulose derivative is preferably added so that the cellulose derivative does not precipitate. .
- a good solvent means the organic solvent which has favorable solubility with respect to a cellulose derivative.
- the solid catalyst as the hydrolysis catalyst is not particularly limited, and those listed below can be used.
- Cation exchange resin Amberlite 15, Amberlite 200C, Amberlist 15 (above, Rohm &Haas); Dowex MWC-1-H, Dowex 88, Dowex HCR-W2 (above, Dow Chemical); Levacit SPC-108, Levacit SPC-118 (manufactured by Bayer); Diaion RCP-150H (Mitsubishi Kasei); Sumikaion KC-470, Duolite C26-C, Duolite C-433, Duolite-464 (The above is manufactured by Sumitomo Chemical Co., Ltd.); Nafion-H (manufactured by DuPont) and the like.
- Anion exchange resin Amberlite IRA-400, Amberlite IRA-45 (above, manufactured by Rohm and Haas), etc.
- Inorganic solid in which a group containing a protonic acid group is bonded to the surface Such as Zr (O 3 PCH 2 CH 2 SO 3 H) 2, Th (O 3 PCH 2 CH 2 COOH) 2.
- Polyorganosiloxane containing protonic acid groups Polyorganosiloxane having a sulfonic acid group.
- Heteropoly acid Cobalt tungstic acid, phosphomolybdic acid, etc.
- Isopolyacid Niobic acid, tantalum acid, molybdic acid, etc.
- Unitary metal oxide Alumina, chromia, zirconia, CaO, MgO, etc.
- Composite metal oxide Silica-alumina, silica-magnesia, silica-zirconia, zeolites, etc.
- Clay mineral Acid clay, activated clay, montmorillonite, kaolinite, etc.
- Metal phosphate Zirconia phosphate, lanthanum phosphate, etc.
- Metal nitrate Such as LiNO 3, Mn (NO 3) 2.
- Inorganic solid in which a group containing an amino group is bonded to the surface Solids obtained by reacting aminopropyltriethoxysilane on silica gel.
- a cation exchange resin is particularly preferable.
- a suspension polymer of polystyrene or divinylbenzene as a skeleton is preferable.
- the types of ion exchange resins are classified into a gel type and a macroporous type.
- the gel type resin does not have pores, and it is difficult for a substance involved in the reaction to enter the inside of the resin, so that the active sites are not effectively used.
- the macroporous resin has large pores, and a substance involved in the reaction can easily reach the active site, and the active site is effectively used.
- the cation exchange resin used in this embodiment is a macroporous material whose pore volume is 0.1 ml / g or more as measured by a mercury injection method.
- the acidic group attached to the resin is a sulfone group, an acrylic group or the like, preferably an H + type, and more preferably a sulfone group.
- ion exchange resins that satisfy these requirements include Amberlyst 15 (manufactured by Rohm and Hers), Diaion PK-208H, PK-216H, PK-228H (manufactured by Mitsubishi Kasei), Burolite CT-175, CT -171, CT-169 (manufactured by Burolite) and the like. Of these, Burolite CT-175 (manufactured by Burolite) is particularly preferable.
- stirring is performed to hydrolyze the reactive metal compound to obtain a hydrolyzate or a condensate thereof.
- the stirring time (reaction time) ) Is preferably 3 minutes or more, particularly preferably 5 minutes or more.
- reaction temperature shall be 0 degreeC or more.
- the reaction time is too long, the molecular weight of the condensate becomes so large that haze may be increased.
- the reaction temperature is preferably 0 to 50 ° C.
- the particle size of the cation exchange resin used in the present embodiment is not particularly limited, but the average particle size is preferably in the range of 10 to 2000 ⁇ m.
- the average particle size is less than 10 ⁇ m, filterability and liquid breakage may be deteriorated during the resin separation after the treatment.
- the average particle size exceeds 2000 ⁇ m, the surface area per mass decreases, and the hydrolysis efficiency There is a problem that is low.
- the particle diameters are uniform, a chipped or cracked particle may be partially mixed.
- the ion exchange capacity of the ion exchange resin is preferably 0.1 milliequivalent / ml or more. If it is less than 0.1 milliequivalent / ml, the hydrolysis efficiency is lowered and productivity may be lowered.
- the addition amount of the ion exchange resin as a solid catalyst is preferably 0.00001 to 30% by mass, more preferably 0.001 based on the reactive metal compound capable of hydrolysis polycondensation. ⁇ 20% by weight. If the amount of the ion exchange resin is too large, the condensation proceeds preferentially, and the molecular weight of the condensate becomes too large. Moreover, when there is too little quantity of an ion exchange resin, sufficient activity required for a hydrolysis cannot be obtained, and a hydrolyzate or its condensate cannot fully be obtained.
- water and alcohol are mixed in advance, a reactive metal compound is added and mixed therein, and then the solid catalyst is added and stirred to proceed the hydrolysis. It is preferable. In addition, it is also preferable that water and alcohol are mixed in advance and the solid catalyst is added thereto, and then the reactive metal compound is further added with stirring to proceed the hydrolysis.
- metal refers to “Chemistry of the Periodic Table” by Iwanami Shoten, Kazuo Saito, p. 71.
- a metal according to 71 that is, a metal containing a semimetallic atom.
- reactive metal compounds capable of hydrolytic polycondensation used in this embodiment include metal alkoxides, metal diketonates, metal alkyl acetoacetates, metal isocyanates, and reactive metal halides.
- the metal species is an alkoxide of Si, Ti, Zr or Al, and particularly preferably an alkoxide of Si.
- Such a reactive metal compound capable of hydrolytic polycondensation has M as the central metal, q as the number of atoms, A as the non-hydrolyzed substituent, p as the number of substituents, B as the hydrolyzable substituent,
- r is the number of substituents, the reaction is ideally completed as shown in the following formula (1), and a metal oxide is obtained.
- Equation (1) A p M q B r ⁇ A p M q O r / 2
- a compound substituted with one, two, or three per atom of the metal by a non-hydrolyzed substituent may be included.
- the amount of the metal compound having a substituent that is not hydrolyzed is preferably 50 mol% or less of the metal compound to be added.
- a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group is preferable.
- an alkyl group for example, methyl group, ethyl group) Group
- cycloalkyl group eg cyclopentyl group, cyclohexyl group etc.
- aralkyl group eg benzyl group, 2-phenethyl group etc.
- aryl group eg phenyl group, naphthyl group etc.
- heterocyclic group eg furan, Thiophene, pyridine etc.
- alkoxy group eg methoxy group, ethoxy group etc.
- aryloxy group eg phenoxy group etc.
- acyl group halogen atom, cyano group, amino group, alkylthio group, glycidyl group, vinyl group
- Examples of reactive metal compounds capable of polycondensation used in this embodiment include silicon compounds such as tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, and tetra-t-butoxysilane. , Tetrakis (methoxyethoxy) silane, tetrakis (methoxypropoxy) silane, tetrachlorosilane, tetraisocyanatosilane and the like.
- silicon compounds having substituent groups that are not hydrolyzed include dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiisopropoxysilane, dimethyldibutoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldiisopropoxysilane, and diethyldiisosilane.
- titanium compounds include titanium methoxide, titanium ethoxide, titanium isopropoxide, titanium-n-butoxide, tetrachlorotitanium, titanium diisopropoxide (bis-2,4-pentanedionate), titanium diiso Propoxide (bis-2,4-ethylacetoacetate), titanium di-n-butoxide (bis-2,4-pentanedionate), titanium acetylacetonate, titanium lactate, titanium triethanolaminate, butyl titanate dimer, etc. Can be mentioned.
- Zirconium compounds include zirconium-n-propoxide, zirconium-n-butoxide, zirconium tri-n-butoxide acetylacetonate, zirconium di-n-butoxide bisacetylacetonate, zirconium acetylacetonate, zirconium acetate, etc. Is mentioned.
- Aluminum compounds include aluminum ethoxide, aluminum isopropoxide, aluminum-n-butoxide, aluminum-s-butoxide, aluminum-di-s-butoxide ethylacetylacetonate, aluminum-t-butoxide, almatrane, aluminum phenoxide. , Aluminum acetylacetonate, aluminum ethylacetylacetonate and the like.
- Examples of the other metal compound include barium isopropoxide, calcium ethoxide, copper ethoxide, magnesium ethoxide, manganese methoxide, strontium isopropoxide, tin ethoxide, zinc methoxyethoxide, trimethoxyborane, Triethoxyborane, antimony ethoxide, arsenic triethoxide, bismuth t-pentoxide, chromium isopropoxide, erbium methoxyethoxide, gallium ethoxide, indium methoxyethoxide, iron ethoxide, lanthanum isopropoxide, neodymium methoxyethoxide, praseodymium methoxy Ethoxide, samarium isopropoxide, vanadium triisobutoxide oxide, yttrium isopropoxide, tetramethoxygermane, teto Ethoxygerman
- the reactive metal compound capable of polycondensation used in this embodiment may be a compound called double metal alkoxide having two metal atoms in the molecular species.
- double metal alkoxides include aluminum copper alkoxide, aluminum titanium alkoxide, aluminum yttrium alkoxide, aluminum zirconium alkoxide, barium titanium alkoxide, barium yttrium alkoxide, barium zirconium alkoxide, indium tin alkoxide, lithium nickel alkoxide manufactured by Gerest Co., Ltd.
- the hydroxyl group-containing polymer compound only needs to contain a hydroxyl group in the molecule, and examples thereof include synthetic polymers such as polyvinyl alcohol, polysaccharides such as starch, cellulose, carboxymethyl cellulose, sodium alginate, and derivatives thereof. It is done. These hydroxyl group-containing polymer compounds can be used singly or in appropriate combination of two or more.
- Synthetic polymers include, for example, vinyl-based, polystyrene-based, polyacrylic-based, polyurethane-based, alkyd-based, melamine-based, urea-based, phenol-based, polyester-based, polyglycerol-based polymer compounds having a hydroxyl group, and multi-branched shapes.
- a high molecular compound having a hydroxyl group having can be used.
- the polymer having a hydroxyl group may be a polymer into which a monomer having a hydroxyl group is introduced. In this case, the amount of hydroxyl groups and the introduction position of the polymer can be adjusted.
- Examples of the monomer having a hydroxyl group include styrenes having a hydroxyl group such as 3-vinylphenol, hydroxymethylstyrene, 4-vinylbenzyl-4-hydroxybutyl ether, 4- (hydroxymethylsilylphenyl) styrene, and hydroxyethyl methacrylate.
- An acrylic resin having a hydroxyl group such as N- (4- (4-hydroxyphenylsulfonyl) phenoxycarbonyl) methacrylamide may be used, and a vinyl monomer is preferable. Two or more kinds of these monomers having a hydroxyl group may be mixed and used.
- Polysaccharides include starch, hydroxymethyl starch, hydroxyethyl starch, hydroxypropyl starch, glycogen, inulin, lichenin, cellulose, hemicellulose, amylopectin, heparin, heparitin sulfate, chondroitin sulfate, hyaluronic acid, keratosulfate, chitin, chitosan, agar , Carrageenan, alginic acid, fur celerane, locust bean gum, galactomannan, guar gum, syrup gum, tamarind gum, gum arabic, tragacanth gum, caraya gum, pectin, arabinogalactan, xanthan gum, gellan gum, pullulan, dextran, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxy Propyl methyl cellulose, carboxymethyl cellulose, methyl cell Over scan, ethyl cellulose, and the
- cellulose derivatives are preferably used.
- DAC diacetyl cellulose
- CAP cellulose acetate propionate
- CAB cellulose acetate butyrate
- cellulose acetate phthalate cellulose Cellulose esters such as acetate trimellitate and cellulose nitrate are preferred.
- the acyl group substitution degree is 0.5 to 2.9, and more preferably, the acyl group substitution degree is 1.0 to 2.6.
- Fine particle additive solution The fine particle dispersion was slowly added to the dissolution tank containing methylene chloride with sufficient stirring. Further, the particles were dispersed by an attritor so that the secondary particles had a predetermined particle size. This was filtered through Finemet NF manufactured by Nippon Seisen Co., Ltd. to prepare a fine particle additive solution. Methylene chloride 5 parts by weight Fine particle dispersion 5 parts by weight
- the dope solution prepared as described above is cast on a stainless steel belt support, and the solvent is evaporated on the stainless steel belt support until the amount of residual solvent in the cast (cast) film reaches 75% by mass. And then peeled off from the stainless steel belt support with a peeling tension of 130 N / m. Thereafter, the peeled film was stretched by 1% in the width direction using a tenter while applying heat at 160 ° C. The residual solvent at the start of stretching was 15% by mass.
- drying was completed while the drying zone was conveyed by a number of rolls.
- the drying temperature was 130 ° C. and the transport tension was 100 N / m.
- a roll-shaped raw film A having a dry film thickness of 102 ⁇ m was obtained.
- the roll-shaped raw film A was set in a slidable feeding device and supplied to an oblique stretching tenter device.
- the tenter was stretched in the width direction at a stretching temperature of 190 ° C. and a stretching ratio of 80%, and then contracted 0.71 times in the direction perpendicular to the stretching when the rail was bent 45 °. Thereafter, both ends of the film were trimmed, the transport direction was changed with a transport direction changing device composed of an airflow roll, and the film was wound up with a winder to obtain a roll-like ⁇ / 4 retardation film A having a width of 2000 mm.
- the film thickness of the ⁇ / 4 retardation film A was 40 ⁇ m
- the in-plane retardation Ro was 140 nm
- the thickness direction retardation Rt was 90 nm.
- Fine particle additive solution The fine particle dispersion was slowly added to the dissolution tank containing methylene chloride with sufficient stirring. Further, the particles were dispersed by an attritor so that the secondary particles had a predetermined particle size. This was filtered through Finemet NF manufactured by Nippon Seisen Co., Ltd. to prepare a fine particle additive solution. Methylene chloride 5 parts by weight Fine particle dispersion 5 parts by weight
- the sugar ester compound A and the polyester B are represented by the following structural formula.
- the dope solution prepared as described above is cast on a stainless steel belt support, and the solvent is evaporated on the stainless steel belt support until the amount of residual solvent in the cast (cast) film reaches 75% by mass. And then peeled off from the stainless steel belt support with a peeling tension of 130 N / m. Thereafter, the peeled film was stretched by 1% in the width direction using a tenter while applying heat at 160 ° C. The residual solvent at the start of stretching was 15% by mass.
- drying was completed while the drying zone was conveyed by a number of rolls.
- the drying temperature was 130 ° C. and the transport tension was 100 N / m.
- a roll-shaped raw film B having a dry film thickness of 73 ⁇ m was obtained.
- the roll-shaped raw film B was set in a slidable feeding device and supplied to an oblique stretching machine of an oblique stretching tenter device.
- the tenter was stretched in the width direction at a stretching temperature of 190 ° C. and a stretching ratio of 1.74 times, and then contracted 0.71 times in the direction perpendicular to the stretching when the rail was bent 45 °.
- both ends of the film were trimmed, the transport direction was changed with a transport direction changing device composed of an airflow roll, and the film was wound up with a slidable winding device to obtain a ⁇ / 4 retardation film B having a width of 2000 mm.
- the film thickness of the ⁇ / 4 retardation film B was 55 ⁇ m
- the in-plane retardation Ro was 140 nm
- the thickness direction retardation Rt was 90 nm.
- ⁇ / 4 retardation film C As ⁇ / 4 retardation film C, Pure Ace (registered trademark) WR, which is a polycarbonate film manufactured by Teijin Ltd., was prepared.
- Example 1 Prepare a thin glass with a thickness of 50 ⁇ m made by Nippon Electric Glass Co., Ltd., apply adhesive A on both sides, laminate ⁇ / 4 retardation film A on one side, and Konica Minolta Advanced on the other side A cellulose triacetate film (KC2UA) manufactured by Layer Co., Ltd. was laminated and heated and bonded to obtain glass with a retardation function.
- the glass with retardation function of Example 1 is referred to as glass 1 with retardation function.
- Example 2 A glass with a retardation function was obtained in the same manner as in Example 1 except that the adhesive B was used in place of the adhesive A. Let the glass with phase difference function of Example 2 be the glass 2 with phase difference function.
- Example 3 A glass with a retardation function was obtained in the same manner as in Example 1 except that the retardation film B was used instead of the retardation film A.
- the glass with retardation function of Example 3 is referred to as glass 3 with retardation function.
- Example 4 A glass with a retardation function was obtained in the same manner as in Example 1 except that the retardation film C was used instead of the retardation film A.
- the glass with retardation function of Example 4 is referred to as glass 4 with retardation function.
- Comparative Example 1 A glass with a retardation function was obtained in the same manner as in Example 1 except that an acrylic pressure-sensitive adhesive (PSA) was used instead of the adhesive A.
- PSA acrylic pressure-sensitive adhesive
- the glass with retardation function of Comparative Example 1 is referred to as glass 5 with retardation function.
- Example 2 A glass with a retardation function was obtained in the same manner as in Example 1 except that a thermosetting epoxy adhesive (Epotech 310 manufactured by Daizonichi Mori Co., Ltd.) was used instead of the adhesive A.
- the glass with retardation function of Comparative Example 2 is referred to as glass 6 with retardation function.
- Table 1 shows the results of evaluating the retardation unevenness by the wet heat durability test for the glasses 1 to 6 with retardation function produced above.
- the adhesive layers A and B correspond to the adhesives A and B described above
- the ⁇ / 4 retardation layers A to C correspond to the ⁇ / 4 retardation films A to C described above. is doing.
- the evaluation method and evaluation criteria for phase difference unevenness are as follows. Glasses 1 to 6 with retardation function were each bonded to AN100 glass manufactured by Asahi Glass Co., Ltd. with a thickness of 0.7 mm using an acrylic pressure-sensitive adhesive so that the ⁇ / 4 retardation layer was on the outside. After heat-moisture treatment at 90 ° C. for 90 hours and humidity control at 23 ° C. and 55% RH for 24 hours, it was placed between polarizing plates arranged in crossed Nicols. And the presence or absence of phase difference nonuniformity was judged by visual observation with five monitors while rotating the glass with a phase difference function between the case of viewing from the front direction and the case of viewing from the oblique direction. The evaluation result of the phase difference unevenness is practically satisfactory if it is ⁇ or more.
- the adhesive layer between the thin film glass and the ⁇ / 4 retardation layer contains a condensate of a reactive metal compound and a hydroxyl group-containing polymer compound, so that the thin film glass and the ⁇ / 4 retardation layer are This is considered to be because the adhesiveness was improved, and the dimensional change of the ⁇ / 4 retardation layer due to environmental fluctuation during the durability test was suppressed.
- the effect of suppressing retardation unevenness is higher than in Example 4 in which the ⁇ / 4 retardation layer is PC (polycarbonate).
- PC polycarbonate
- the organic EL display device and the liquid crystal display device described in the present embodiment may have the following configurations.
- the organic EL display device of this embodiment includes a polarizing plate that transmits linearly polarized light, and a circularly polarizing plate may be configured by the above-described film with retardation function and the polarizing plate.
- the liquid crystal display device of this embodiment includes a polarizing plate that transmits linearly polarized light, and a circularly polarizing plate may be configured by the above-described film with retardation function and the polarizing plate.
- the polarizing plate may be bonded to the ⁇ / 4 retardation layer of the film having a retardation function.
- the polarizing plate includes a polarizing layer that transmits linearly polarized light and a protective layer that protects one surface of the polarizing layer, and the polarizing layer may be bonded to the ⁇ / 4 retardation layer.
- the polarizing plate is configured by sandwiching a polarizing layer that transmits linearly polarized light from both sides with two protective layers, and one protective layer is a ⁇ / 4 retardation layer. It may be pasted.
- the glass with a retardation function of the present invention can be used for an organic EL display device and a liquid crystal display device.
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Abstract
A glass with phase differentiation function (3), wherein a thin-film glass (31) and a λ/4 phase difference layer (33) are laminated with an adhesive layer (32) interposed therebetween. The adhesive layer (32) contains a condensate of a reactive metal compound and a hydroxyl group-containing polymer compound.
Description
本発明は、薄膜ガラスにλ/4位相差層を設けた位相差機能付きガラスと、それを備えた有機EL(Electro-Luminescence)表示装置および液晶表示装置とに関するものである。
The present invention relates to a glass with a retardation function in which a λ / 4 retardation layer is provided on a thin film glass, and an organic EL (Electro-Luminescence) display device and a liquid crystal display device including the glass.
近年、表示装置の大型化が進む一方でモバイル化も進んでおり、薄型・軽量な表示装置が必要とされている。表示装置には、一般的にガラス基板が使用されており、このガラス基板を薄膜化することで、表示装置を薄型・軽量にすることができる。しかし、ガラス基板を薄膜化すると、ガラス基板が割れやすくなり、ハンドリング性が悪くなる。
In recent years, the size of display devices has been increasing, and mobile devices have also been increasing. Thus, thin and lightweight display devices are required. A glass substrate is generally used for the display device, and the display device can be made thin and light by thinning the glass substrate. However, when the glass substrate is thinned, the glass substrate is easily broken and the handling property is deteriorated.
そこで、特許文献1では、厚さ0.1μm~100μmのガラスフィルムに接着剤を介して樹脂フィルムを接着することで、ガラスフィルムを取り扱う際の破損低減を図っている。このように、薄膜ガラスに接着剤を介してフィルムを貼り合わせる手法は、特許文献2でも提案されている。
Therefore, in Patent Document 1, a resin film is bonded to a glass film having a thickness of 0.1 μm to 100 μm via an adhesive to reduce damage when the glass film is handled. As described above, Patent Document 2 also proposes a method of attaching a film to a thin film glass via an adhesive.
一方、特許文献3では、厚さ50μmの極薄ガラスを、接着剤の付いたPET(ポリエチレンテレフタレート)フィルムの間に挟み込み、ラミネートすることで、フィルム全体に可撓性を持たせながら強度を強めるようにしている。
On the other hand, in Patent Document 3, an ultrathin glass with a thickness of 50 μm is sandwiched and laminated between PET (polyethylene terephthalate) films with an adhesive to increase the strength while giving flexibility to the entire film. I am doing so.
なお、用いる接着剤の例としては、特許文献1ではアクリル系粘着剤が挙げられており、特許文献2では熱硬化性のエポキシ樹脂が挙げられているが、特許文献3ではその具体例は開示されていない。
In addition, as an example of the adhesive to be used, Patent Document 1 mentions an acrylic pressure-sensitive adhesive, and Patent Document 2 mentions a thermosetting epoxy resin, but Patent Document 3 discloses a specific example thereof. It has not been.
ところで、フィルム付き薄膜ガラスに、透過光に対して波長λ(nm)の1/4程度の面内位相差を付与するλ/4位相差フィルムを貼り合わせることで、位相差機能付きガラスを構成することができるが、フィルム付き薄膜ガラスのフィルム自体にλ/4位相差フィルムとしての機能を持たせることができれば、λ/4位相差フィルムを別途貼り合わせる構成に比べて、全体の層数を1つ減らすことができるため、薄型化およびコスト低減に有利となる。
By the way, a glass with a retardation function is formed by laminating a λ / 4 retardation film that gives an in-plane retardation of about ¼ of a wavelength λ (nm) to transmitted light on a thin film glass with a film. However, if the film itself of the thin film glass with a film can be provided with a function as a λ / 4 retardation film, the total number of layers can be reduced as compared with a configuration in which the λ / 4 retardation film is separately bonded. Since it can be reduced by one, it is advantageous for thinning and cost reduction.
このとき、λ/4位相差フィルムとしての機能を持つ層(以下、λ/4位相差層と称する)が、従来の接着剤(アクリル系粘着剤やエポキシ樹脂)によって薄膜ガラスに接着されていると、以下の問題が生ずる。
At this time, a layer having a function as a λ / 4 retardation film (hereinafter referred to as λ / 4 retardation layer) is adhered to the thin film glass with a conventional adhesive (acrylic adhesive or epoxy resin). The following problems arise.
すなわち、上記の位相差機能付きガラスは、例えば有機EL表示装置の封止ガラスに適用することが可能であるが、薄膜ガラスに対してλ/4位相差層が有機EL素子側に位置するように位相差機能付きガラスを配置すると、使用時に有機EL素子にて発生した熱(発光層の熱)が薄膜ガラスよりも内側(有機EL素子側)に閉じ込められるため、その熱の影響でλ/4位相差層の寸法変化(樹脂の伸縮)が起こりやすくなり、位相差ムラが発生しやすくなる。
That is, the above glass with retardation function can be applied to, for example, a sealing glass of an organic EL display device, but the λ / 4 retardation layer is positioned on the organic EL element side with respect to the thin film glass. If a glass with a retardation function is placed on the surface, the heat generated in the organic EL element during use (heat of the light emitting layer) is confined to the inner side (on the organic EL element side) than the thin film glass. The dimensional change (resin expansion and contraction) of the four retardation layers is likely to occur, and uneven retardation is likely to occur.
したがって、位相差機能付きガラスを有機EL表示装置に適用する場合は、薄膜ガラスに対してλ/4位相差層が有機EL素子とは反対側に位置するように位相差機能付きガラスを配置する使用形態であることが望ましい。しかし、この場合は、λ/4位相差層が薄膜ガラスよりも外側に位置するため、湿熱耐久試験を行ったときに、温度変化や湿度変化などの環境変動によってλ/4位相差層の寸法変化が起こりやすくなり、位相差ムラが発生しやすくなる。
Therefore, when the glass with retardation function is applied to the organic EL display device, the glass with retardation function is arranged so that the λ / 4 retardation layer is located on the opposite side of the organic EL element with respect to the thin film glass. It is desirable to be in a usage form. However, in this case, since the λ / 4 retardation layer is located outside the thin film glass, when the wet heat durability test is performed, the dimension of the λ / 4 retardation layer is affected by environmental changes such as temperature change and humidity change. Changes are likely to occur and phase difference unevenness is likely to occur.
なお、上記の位相差機能付きガラスは、例えば液晶表示装置の液晶セルのガラス基板にも適用することができるが、薄膜ガラスに対してλ/4位相差層が液晶層とは反対側に位置する場合には、λ/4位相差層は耐久試験時の環境変動の影響を受けるため、上記と同様の問題が起こり得る。
The above-mentioned glass with retardation function can be applied to, for example, a glass substrate of a liquid crystal cell of a liquid crystal display device. In this case, since the λ / 4 retardation layer is affected by environmental fluctuations during the durability test, the same problem as described above may occur.
本発明の目的は、前記の事情に鑑み、薄膜ガラス上に接着剤を介してλ/4位相差層を積層した構成であっても、耐久試験時の環境変動によるλ/4位相差層の寸法変化を抑えて位相差ムラを抑えることができる位相差機能付きガラスと、それを備えた有機EL表示装置および液晶表示装置とを提供することにある。
In view of the above-described circumstances, the object of the present invention is to provide a λ / 4 retardation layer that has a structure in which a λ / 4 retardation layer is laminated on a thin film glass via an adhesive. An object of the present invention is to provide a glass with a retardation function capable of suppressing dimensional changes and suppressing retardation unevenness, and an organic EL display device and a liquid crystal display device including the glass.
本発明の上記目的は以下の構成により達成される。
The above object of the present invention is achieved by the following configuration.
1.薄膜ガラスとλ/4位相差層とが接着層を介して積層されており、
前記接着層は、反応性金属化合物と水酸基含有高分子化合物との縮合物を含んでいることを特徴とする位相差機能付きガラス。 1. A thin film glass and a λ / 4 retardation layer are laminated via an adhesive layer,
The adhesive layer contains a condensate of a reactive metal compound and a hydroxyl group-containing polymer compound.
前記接着層は、反応性金属化合物と水酸基含有高分子化合物との縮合物を含んでいることを特徴とする位相差機能付きガラス。 1. A thin film glass and a λ / 4 retardation layer are laminated via an adhesive layer,
The adhesive layer contains a condensate of a reactive metal compound and a hydroxyl group-containing polymer compound.
2.前記λ/4位相差層は、セルロース系樹脂を含んでいることを特徴とする前記1に記載の位相差機能付きガラス。
2. 2. The glass with retardation function as described in 1 above, wherein the λ / 4 retardation layer contains a cellulose resin.
3.前記接着層を第1の接着層とすると、
前記薄膜ガラスに対して前記λ/4位相差層とは反対側に、第2の接着層を介して樹脂層が積層されていることを特徴とする前記1または2に記載の位相差機能付きガラス。 3. When the adhesive layer is a first adhesive layer,
3. The phase difference function according to 1 or 2 above, wherein a resin layer is laminated on a side opposite to the λ / 4 phase difference layer with respect to the thin film glass via a second adhesive layer. Glass.
前記薄膜ガラスに対して前記λ/4位相差層とは反対側に、第2の接着層を介して樹脂層が積層されていることを特徴とする前記1または2に記載の位相差機能付きガラス。 3. When the adhesive layer is a first adhesive layer,
3. The phase difference function according to 1 or 2 above, wherein a resin layer is laminated on a side opposite to the λ / 4 phase difference layer with respect to the thin film glass via a second adhesive layer. Glass.
4.前記樹脂層は、セルロース系樹脂からなることを特徴とする前記3に記載の位相差機能付きガラス。
4. 4. The glass with retardation function as described in 3 above, wherein the resin layer is made of a cellulose-based resin.
5.前記樹脂層の面内位相差Roが0~5nmであり、厚み方向の位相差Rtが-10~10nmであることを特徴とする前記3または4に記載の位相差機能付きガラス。
5. 5. The glass with retardation function as described in 3 or 4 above, wherein the resin layer has an in-plane retardation Ro of 0 to 5 nm and a thickness direction retardation Rt of −10 to 10 nm.
6.前記水酸基含有高分子化合物が、総アシル基置換度が1.0~2.6のセルロースエステルであることを特徴とする前記1から5のいずれかに記載の偏光機能付きガラス。
6. 6. The glass with a polarizing function according to any one of 1 to 5, wherein the hydroxyl group-containing polymer compound is a cellulose ester having a total acyl group substitution degree of 1.0 to 2.6.
7.前記反応性金属化合物が、シリコンアルコキシドを含むことを特徴とする前記1から6のいずれかに記載の位相差機能付きガラス。
7. 7. The glass with retardation function according to any one of 1 to 6, wherein the reactive metal compound contains silicon alkoxide.
8.前記1から7のいずれかに記載の位相差機能付きガラスを有機EL素子上に備えていることを特徴とする有機EL表示装置。
8. An organic EL display device comprising the glass with a retardation function according to any one of 1 to 7 on an organic EL element.
9.2つの基板で液晶層を挟持してなる液晶表示装置であって、
前記2つの基板の少なくとも一方が、前記1から7のいずれかに記載の位相差機能付きガラスで構成されていることを特徴とする液晶表示装置。 9. A liquid crystal display device having a liquid crystal layer sandwiched between two substrates,
8. A liquid crystal display device, wherein at least one of the two substrates is made of the glass with a retardation function according to any one of 1 to 7.
前記2つの基板の少なくとも一方が、前記1から7のいずれかに記載の位相差機能付きガラスで構成されていることを特徴とする液晶表示装置。 9. A liquid crystal display device having a liquid crystal layer sandwiched between two substrates,
8. A liquid crystal display device, wherein at least one of the two substrates is made of the glass with a retardation function according to any one of 1 to 7.
反応性金属化合物に含まれる金属成分は、ガラス成分と共有結合することができる。一方、水酸基含有高分子化合物は、水酸基を含んでおり、樹脂との親和性が高い。このため、薄膜ガラスとλ/4位相差層とを接着する接着層が、反応性金属化合物と水酸基含有高分子化合物との縮合物であり、反応性金属化合物の特性と水酸基含有高分子化合物の特性とを両方持つことにより、薄膜ガラスとλ/4位相差層との両方に対して良好な接着性を確保することができる。そして、上記接着層を介して、薄膜ガラスとλ/4位相差層との密着性を向上させることができる。これにより、耐久試験時の環境変動によるλ/4位相差層の寸法変化を抑えることができ、位相差ムラが発生するのを抑えることができる。また、一般的に、有機系の化合物と無機系の化合物とは相溶性に乏しいが、これらの縮合物を構成することで、単層構造で双方の特性を有する接着層を容易に実現することができる。
The metal component contained in the reactive metal compound can be covalently bonded to the glass component. On the other hand, the hydroxyl group-containing polymer compound contains a hydroxyl group and has high affinity with the resin. For this reason, the adhesive layer that adheres the thin film glass and the λ / 4 retardation layer is a condensate of the reactive metal compound and the hydroxyl group-containing polymer compound. By having both of the characteristics, good adhesion to both the thin film glass and the λ / 4 retardation layer can be ensured. And the adhesiveness of thin film glass and (lambda) / 4 phase difference layer can be improved through the said contact bonding layer. Thereby, the dimensional change of the λ / 4 retardation layer due to the environmental fluctuation during the durability test can be suppressed, and the occurrence of the retardation unevenness can be suppressed. In general, organic compounds and inorganic compounds are poorly compatible, but by forming these condensates, it is possible to easily realize an adhesive layer having both characteristics in a single layer structure. Can do.
本発明の実施の一形態について、図面に基づいて説明すれば以下の通りである。なお、本明細書において、数値範囲をA~Bと表記した場合、その数値範囲に下限Aおよび上限Bの値は含まれるものとする。
An embodiment of the present invention will be described below with reference to the drawings. In this specification, when the numerical range is expressed as A to B, the numerical value range includes the values of the lower limit A and the upper limit B.
〔有機EL表示装置の構成〕
図1は、本実施形態の有機EL表示装置1の概略の構成を示す断面図である。有機EL表示装置1は、有機EL素子2と、位相差機能付きガラス3と、偏光板4とをこの順で積層して構成されている。なお、同図では、有機EL素子2、位相差機能付きガラス3、偏光板4を明確に区別する目的で、これらを離間して示している。 [Configuration of organic EL display device]
FIG. 1 is a cross-sectional view showing a schematic configuration of an organic EL display device 1 of the present embodiment. The organic EL display device 1 is configured by laminating anorganic EL element 2, a glass 3 with a retardation function, and a polarizing plate 4 in this order. In the figure, the organic EL element 2, the glass with phase difference function 3, and the polarizing plate 4 are shown separated from each other for the purpose of clearly distinguishing them.
図1は、本実施形態の有機EL表示装置1の概略の構成を示す断面図である。有機EL表示装置1は、有機EL素子2と、位相差機能付きガラス3と、偏光板4とをこの順で積層して構成されている。なお、同図では、有機EL素子2、位相差機能付きガラス3、偏光板4を明確に区別する目的で、これらを離間して示している。 [Configuration of organic EL display device]
FIG. 1 is a cross-sectional view showing a schematic configuration of an organic EL display device 1 of the present embodiment. The organic EL display device 1 is configured by laminating an
有機EL素子2は、OLED(Organic light-Emitting Diode)とも呼ばれる表示ディスプレイであり、ガラスやポリイミド等を用いた基板21上に、順に、例えばアルミニウムからなる金属電極22、発光層23および透明電極(例えばITO;Indium Tin Oxide)24を有して構成されている。なお、本来、透明電極24上には、表面保護のための封止ガラスが設けられるが、本実施形態では、偏光板4を貼り合わせた位相差機能付きガラス3を、この封止ガラスの代わりとして用いている。
The organic EL element 2 is a display called OLED (Organic light-Emitting Diode), and on a substrate 21 made of glass, polyimide, or the like, in order, for example, a metal electrode 22 made of aluminum, a light emitting layer 23, and a transparent electrode ( For example, an ITO (Indium TinTOxide) 24 is included. Originally, a sealing glass for protecting the surface is provided on the transparent electrode 24, but in this embodiment, the glass 3 with a retardation function to which the polarizing plate 4 is bonded is used instead of the sealing glass. It is used as.
金属電極22と透明電極24とに電圧を印加すると、発光層23に対して、金属電極22および透明電極24のうちで陰極となる電極から電子が注入され、陽極となる電極から正孔が注入され、両者が発光層23で再結合することにより、発光層23の発光特性に対応した可視光線の発光が生じる。発光層23で生じた光は、直接、または金属電極22で反射した後、透明電極24および位相差機能付きガラス3を介して外部に取り出されることになる。
When a voltage is applied to the metal electrode 22 and the transparent electrode 24, electrons are injected from the electrode serving as the cathode among the metal electrode 22 and the transparent electrode 24 into the light emitting layer 23, and holes are injected from the electrode serving as the anode. Then, when the two recombine at the light emitting layer 23, visible light emission corresponding to the light emission characteristics of the light emitting layer 23 occurs. The light generated in the light emitting layer 23 is taken out to the outside directly or after being reflected by the metal electrode 22 through the transparent electrode 24 and the glass 3 with a retardation function.
位相差機能付きガラス3は、透過光に対して波長λ(nm)の1/4程度の面内位相差を付与する機能を有しているが、その詳細な構成ついては後述する。
The glass with phase difference function 3 has a function of imparting an in-plane phase difference of about ¼ of the wavelength λ (nm) to transmitted light, and the detailed configuration thereof will be described later.
偏光板4は、所定の直線偏光を透過するものであり、偏光層41(偏光子)と保護層42とを積層して構成されている。偏光層41は、例えばポリビニルアルコールフィルムを二色性色素で染色し、高倍率延伸することで得られる。偏光層41の厚さは、例えば10μm以下である。保護層42は、例えばセルロース系樹脂やハードコート層で構成されており、偏光層41の表面を保護する目的で設けられている。保護層42は、紫外線硬化型接着剤を介して偏光層41に接着されたり、ポリビニルアルコール水溶液を接着剤(水糊)として偏光層41に貼り合わせられる。
The polarizing plate 4 transmits predetermined linearly polarized light, and is configured by laminating a polarizing layer 41 (polarizer) and a protective layer 42. The polarizing layer 41 is obtained, for example, by dyeing a polyvinyl alcohol film with a dichroic dye and stretching the film at a high magnification. The thickness of the polarizing layer 41 is, for example, 10 μm or less. The protective layer 42 is composed of, for example, a cellulose resin or a hard coat layer, and is provided for the purpose of protecting the surface of the polarizing layer 41. The protective layer 42 is bonded to the polarizing layer 41 via an ultraviolet curable adhesive, or is bonded to the polarizing layer 41 using a polyvinyl alcohol aqueous solution as an adhesive (water glue).
なお、図1では、偏光層41の片側のみに保護層42を形成して偏光板4を構成しているが、図2に示すように、偏光層41を両側から保護層42・42で挟んで偏光板4を構成してもよい。
In FIG. 1, the protective layer 42 is formed only on one side of the polarizing layer 41 to constitute the polarizing plate 4. However, as shown in FIG. 2, the polarizing layer 41 is sandwiched between the protective layers 42 and 42 from both sides. The polarizing plate 4 may be configured as follows.
上記のように、有機EL素子2の外光入射側に、位相差機能付きガラス3および偏光板4を配置することにより、これらは、有機EL素子2に入射する外光の反射を防止する円偏光板として機能する。すなわち、偏光板4に入射する外光のうち、偏光層41を透過した光(直線偏光)は、位相差機能付きガラス3によって円偏光に変換され、有機EL素子2の金属電極22で反射される際に位相が180°反転し、逆回りの円偏光として反射される。この反射光は、再び位相差機能付きガラス3に入射して、偏光層41の透過軸に垂直な直線偏光に変換され、偏光層41で全て吸収されることになる。
As described above, by arranging the glass with phase difference function 3 and the polarizing plate 4 on the outside light incident side of the organic EL element 2, these prevent the reflection of the outside light incident on the organic EL element 2. Functions as a polarizing plate. That is, out of the external light incident on the polarizing plate 4, the light transmitted through the polarizing layer 41 (linearly polarized light) is converted to circularly polarized light by the glass 3 with a retardation function, and reflected by the metal electrode 22 of the organic EL element 2. In this case, the phase is inverted by 180 ° and reflected as a reverse circularly polarized light. The reflected light again enters the glass with phase difference function 3, is converted into linearly polarized light perpendicular to the transmission axis of the polarizing layer 41, and is completely absorbed by the polarizing layer 41.
〔位相差機能付きガラスの詳細〕
次に、上記した位相差機能付きガラス3の詳細について説明する。図1に示すように、位相差機能付きガラス3は、薄膜ガラス31の一方の面側に、接着層32(第1の接着層)、λ/4位相差層33をこの順で積層し、他方の面側に、接着層34(第2の接着層)および樹脂層35をこの順で積層して構成されている。本実施形態では、位相差機能付きガラス3は、λ/4位相差層33が薄膜ガラス31に対して有機EL素子2とは反対側に位置するように配置されており、λ/4位相差層33に上記の偏光層41が貼り合わされている。なお、位相差機能付きガラス3は、上記の接着層34および樹脂層35を省略した構成であってもよい。つまり、図3に示すように、薄膜ガラス31の一方の面側に、接着層32およびλ/4位相差層33を積層し、他方の面側には樹脂層を設けない構成であってもよい。 [Details of glass with retardation function]
Next, the detail of the above-mentionedglass 3 with a phase difference function is demonstrated. As shown in FIG. 1, the glass 3 with retardation function is formed by laminating an adhesive layer 32 (first adhesive layer) and a λ / 4 retardation layer 33 in this order on one surface side of the thin film glass 31. On the other surface side, an adhesive layer 34 (second adhesive layer) and a resin layer 35 are laminated in this order. In the present embodiment, the glass 3 with a retardation function is disposed so that the λ / 4 retardation layer 33 is located on the opposite side of the organic EL element 2 with respect to the thin film glass 31, and the λ / 4 retardation is obtained. The polarizing layer 41 is bonded to the layer 33. The glass with phase difference function 3 may have a configuration in which the adhesive layer 34 and the resin layer 35 are omitted. That is, as shown in FIG. 3, even if the adhesive layer 32 and the λ / 4 retardation layer 33 are laminated on one surface side of the thin film glass 31, and the resin layer is not provided on the other surface side. Good.
次に、上記した位相差機能付きガラス3の詳細について説明する。図1に示すように、位相差機能付きガラス3は、薄膜ガラス31の一方の面側に、接着層32(第1の接着層)、λ/4位相差層33をこの順で積層し、他方の面側に、接着層34(第2の接着層)および樹脂層35をこの順で積層して構成されている。本実施形態では、位相差機能付きガラス3は、λ/4位相差層33が薄膜ガラス31に対して有機EL素子2とは反対側に位置するように配置されており、λ/4位相差層33に上記の偏光層41が貼り合わされている。なお、位相差機能付きガラス3は、上記の接着層34および樹脂層35を省略した構成であってもよい。つまり、図3に示すように、薄膜ガラス31の一方の面側に、接着層32およびλ/4位相差層33を積層し、他方の面側には樹脂層を設けない構成であってもよい。 [Details of glass with retardation function]
Next, the detail of the above-mentioned
なお、接着層32、34が明確に層として存在していない場合も本発明の範囲に含まれる。すなわち、接着層32に含まれる成分がλ/4位相差層33あるいは偏光層41へ浸透し、反応することにより、一体化した状態や、接着層34に含まれる成分が樹脂層35へ浸透し、反応することにより、一体化した状態も本発明の範囲に含まれる。
Note that the case where the adhesive layers 32 and 34 are not clearly present as layers is also included in the scope of the present invention. That is, the component contained in the adhesive layer 32 permeates into the λ / 4 retardation layer 33 or the polarizing layer 41 and reacts, so that the integrated state or the component contained in the adhesive layer 34 penetrates into the resin layer 35. The integrated state by reacting is also included in the scope of the present invention.
λ/4位相差層33は、透過光に対して波長の1/4程度の面内位相差を付与する層である。λ/4位相差層33の遅相軸と偏光層41の吸収軸とのなす角度は、30~60°に設定されている。これにより、λ/4位相差層33と偏光層41との組み合わせで、入射光の偏光状態を直線偏光と円偏光(または楕円偏光)との間で切り替えることが可能となる。
The λ / 4 retardation layer 33 is a layer that imparts an in-plane retardation of about ¼ of the wavelength to the transmitted light. The angle formed between the slow axis of the λ / 4 retardation layer 33 and the absorption axis of the polarizing layer 41 is set to 30 to 60 °. Thereby, it becomes possible to switch the polarization state of incident light between linearly polarized light and circularly polarized light (or elliptically polarized light) by the combination of the λ / 4 retardation layer 33 and the polarizing layer 41.
なお、偏光層41がλ/4位相差層33に直接貼り合わされていることにより、環境変動(例えば温度変化)による影響は、偏光層41もλ/4位相差層33も同じように受ける。このため、環境変動によって、λ/4位相差層33の遅相軸の方向と、偏光層41の吸収軸の方向とがずれる、いわゆる軸ズレが生じることはほとんどない。
Note that, since the polarizing layer 41 is directly bonded to the λ / 4 retardation layer 33, the influence of environmental fluctuations (for example, temperature change) is similarly received by the polarizing layer 41 and the λ / 4 retardation layer 33. For this reason, there is almost no so-called axial deviation in which the direction of the slow axis of the λ / 4 retardation layer 33 and the direction of the absorption axis of the polarizing layer 41 are shifted due to environmental fluctuations.
λ/4位相差層33は、セルロース系樹脂やポリカーボネート樹脂(PC)を含んで構成されるが、耐久試験時の耐熱性の観点からは、耐熱性を有するセルロース系樹脂を含んでいることが望ましい。このようなセルロース系樹脂としては、例えばジアセチルセルロース(DAC)やセルロースアセテートプロピオネート(CAP)を用いることができる。
The λ / 4 retardation layer 33 includes a cellulose resin or a polycarbonate resin (PC). From the viewpoint of heat resistance during a durability test, the λ / 4 retardation layer 33 may include a cellulose resin having heat resistance. desirable. As such a cellulose resin, for example, diacetyl cellulose (DAC) or cellulose acetate propionate (CAP) can be used.
薄膜ガラス31とλ/4位相差層33とを接着する接着層32は、反応性金属化合物(無機系の化合物)と水酸基含有高分子化合物(有機系の化合物)との縮合物を含む、有機-無機ハイブリッド型の接着層(HB糊)である。反応性金属化合物と水酸基含有高分子化合物との縮合物とは、反応性金属化合物から生じた水酸基と水酸基含有高分子化合物中の水酸基とが縮合反応した構造を含むことを意味する。反応性金属化合物としては、例えばテトラエトキシシラン(TEOS)やテトラメトキシシラン(TMOS)などのシリコンアルコキシドを用いることができる。また、水酸基含有高分子化合物としては、例えばジアセチルセルロース(DAC)やセルロースアセテートプロピオネート(CAP)を用いることができる。なお、反応性金属化合物および水酸基含有高分子化合物の詳細については後述する。
The adhesive layer 32 that bonds the thin film glass 31 and the λ / 4 retardation layer 33 is an organic material containing a condensate of a reactive metal compound (inorganic compound) and a hydroxyl group-containing polymer compound (organic compound). -An inorganic hybrid adhesive layer (HB glue). The condensate of a reactive metal compound and a hydroxyl group-containing polymer compound means that it includes a structure in which a hydroxyl group generated from the reactive metal compound and a hydroxyl group in the hydroxyl group-containing polymer compound are condensed. As the reactive metal compound, for example, silicon alkoxide such as tetraethoxysilane (TEOS) or tetramethoxysilane (TMOS) can be used. As the hydroxyl group-containing polymer compound, for example, diacetyl cellulose (DAC) or cellulose acetate propionate (CAP) can be used. Details of the reactive metal compound and the hydroxyl group-containing polymer compound will be described later.
反応性金属化合物に含まれる金属成分は、共有結合などの化学結合により、ガラスの材料成分と強固に結びつきやすい。また、水酸基含有高分子化合物は水酸基を含んでいるため、樹脂との親和性が高く、接着性を向上させることができる。したがって、上記の有機-無機ハイブリッド型の接着層32を用いることにより、この接着層32を介して薄膜ガラス31とλ/4位相差層33との密着性を向上させることができる。これにより、耐久試験時の環境変動(温度変化、湿度変化)によるλ/4位相差層33の寸法変化(樹脂の伸縮)を抑えることができ、λ/4位相差層33の遅相軸の方向が所定の方向からずれるのを抑えることができる。その結果、λ/4位相差層33によって透過光に付与される位相差にムラが生じるのを抑えることができる。また、一般的に、有機系の化合物と無機系の化合物とは相溶性に乏しいが、これらの縮合物を構成することで、単層構造で双方の特性を有する接着層32を容易に実現することができる。
The metal component contained in the reactive metal compound is likely to be strongly bonded to the glass material component by a chemical bond such as a covalent bond. Moreover, since the hydroxyl group-containing polymer compound contains a hydroxyl group, it has high affinity with the resin and can improve adhesiveness. Therefore, by using the organic-inorganic hybrid adhesive layer 32, the adhesion between the thin film glass 31 and the λ / 4 retardation layer 33 can be improved through the adhesive layer 32. Thereby, the dimensional change (resin expansion and contraction) of the λ / 4 retardation layer 33 due to the environmental change (temperature change, humidity change) during the durability test can be suppressed, and the slow axis of the λ / 4 retardation layer 33 can be suppressed. It is possible to prevent the direction from deviating from a predetermined direction. As a result, the occurrence of unevenness in the phase difference imparted to the transmitted light by the λ / 4 retardation layer 33 can be suppressed. In general, an organic compound and an inorganic compound are poorly compatible, but by forming these condensates, an adhesive layer 32 having both characteristics in a single layer structure can be easily realized. be able to.
樹脂層35は、位相差機能付きガラス3の強度をさらに向上させる目的で、薄膜ガラス31に対してλ/4位相差層33とは反対側に、接着層34を介して積層されている。つまり、樹脂層35を設けることにより、薄膜ガラス31は両側から樹脂層(λ/4位相差層33、樹脂層35)で挟まれるため、薄膜ガラス31の片面にのみ樹脂層(λ/4位相差層33)を設ける構成に比べて、位相差機能付きガラス3全体の強度をさらに向上させることができる。この結果、位相差機能付きガラス3のハンドリング性が良好となり、取り扱い時に破損しにくくなる。
The resin layer 35 is laminated on the thin film glass 31 on the opposite side to the λ / 4 retardation layer 33 with an adhesive layer 34 for the purpose of further improving the strength of the glass 3 with retardation function. That is, by providing the resin layer 35, the thin film glass 31 is sandwiched between the resin layers (λ / 4 retardation layer 33, resin layer 35) from both sides, and therefore the resin layer (λ / 4 position) only on one surface of the thin film glass 31. Compared with the configuration in which the phase difference layer 33) is provided, the strength of the entire glass 3 with a phase difference function can be further improved. As a result, the handling property of the glass 3 with a retardation function is improved, and it is difficult to break during handling.
ここで、上記した有機EL素子2の発光層23が例えば白色を発光するように構成されている場合、カラー表示に対応するためには、R(赤)・G(緑)・B(青)のカラーフィルタが必要となる。この場合、例えばラテント顔料をインクとして用い、インクジェット方式によって位相差機能付きガラス3の樹脂層35側にカラーフィルタを形成する手法がある。この方式では、ラテント顔料の定着のために加熱が必要となる。そこで、この加熱に対する耐熱性の観点から、樹脂層35としては、トリアセチルセルロース(TAC)など、耐熱性を有するセルロース系樹脂を用いることが望ましい。
Here, when the light emitting layer 23 of the organic EL element 2 described above is configured to emit white light, for example, R (red), G (green), and B (blue) in order to support color display. Color filters are required. In this case, for example, there is a method of forming a color filter on the resin layer 35 side of the phase difference function glass 3 by an ink jet method using a latent pigment as ink. In this method, heating is required for fixing the latent pigment. Therefore, from the viewpoint of heat resistance against heating, it is desirable to use a cellulose resin having heat resistance such as triacetyl cellulose (TAC) as the resin layer 35.
なお、発光層23がRGBのそれぞれ光を発光するように構成されている場合、樹脂層35には上記したカラーフィルタ形成時の耐熱性は不要であるため、樹脂層35をセルロース系樹脂以外の樹脂(例えばポリカーボネート樹脂)で構成することができる。
In addition, when the light emitting layer 23 is comprised so that each light of RGB may be light-emitted, since the heat resistance at the time of the above-mentioned color filter formation is unnecessary for the resin layer 35, the resin layer 35 other than a cellulose resin is used. Resin (for example, polycarbonate resin) can be used.
薄膜ガラス31と樹脂層35とを接着する接着層34は、薄膜ガラス31と樹脂層35とを接着できるものあれば、どのような材料で構成されてもよく、公知のアクリル系の粘着剤(例えばPSA;Pressure Sensitive Adhesive 、感圧接着剤)や熱硬化性のエポキシ樹脂を用いて構成することが可能であるが、本実施形態では、接着層32と同様の有機-無機ハイブリッド型の接着層で構成されている。
The adhesive layer 34 that bonds the thin film glass 31 and the resin layer 35 may be made of any material as long as the thin film glass 31 and the resin layer 35 can be bonded to each other, and a known acrylic pressure-sensitive adhesive ( For example, PSA (Pressure Sensitive (Adhesive), pressure-sensitive adhesive) or thermosetting epoxy resin can be used. In the present embodiment, the same organic-inorganic hybrid adhesive layer as the adhesive layer 32 is used. It consists of
上記したように、反応性金属化合物に含まれる金属成分はガラスの材料成分と強固に結びつきやすく、水酸基含有高分子化合物は樹脂との親和性が高いため、薄膜ガラス31と樹脂層35との接着層34として、接着層32と同様の有機-無機ハイブリッド型の接着層を用いることにより、薄膜ガラス31と樹脂層35との密着性を向上させることができる。これにより、使用時の有機EL素子2からの熱によって樹脂層35が劣化して、その光学特性(例えば位相差(リタデーション))が変動するのを抑えることができる。
As described above, the metal component contained in the reactive metal compound is likely to be firmly bonded to the glass material component, and the hydroxyl group-containing polymer compound has a high affinity with the resin, so that the thin film glass 31 and the resin layer 35 are bonded. By using an organic-inorganic hybrid adhesive layer similar to the adhesive layer 32 as the layer 34, the adhesion between the thin film glass 31 and the resin layer 35 can be improved. Thereby, it can suppress that the resin layer 35 deteriorates with the heat | fever from the organic EL element 2 at the time of use, and the optical characteristic (for example, phase difference (retardation)) fluctuates.
また、上記の水酸基含有高分子化合物は、総アシル基置換度が1.0~2.6のセルロースエステル(例えばDACやCAP)であることが望ましい。このようなセルロースエステルは、水酸基を含有し、樹脂からなるλ/4位相差層33または樹脂層35との親和性が向上するため、薄膜ガラス31とλ/4位相差層33との接着性、または薄膜ガラス31と樹脂層35との接着性を向上させる材料として非常に有効である。
The hydroxyl group-containing polymer compound is desirably a cellulose ester (for example, DAC or CAP) having a total acyl group substitution degree of 1.0 to 2.6. Such a cellulose ester contains a hydroxyl group and improves the affinity with the λ / 4 retardation layer 33 or the resin layer 35 made of a resin. Therefore, the adhesion between the thin film glass 31 and the λ / 4 retardation layer 33 is improved. Alternatively, it is very effective as a material for improving the adhesion between the thin film glass 31 and the resin layer 35.
上記した位相差機能付きガラス3の構成によれば、耐久試験時の環境変動による位相差ムラを抑えることができるので、位相差機能付きガラス3を有機EL素子2上に備えた有機EL表示装置1においては、外光入射側に偏光板4を配置したときに、使用環境によらず外光の反射光の漏れを均一に低減することができる。
According to the configuration of the glass 3 with phase difference function described above, unevenness in the phase difference due to environmental fluctuations during the durability test can be suppressed, and thus the organic EL display device including the glass 3 with phase difference function on the organic EL element 2. In 1, when the polarizing plate 4 is arranged on the outside light incident side, leakage of reflected light of outside light can be uniformly reduced regardless of the use environment.
〔液晶表示装置の構成〕
図4は、本実施形態の液晶表示装置51の概略の構成を示す断面図である。上記した位相差機能付きガラス3は、液晶表示装置51にも適用することができる。 [Configuration of liquid crystal display device]
FIG. 4 is a cross-sectional view showing a schematic configuration of the liquidcrystal display device 51 of the present embodiment. The above-described glass 3 with a retardation function can also be applied to the liquid crystal display device 51.
図4は、本実施形態の液晶表示装置51の概略の構成を示す断面図である。上記した位相差機能付きガラス3は、液晶表示装置51にも適用することができる。 [Configuration of liquid crystal display device]
FIG. 4 is a cross-sectional view showing a schematic configuration of the liquid
液晶表示装置51は、液晶パネル52と、液晶パネル52を照明するバックライト53とを有している。液晶パネル52は、2枚の基板61・62で液晶層63を挟持して構成されている。液晶層63は、2枚の基板61・62間でシール材64によってシールされている。また、基板61・62の外側(液晶層63とは反対側)には、偏光板(図示せず)がクロスニコル状態で配置されている。
The liquid crystal display device 51 includes a liquid crystal panel 52 and a backlight 53 that illuminates the liquid crystal panel 52. The liquid crystal panel 52 is configured by sandwiching a liquid crystal layer 63 between two substrates 61 and 62. The liquid crystal layer 63 is sealed between the two substrates 61 and 62 by a sealing material 64. A polarizing plate (not shown) is disposed in a crossed Nicols state on the outside of the substrates 61 and 62 (on the side opposite to the liquid crystal layer 63).
2枚の基板61・62は、それぞれ上記の位相差機能付きガラス3で構成されている。このとき、使用時に発生する熱(例えば液晶セルの電極で発生する熱)によるλ/4位相差層33の寸法変化を抑えるため、位相差機能付きガラス3は、λ/4位相差層33が薄膜ガラス31に対して液晶層63とは反対側に位置するように配置される。また、基板61・62においては、λ/4位相差層33の遅相軸は互いに垂直となるようにし、外側の2枚の偏光板の透過軸も互いに垂直となるようにする。
The two substrates 61 and 62 are each composed of the glass 3 with a retardation function. At this time, in order to suppress the dimensional change of the λ / 4 retardation layer 33 due to heat generated at the time of use (for example, heat generated at the electrode of the liquid crystal cell), the glass 3 with a retardation function has the λ / 4 retardation layer 33. It arrange | positions so that the liquid crystal layer 63 may be located with respect to the thin film glass 31. FIG. In the substrates 61 and 62, the slow axes of the λ / 4 retardation layer 33 are perpendicular to each other, and the transmission axes of the two outer polarizing plates are also perpendicular to each other.
基板62の液晶層63側には、各画素に対応する画素電極と、各画素における表示のON/OFFを制御するためのスイッチング素子であるTFT(Thin Film Transistor)と、TFTと接続される各種配線(走査線、信号線を含む)と、液晶分子を配向させるための配向膜とが形成されている。基板61の液晶層63側には、共通電極と、カラー表示を行うためのカラーフィルタと、配向膜とが形成されている。
On the liquid crystal layer 63 side of the substrate 62, a pixel electrode corresponding to each pixel, a TFT (Thin Film Transistor) that is a switching element for controlling ON / OFF of display in each pixel, and various types of devices connected to the TFT Wiring (including scanning lines and signal lines) and an alignment film for aligning liquid crystal molecules are formed. A common electrode, a color filter for performing color display, and an alignment film are formed on the liquid crystal layer 63 side of the substrate 61.
上記の構成において、バックライト53から出射された光のうち、基板62の外側の偏光板を透過した光(直線偏光)は、基板62を介して液晶層63に入射し、液晶層63の厚み方向に伝播しながら、液晶のもつ屈折率異方性(複屈折)に応じてその偏光状態が変化する。液晶層63を介して基板61に入射した光のうち、特定方向の偏光成分の光だけが基板61の外側の偏光板を通過し、表示光として視認側に出射される。したがって、TFTのON/OFF制御により、各画素ごとに液晶層63に印加する電圧を変化させて液晶分子の配向を変化させることにより、映像を表示することができる。
In the above configuration, of the light emitted from the backlight 53, the light (linearly polarized light) transmitted through the polarizing plate outside the substrate 62 enters the liquid crystal layer 63 through the substrate 62, and the thickness of the liquid crystal layer 63 is increased. While propagating in the direction, the polarization state changes according to the refractive index anisotropy (birefringence) of the liquid crystal. Of the light incident on the substrate 61 via the liquid crystal layer 63, only the light of the polarization component in a specific direction passes through the polarizing plate outside the substrate 61 and is emitted to the viewer side as display light. Therefore, an image can be displayed by changing the orientation of the liquid crystal molecules by changing the voltage applied to the liquid crystal layer 63 for each pixel by ON / OFF control of the TFT.
また、液晶層63を挟むように、λ/4位相差層33を位置させることで、液晶のディスクリネーション部分(液晶の配向が不連続となる部位)が存在することによる輝度低下を改善することができるが、位相差機能付きガラス3を用いることで、耐久試験時の環境変動による位相差ムラの発生を抑えることができるので、環境変動に関係なく上記した輝度低下の改善を画面全体で均一に図ることができる。
In addition, by positioning the λ / 4 retardation layer 33 so as to sandwich the liquid crystal layer 63, luminance reduction due to the presence of a liquid crystal disclination portion (a portion where the liquid crystal alignment is discontinuous) is improved. However, by using the glass 3 with a phase difference function, it is possible to suppress the occurrence of phase difference unevenness due to environmental fluctuations during the durability test. Uniformity can be achieved.
なお、このような効果は、2枚の基板61・62の一方のみが位相差機能付きガラス3で構成されていても(他方の基板がPSAなどの従来の接着剤によってλ/4位相差層とガラスとを接着したものであっても)得ることができるが、両方の基板61・62を位相差機能付きガラス3で構成することで、その効果を最大限得ることができる。
In addition, even if only one of the two substrates 61 and 62 is composed of the phase difference function glass 3 (the other substrate is a λ / 4 retardation layer by a conventional adhesive such as PSA). Even if the substrates 61 and 62 are made of the glass 3 with a phase difference function, the effect can be obtained to the maximum.
上記のように位相差機能付きガラス3を液晶表示装置51に適用する場合においても、位相差機能付きガラス3のλ/4位相差層33は、TACなどの耐熱性を有するセルロース系樹脂で構成されることが望ましい。これは、ラテント顔料を用いてインクジェット方式によってカラーフィルタを基板61(位相差機能付きガラス3)上に形成する場合には、ラテント顔料の定着時の加熱に対する耐熱性が必要となるからである。
Even when the glass 3 with retardation function is applied to the liquid crystal display device 51 as described above, the λ / 4 retardation layer 33 of the glass 3 with retardation function is made of a cellulose resin having heat resistance such as TAC. It is desirable that This is because when a color filter is formed on the substrate 61 (the glass 3 with retardation function) by using an inkjet method using a latent pigment, heat resistance against heating at the time of fixing the latent pigment is required.
なお、TFTが形成される基板62側にカラーフィルタを形成した、いわゆるCOA(Color filter On Array)方式の液晶表示装置においては、基板61として用いられる位相差機能付きガラス3のλ/4位相差層33には、カラーフィルタ形成時の耐熱性は不要であるため、λ/4位相差層33をセルロース系樹脂以外の樹脂で構成することができる。
In a so-called COA (Color filter On On Array) type liquid crystal display device in which a color filter is formed on the substrate 62 side where the TFT is formed, the λ / 4 phase difference of the phase difference function glass 3 used as the substrate 61 is used. Since the layer 33 does not need heat resistance when forming the color filter, the λ / 4 retardation layer 33 can be made of a resin other than the cellulose resin.
本実施形態の位相差機能付きガラス3は、TN(Twisted Nematic)、IPS(In-Plane Switching)、FLC(Ferroelectric Liquid Crystal)、AFLC(Anti-ferroelectric Liquid Crystal)、OCB(Optically Compensatory Bend)、STN(Supper Twisted Nematic)、VA(Vertical Alignment)、HAN(Hybrid Aligned Nematic)といった様々な表示モードの液晶表示装置のセル基板として用いることができる。
The phase difference function glass 3 of this embodiment includes TN (Twisted Nematic), IPS (In-Plane Switching), FLC (Ferroelectric Liquid Crystal), AFLC (Anti-ferroelectric Liquid Crystal), OCB (Optically Compensatory Bend), STN. (Supper Twisted Nematic), VA (Vertical Alignment), HAN (Hybrid Aligned Nematic) can be used as a cell substrate for liquid crystal display devices in various display modes.
中でも、IPS方式は、TN方式やVA方式に比べて視野角性能に優れているという特徴があるため、本実施形態の位相差機能付きガラス3(樹脂層35付き)をIPS方式のセル基板として用いる場合は、樹脂層35における位相差はほとんどゼロであることが望ましい(位相差がゼロに近いほうが視認性を向上させることができる)。このことから、樹脂層35の面内位相差Roは0~5nmであり、厚み方向の位相差Rtは-10~10nmであることが望ましい。
Among them, since the IPS method has a feature that the viewing angle performance is superior to the TN method and the VA method, the glass 3 with the retardation function (with the resin layer 35) of the present embodiment is used as the cell substrate of the IPS method. When used, it is desirable that the phase difference in the resin layer 35 is almost zero (the visibility is improved when the phase difference is close to zero). Therefore, it is desirable that the in-plane retardation Ro of the resin layer 35 is 0 to 5 nm and the thickness direction retardation Rt is −10 to 10 nm.
〔各層の詳細について〕
以下、位相差機能付きガラスを構成する各層の詳細について説明する。 [Details of each layer]
Hereinafter, the detail of each layer which comprises the glass with a phase difference function is demonstrated.
以下、位相差機能付きガラスを構成する各層の詳細について説明する。 [Details of each layer]
Hereinafter, the detail of each layer which comprises the glass with a phase difference function is demonstrated.
(薄膜ガラス)
位相差機能付きガラスを構成する薄膜ガラスとしては、各種成形法によって成形されたものを使用することができる。例えばロールアウト法、リドロー法、ダウンドロー法、フロート法等によって成形された薄膜ガラスを使用できる。 (Thin glass)
As thin film glass which comprises glass with a phase difference function, what was shape | molded by various shaping | molding methods can be used. For example, a thin film glass formed by a rollout method, a redraw method, a downdraw method, a float method, or the like can be used.
位相差機能付きガラスを構成する薄膜ガラスとしては、各種成形法によって成形されたものを使用することができる。例えばロールアウト法、リドロー法、ダウンドロー法、フロート法等によって成形された薄膜ガラスを使用できる。 (Thin glass)
As thin film glass which comprises glass with a phase difference function, what was shape | molded by various shaping | molding methods can be used. For example, a thin film glass formed by a rollout method, a redraw method, a downdraw method, a float method, or the like can be used.
薄膜ガラスの形状については特に限定はなく、チップカット形状であってもよいが、ロール・トゥ・ロールでの生産の適性の観点から、ロール状であることが好ましい。
The shape of the thin film glass is not particularly limited and may be a chip cut shape, but is preferably a roll shape from the viewpoint of suitability for production on a roll-to-roll basis.
薄膜ガラスの平均厚さは、5~200μmであることが好ましく、5~100μmであることがより好ましい。厚さが5μm未満では、搬送などの取り扱いが難しく、厚さが200μmを超えると、薄膜の価値が薄れてしまう。
The average thickness of the thin film glass is preferably 5 to 200 μm, and more preferably 5 to 100 μm. When the thickness is less than 5 μm, handling such as conveyance is difficult, and when the thickness exceeds 200 μm, the value of the thin film is diminished.
薄膜ガラスは、多成分系酸化物ガラスであれば特に限定はない。例えば、無アルカリガラス、硼珪酸ガラス、アルミノシリケートガラス等が薄膜ガラスとして特に好適であり、その中でも無アルカリガラスは最も好ましい。
The thin film glass is not particularly limited as long as it is a multi-component oxide glass. For example, alkali-free glass, borosilicate glass, aluminosilicate glass and the like are particularly suitable as the thin film glass, and among them, alkali-free glass is most preferred.
薄膜ガラスの表面は、適切に洗浄されていることが好ましい。皮脂やほこりなどの有機物が付着していると、接着層との接着性が低下してしまう。洗浄方法は公知のガラス洗浄方法に従うが、例えば、アルカリ洗浄、酸洗浄、洗剤洗浄、溶媒洗浄、液体噴射洗浄、UV洗浄、エキシマー洗浄、プラズマ洗浄、イオン洗浄、スパッター洗浄、加熱洗浄、ドライアイス噴射洗浄等が洗浄方法として好適であり、その中でもアルカリ洗浄、UV洗浄、エキシマー洗浄が好ましい。また、薄膜ガラスに予め表面処理が施されていてもよい。例えば、TEOSやTMOSなどのシリコンアルコキシドや、シランカップリング剤で表面処理が施されていることが好ましい。
The surface of the thin film glass is preferably washed appropriately. If organic substances such as sebum and dust are attached, the adhesiveness with the adhesive layer is lowered. The cleaning method follows a known glass cleaning method. For example, alkali cleaning, acid cleaning, detergent cleaning, solvent cleaning, liquid jet cleaning, UV cleaning, excimer cleaning, plasma cleaning, ion cleaning, sputter cleaning, heat cleaning, dry ice jet Cleaning or the like is suitable as a cleaning method, and among them, alkali cleaning, UV cleaning, and excimer cleaning are preferable. Moreover, surface treatment may be performed in advance on the thin film glass. For example, it is preferable that the surface treatment is performed with a silicon alkoxide such as TEOS or TMOS, or a silane coupling agent.
(偏光層)
偏光層は、一定方向の偏波面の光だけを通す素子(偏光子)である。偏光層として現在用いられている代表的な素子としては、ポリビニルアルコール系樹脂を用いた偏光子があり、これには、ポリビニルアルコール系樹脂にヨウ素を染色させたものと二色性染料を染色させたものとがある。 (Polarizing layer)
The polarizing layer is an element (polarizer) that passes only light having a plane of polarization in a certain direction. As a typical element currently used as a polarizing layer, there is a polarizer using a polyvinyl alcohol-based resin, which includes a polyvinyl alcohol-based resin dyed with iodine and a dichroic dye. There is something.
偏光層は、一定方向の偏波面の光だけを通す素子(偏光子)である。偏光層として現在用いられている代表的な素子としては、ポリビニルアルコール系樹脂を用いた偏光子があり、これには、ポリビニルアルコール系樹脂にヨウ素を染色させたものと二色性染料を染色させたものとがある。 (Polarizing layer)
The polarizing layer is an element (polarizer) that passes only light having a plane of polarization in a certain direction. As a typical element currently used as a polarizing layer, there is a polarizer using a polyvinyl alcohol-based resin, which includes a polyvinyl alcohol-based resin dyed with iodine and a dichroic dye. There is something.
偏光子としては、ポリビニルアルコール水溶液をフィルム状に製膜し、これを原反として一軸延伸させて染色するか、染色した後一軸延伸してから、好ましくはホウ素化合物で耐久性処理を行ったものを用いることができる。原反の膜厚を薄くすることで、薄膜の偏光子を得ることができる。
As a polarizer, a polyvinyl alcohol aqueous solution is formed into a film, and this is uniaxially stretched and dyed as a raw fabric, or is uniaxially stretched after being dyed, and preferably subjected to a durability treatment with a boron compound. Can be used. A thin film polarizer can be obtained by reducing the thickness of the original film.
また、延伸用フィルム基材上にポリビニルアルコール水溶液を塗布・乾燥した積層体を延伸・染色・架橋することで得られた塗布型の薄膜偏光子を用いることもできる。例えば、特許第4279944号、特開2009-93074号、特許第4691205号、特許第4751481号、特許第4804588号、特許第4804589号、特許第1701555号、特開2011-248293号、の各公報などを参考にして塗布型の薄膜偏光子を得ることができる。
Also, a coating-type thin film polarizer obtained by stretching, dyeing, and crosslinking a laminate obtained by coating and drying a polyvinyl alcohol aqueous solution on a stretching film substrate can be used. For example, Japanese Patent Nos. 4279944, 2009-93074, JP 4691205, JP 4751481, JP 4804588, JP 4804589, JP 1701555, JP 2011-248293, etc. A coating-type thin film polarizer can be obtained with reference to FIG.
延伸用フィルム基材の上で作製された偏光子をλ/4位相差層上に転写後、延伸用フィルム基材を剥離してもよいし、剥離せずにそのまま保護層として活用してもよい。塗布型の薄膜偏光子は、フィルム原反を用いる偏光子よりも薄膜化が容易であるため、好ましく用いられる。
After transferring the polarizer produced on the stretching film substrate onto the λ / 4 retardation layer, the stretching film substrate may be peeled off, or may be used as it is as a protective layer without peeling. Good. A coating-type thin film polarizer is preferably used because it can be made thinner than a polarizer using an original film.
また、偏光層におけるλ/4位相差層との接着側とは反対側の面には、別途保護層を形成してもよい。保護層を粘着剤、水糊、紫外線(UV)硬化型接着剤などの接着剤を使用して偏光層に貼合してもよいし、偏光子の表面にハードコート(HC)などの表面加工を施すことで保護層を形成してもよい。
Further, a protective layer may be separately formed on the surface of the polarizing layer opposite to the side bonded to the λ / 4 retardation layer. The protective layer may be bonded to the polarizing layer using an adhesive such as an adhesive, water glue, or ultraviolet (UV) curable adhesive, or a surface treatment such as a hard coat (HC) on the surface of the polarizer. The protective layer may be formed by applying
偏光層の厚さは、2~10μmであることが好ましい。厚さが2μm未満では、ガラス強度が不足し、厚さが10μmを超えると薄型化の意味が薄れる。
The thickness of the polarizing layer is preferably 2 to 10 μm. When the thickness is less than 2 μm, the glass strength is insufficient, and when the thickness exceeds 10 μm, the meaning of thinning is reduced.
(λ/4位相差層)
λ/4位相差層は、所定の光の波長(通常、可視光領域)に対して、フィルムの面内位相差が約1/4となるフィルムをいう。λ/4位相差層は、可視光の波長の範囲においてほぼ完全な円偏光を得るため、可視光の波長の範囲において概ね波長の1/4の位相差を有する広帯域λ/4位相差フィルムであることが好ましい。 (Λ / 4 retardation layer)
The λ / 4 retardation layer refers to a film having an in-plane retardation of the film of about ¼ with respect to a predetermined light wavelength (usually in the visible light region). The λ / 4 retardation layer is a broadband λ / 4 retardation film having a phase difference of approximately 1/4 of the wavelength in the visible light wavelength range in order to obtain almost perfect circularly polarized light in the visible light wavelength range. Preferably there is.
λ/4位相差層は、所定の光の波長(通常、可視光領域)に対して、フィルムの面内位相差が約1/4となるフィルムをいう。λ/4位相差層は、可視光の波長の範囲においてほぼ完全な円偏光を得るため、可視光の波長の範囲において概ね波長の1/4の位相差を有する広帯域λ/4位相差フィルムであることが好ましい。 (Λ / 4 retardation layer)
The λ / 4 retardation layer refers to a film having an in-plane retardation of the film of about ¼ with respect to a predetermined light wavelength (usually in the visible light region). The λ / 4 retardation layer is a broadband λ / 4 retardation film having a phase difference of approximately 1/4 of the wavelength in the visible light wavelength range in order to obtain almost perfect circularly polarized light in the visible light wavelength range. Preferably there is.
本実施形態のλ/4位相差層の面内位相差Roおよび膜厚方向の位相差Rtは、それぞれ以下の式で表される。なお、位相差の値は、たとえばAxometrcs社製のAxoscanを用いて、23℃、55%RHの環境下で、各波長での複屈折率を測定することにより算出することができる。
The in-plane retardation Ro and the film thickness direction retardation Rt of the λ / 4 retardation layer of the present embodiment are expressed by the following equations, respectively. Note that the value of the phase difference can be calculated by measuring the birefringence at each wavelength in an environment of 23 ° C. and 55% RH using, for example, Axoscan manufactured by Axometrcs.
Ro=(nx-ny)×d
Rt=〔(nx+ny)/2-nz〕×d
ただし、式中、nx、ny、nzは、それぞれ23℃、55%RHの環境下で測定した、550nmにおける屈折率であり、nxはフィルムの面内の最大の屈折率(遅相軸方向の屈折率)であり、nyはフィルム面内で遅相軸に直交する方向の屈折率であり、nzはフィルム面内に垂直な厚さ方向の屈折率であり、dはフィルムの厚さ(nm)である。 Ro = (nx−ny) × d
Rt = [(nx + ny) / 2−nz] × d
In the formula, nx, ny, and nz are refractive indexes at 550 nm measured in an environment of 23 ° C. and 55% RH, respectively, and nx is the maximum refractive index in the plane of the film (in the slow axis direction). Ny is the refractive index in the direction perpendicular to the slow axis in the film plane, nz is the refractive index in the thickness direction perpendicular to the film plane, and d is the film thickness (nm). ).
Rt=〔(nx+ny)/2-nz〕×d
ただし、式中、nx、ny、nzは、それぞれ23℃、55%RHの環境下で測定した、550nmにおける屈折率であり、nxはフィルムの面内の最大の屈折率(遅相軸方向の屈折率)であり、nyはフィルム面内で遅相軸に直交する方向の屈折率であり、nzはフィルム面内に垂直な厚さ方向の屈折率であり、dはフィルムの厚さ(nm)である。 Ro = (nx−ny) × d
Rt = [(nx + ny) / 2−nz] × d
In the formula, nx, ny, and nz are refractive indexes at 550 nm measured in an environment of 23 ° C. and 55% RH, respectively, and nx is the maximum refractive index in the plane of the film (in the slow axis direction). Ny is the refractive index in the direction perpendicular to the slow axis in the film plane, nz is the refractive index in the thickness direction perpendicular to the film plane, and d is the film thickness (nm). ).
λ/4位相差層の面内位相差Roは、115~160nmであればよく、好ましくは120~160nmであり、より好ましくは130~150nmである。Roが115~160nmの範囲を超える場合、波長550nmにおける位相差が概ね1/4波長とならず、このようなフィルムを用いて長尺円偏光板を作製して例えば有機ELディスプレイに適用した場合に、室内照明の映り込みなどが激しく、明所では黒色が表現できなくなる傾向がある。
The in-plane retardation Ro of the λ / 4 retardation layer may be 115 to 160 nm, preferably 120 to 160 nm, more preferably 130 to 150 nm. When Ro exceeds the range of 115 to 160 nm, the phase difference at a wavelength of 550 nm does not become a quarter wavelength, and a long circular polarizing plate is produced using such a film and applied to an organic EL display, for example. In addition, the reflection of indoor lighting is intense, and there is a tendency that black color cannot be expressed in a bright place.
λ/4位相差層の膜厚方向の位相差Rtは、60~200nmの範囲内であることが好ましく、70~150nmの範囲内であることがより好ましく、70~100nmの範囲内であることがさらに好ましい。Rtが60~200nmの範囲を超える場合、大画面で斜めから見たときの色相が劣化してしまう傾向がある。
The retardation Rt in the film thickness direction of the λ / 4 retardation layer is preferably in the range of 60 to 200 nm, more preferably in the range of 70 to 150 nm, and in the range of 70 to 100 nm. Is more preferable. When Rt exceeds the range of 60 to 200 nm, there is a tendency that the hue when viewed obliquely on a large screen is deteriorated.
λ/4位相差層としては、光学的に透明な樹脂であれば特に限定はなく、例えば、アクリル系樹脂、ポリカーボネート系樹脂、シクロオレフィン系樹脂、ポリエステル系樹脂、ポリ乳酸系樹脂、ポリビニルアルコール系樹脂、セルロース系樹脂などを用いることができる。
The λ / 4 retardation layer is not particularly limited as long as it is an optically transparent resin. For example, acrylic resin, polycarbonate resin, cycloolefin resin, polyester resin, polylactic acid resin, polyvinyl alcohol type Resins, cellulose resins, and the like can be used.
中でも、λ/4位相差層としては、耐久試験時の耐熱性を考慮して、セルロース系樹脂を用いることが好ましい。
Among them, as the λ / 4 retardation layer, it is preferable to use a cellulose-based resin in consideration of heat resistance during a durability test.
(樹脂層)
薄膜ガラスに対してλ/4位相差層とは反対側に、接着層を介して樹脂層が形成されていることが、ガラスの強度向上の点から好ましい。樹脂層としては、光学的に透明な樹脂であれば特に限定はなく、例えば、アクリル系樹脂、ポリカーボネート系樹脂、シクロオレフィン系樹脂、ポリエステル系樹脂、ポリ乳酸系樹脂、ポリビニルアルコール系樹脂、セルロース系樹脂などを用いることができる。 (Resin layer)
From the viewpoint of improving the strength of the glass, it is preferable that a resin layer is formed on the side opposite to the λ / 4 retardation layer with respect to the thin film glass via an adhesive layer. The resin layer is not particularly limited as long as it is an optically transparent resin. For example, acrylic resin, polycarbonate resin, cycloolefin resin, polyester resin, polylactic acid resin, polyvinyl alcohol resin, and cellulose resin. Resins can be used.
薄膜ガラスに対してλ/4位相差層とは反対側に、接着層を介して樹脂層が形成されていることが、ガラスの強度向上の点から好ましい。樹脂層としては、光学的に透明な樹脂であれば特に限定はなく、例えば、アクリル系樹脂、ポリカーボネート系樹脂、シクロオレフィン系樹脂、ポリエステル系樹脂、ポリ乳酸系樹脂、ポリビニルアルコール系樹脂、セルロース系樹脂などを用いることができる。 (Resin layer)
From the viewpoint of improving the strength of the glass, it is preferable that a resin layer is formed on the side opposite to the λ / 4 retardation layer with respect to the thin film glass via an adhesive layer. The resin layer is not particularly limited as long as it is an optically transparent resin. For example, acrylic resin, polycarbonate resin, cycloolefin resin, polyester resin, polylactic acid resin, polyvinyl alcohol resin, and cellulose resin. Resins can be used.
中でも、樹脂層としては、カラーフィルタ形成時の耐熱性を考慮して、セルロース系樹脂を用いることが好ましい。
Among them, it is preferable to use a cellulose-based resin as the resin layer in consideration of heat resistance when forming the color filter.
樹脂層は、面内方向位相差(リタデーション)Roと厚み方向位相差(リタデーション)Rtが両方とも小さいことが好ましく、さらに好ましくは、Roが0~5nmの範囲であり、かつ、Rtが-10~10nmの範囲である。
The resin layer preferably has a small in-plane direction retardation (retardation) Ro and a thickness direction retardation (retardation) Rt, and more preferably, Ro is in the range of 0 to 5 nm and Rt is −10. It is in the range of ˜10 nm.
また、上記のRoおよびRtは、以下の方法によっても求めることができる。
1)得られた樹脂層を、23℃55%RHで調湿する。調湿後の樹脂層の平均屈折率を、アッベ屈折計にて測定する。
2)調湿後の樹脂層に、樹脂層法線方向から測定波長590nmの光を入射させたときのRoを、KOBRA 21ADH(王子計測機器(株)製)にて測定する。
3)KOBRA 21ADH(王子計測機器(株)製)により、樹脂層法線方向に対してθの角度(入射角(θ))から測定波長590nmの光を入射させたときのリタデーション値R(θ)を測定する。θは、好ましくは30°~50°としうる。
4)測定されたRoおよびR(θ)と、前述の平均屈折率と膜厚とから、KOBRA 21ADH(王子計測機器(株)製)により、nx、nyおよびnzを算出して、測定波長590nmでのRtを算出する。リタデーションの測定は、23℃55%RH条件下で例えば12時間程度調質処理を行った後に行うことができる。 The above Ro and Rt can also be obtained by the following method.
1) The obtained resin layer is conditioned at 23 ° C. and 55% RH. The average refractive index of the resin layer after humidity adjustment is measured with an Abbe refractometer.
2) Ro is measured with KOBRA 21ADH (manufactured by Oji Scientific Instruments) when light having a measurement wavelength of 590 nm is incident on the resin layer after humidity adjustment from the normal direction of the resin layer.
3) Retardation value R (θ) when light having a measurement wavelength of 590 nm is incident from the angle θ (incident angle (θ)) with respect to the normal direction of the resin layer by KOBRA 21ADH (manufactured by Oji Scientific Instruments). ). θ can be preferably 30 ° to 50 °.
4) nx, ny, and nz are calculated by KOBRA 21ADH (manufactured by Oji Scientific Instruments) from the measured Ro and R (θ) and the above-described average refractive index and film thickness, and the measurement wavelength is 590 nm. Rt at is calculated. The retardation can be measured after tempering for about 12 hours, for example, at 23 ° C. and 55% RH.
1)得られた樹脂層を、23℃55%RHで調湿する。調湿後の樹脂層の平均屈折率を、アッベ屈折計にて測定する。
2)調湿後の樹脂層に、樹脂層法線方向から測定波長590nmの光を入射させたときのRoを、KOBRA 21ADH(王子計測機器(株)製)にて測定する。
3)KOBRA 21ADH(王子計測機器(株)製)により、樹脂層法線方向に対してθの角度(入射角(θ))から測定波長590nmの光を入射させたときのリタデーション値R(θ)を測定する。θは、好ましくは30°~50°としうる。
4)測定されたRoおよびR(θ)と、前述の平均屈折率と膜厚とから、KOBRA 21ADH(王子計測機器(株)製)により、nx、nyおよびnzを算出して、測定波長590nmでのRtを算出する。リタデーションの測定は、23℃55%RH条件下で例えば12時間程度調質処理を行った後に行うことができる。 The above Ro and Rt can also be obtained by the following method.
1) The obtained resin layer is conditioned at 23 ° C. and 55% RH. The average refractive index of the resin layer after humidity adjustment is measured with an Abbe refractometer.
2) Ro is measured with KOBRA 21ADH (manufactured by Oji Scientific Instruments) when light having a measurement wavelength of 590 nm is incident on the resin layer after humidity adjustment from the normal direction of the resin layer.
3) Retardation value R (θ) when light having a measurement wavelength of 590 nm is incident from the angle θ (incident angle (θ)) with respect to the normal direction of the resin layer by KOBRA 21ADH (manufactured by Oji Scientific Instruments). ). θ can be preferably 30 ° to 50 °.
4) nx, ny, and nz are calculated by KOBRA 21ADH (manufactured by Oji Scientific Instruments) from the measured Ro and R (θ) and the above-described average refractive index and film thickness, and the measurement wavelength is 590 nm. Rt at is calculated. The retardation can be measured after tempering for about 12 hours, for example, at 23 ° C. and 55% RH.
樹脂層は、予めフィルム状に形成したものを準備し、接着層を介してガラスに接着してもよいし、ガラス上に接着層を形成した上に、樹脂層を直接塗布や流延することによって形成してもよい。
The resin layer prepared in advance in the form of a film may be adhered to the glass via the adhesive layer, or the adhesive layer is formed on the glass, and the resin layer is directly applied or cast. May be formed.
<セルロース系樹脂>
本実施形態の樹脂層で用いるセルロース系樹脂としては、メチルセルロース、エチルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、シアノエチルセルロースなどのセルロースエーテル類と、トリアセチルセルロース(TAC)、ジアセチルセルロース(DAC)、セルロースアセテートプロピオネート(CAP)、セルロースアセテートブチレート(CAB)、セルロースアセテートフタレート、セルロースアセテートトリメリテート、硝酸セルロース等のセルロースエステル類が挙げられるが、好ましくはセルロースエステル類である。あるいは、特開2002-179701号公報の段落番号[0010]~[0027]記載の芳香族カルボン酸エステルが用いられ、特に特開2002-17979号公報の段落番号[0028]~[0036]のセルロースアシレートが好ましく用いられる。 <Cellulosic resin>
Cellulosic resins used in the resin layer of the present embodiment include cellulose ethers such as methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, cyanoethyl cellulose, triacetyl cellulose (TAC), diacetyl cellulose (DAC), cellulose acetate pro Examples include cellulose esters such as pionate (CAP), cellulose acetate butyrate (CAB), cellulose acetate phthalate, cellulose acetate trimellitate, and cellulose nitrate, and cellulose esters are preferred. Alternatively, aromatic carboxylic acid esters described in paragraph numbers [0010] to [0027] of JP-A No. 2002-179701 are used, and in particular, celluloses of paragraph numbers [0028] to [0036] of JP-A No. 2002-17979. Acylate is preferably used.
本実施形態の樹脂層で用いるセルロース系樹脂としては、メチルセルロース、エチルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、シアノエチルセルロースなどのセルロースエーテル類と、トリアセチルセルロース(TAC)、ジアセチルセルロース(DAC)、セルロースアセテートプロピオネート(CAP)、セルロースアセテートブチレート(CAB)、セルロースアセテートフタレート、セルロースアセテートトリメリテート、硝酸セルロース等のセルロースエステル類が挙げられるが、好ましくはセルロースエステル類である。あるいは、特開2002-179701号公報の段落番号[0010]~[0027]記載の芳香族カルボン酸エステルが用いられ、特に特開2002-17979号公報の段落番号[0028]~[0036]のセルロースアシレートが好ましく用いられる。 <Cellulosic resin>
Cellulosic resins used in the resin layer of the present embodiment include cellulose ethers such as methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, cyanoethyl cellulose, triacetyl cellulose (TAC), diacetyl cellulose (DAC), cellulose acetate pro Examples include cellulose esters such as pionate (CAP), cellulose acetate butyrate (CAB), cellulose acetate phthalate, cellulose acetate trimellitate, and cellulose nitrate, and cellulose esters are preferred. Alternatively, aromatic carboxylic acid esters described in paragraph numbers [0010] to [0027] of JP-A No. 2002-179701 are used, and in particular, celluloses of paragraph numbers [0028] to [0036] of JP-A No. 2002-17979. Acylate is preferably used.
本実施形態の樹脂層で用いるセルロース系樹脂の原料のセルロースとしては、特に限定はないが、綿花リンター、木材パルプ、ケナフなどを挙げることができる。また、これらから得られたセルロース系樹脂は、それぞれを単独あるいは任意の割合で混合使用することができるが、綿花リンターを50質量%以上使用することが好ましい。
The raw material cellulose of the cellulose resin used in the resin layer of the present embodiment is not particularly limited, and examples thereof include cotton linter, wood pulp, and kenaf. Moreover, although the cellulose resin obtained from these can be used individually or in mixture of arbitrary ratios, it is preferable to use 50 mass% or more of cotton linters.
セルロースエステルの分子量が大きいと弾性率が大きくなるが、分子量を上げ過ぎるとセルロースエステルの溶解液の粘度が高くなり過ぎるため生産性が低下する。セルロースエステルの分子量は数平均分子量で70000~200000のものが好ましく、100000~200000のものが更に好ましい。本実施形態で用いるセルロースエステルは、重量平均分子量をMwとし、数平均分子量をMnとして、Mw/Mn比が1.4~3.0であることが好ましく、更に好ましくは1.4~2.3である。
When the molecular weight of the cellulose ester is large, the elastic modulus is increased. However, when the molecular weight is excessively increased, the viscosity of the solution of the cellulose ester becomes too high, and the productivity is lowered. The molecular weight of the cellulose ester is preferably 70000-200000 in terms of number average molecular weight, more preferably 100000-200000. The cellulose ester used in the present embodiment preferably has a weight average molecular weight of Mw, a number average molecular weight of Mn, and a Mw / Mn ratio of 1.4 to 3.0, more preferably 1.4 to 2. 3.
セルロースエステルの平均分子量及び分子量分布は、高速液体クロマトグラフィーを用いて測定することができるので、これを用いて数平均分子量(Mn)、重量平均分子量(Mw)を算出し、その比を計算することができる。なお、測定条件は以下の通りである。
Since the average molecular weight and molecular weight distribution of cellulose ester can be measured using high performance liquid chromatography, the number average molecular weight (Mn) and the weight average molecular weight (Mw) are calculated using this, and the ratio is calculated. be able to. Measurement conditions are as follows.
溶媒: メチレンクロライド
カラム: Shodex K806,K805,K803G(昭和電工(株)製を3本接続して使用した)
カラム温度:25℃
試料濃度: 0.1質量%
検出器: RI Model 504(GLサイエンス社製)
ポンプ: L6000(日立製作所(株)製)
流量: 1.0ml/min
校正曲線: 標準ポリスチレンSTK standard ポリスチレン(東ソー(株)製)Mw=1,000,000~500迄の13サンプルによる校正曲線を使用した。13サンプルは、ほぼ等間隔に用いることが好ましい。 Solvent: Methylene chloride Column: Shodex K806, K805, K803G (Used by connecting three Showa Denko Co., Ltd.)
Column temperature: 25 ° C
Sample concentration: 0.1% by mass
Detector: RI Model 504 (manufactured by GL Sciences)
Pump: L6000 (manufactured by Hitachi, Ltd.)
Flow rate: 1.0ml / min
Calibration curve: Standard polystyrene STK standard polystyrene (manufactured by Tosoh Co., Ltd.) Mw = 1,000,000-500 calibration curves with 13 samples were used. The 13 samples are preferably used at approximately equal intervals.
カラム: Shodex K806,K805,K803G(昭和電工(株)製を3本接続して使用した)
カラム温度:25℃
試料濃度: 0.1質量%
検出器: RI Model 504(GLサイエンス社製)
ポンプ: L6000(日立製作所(株)製)
流量: 1.0ml/min
校正曲線: 標準ポリスチレンSTK standard ポリスチレン(東ソー(株)製)Mw=1,000,000~500迄の13サンプルによる校正曲線を使用した。13サンプルは、ほぼ等間隔に用いることが好ましい。 Solvent: Methylene chloride Column: Shodex K806, K805, K803G (Used by connecting three Showa Denko Co., Ltd.)
Column temperature: 25 ° C
Sample concentration: 0.1% by mass
Detector: RI Model 504 (manufactured by GL Sciences)
Pump: L6000 (manufactured by Hitachi, Ltd.)
Flow rate: 1.0ml / min
Calibration curve: Standard polystyrene STK standard polystyrene (manufactured by Tosoh Co., Ltd.) Mw = 1,000,000-500 calibration curves with 13 samples were used. The 13 samples are preferably used at approximately equal intervals.
本実施形態の樹脂層で用いるセルロースエステルの総アシル基置換度は1.0~2.9のものが好ましく用いられ、更に好ましくは1.5~2.9である。総アシル基置換度はASTM-D817-96に準じて測定することができる。
The total acyl group substitution degree of the cellulose ester used in the resin layer of this embodiment is preferably 1.0 to 2.9, and more preferably 1.5 to 2.9. The total degree of acyl group substitution can be measured according to ASTM-D817-96.
〈添加剤〉
本実施形態の樹脂フィルムには、フィルムに加工性・柔軟性・防湿性を付与する可塑剤、紫外線吸収機能を付与する紫外線吸収剤、フィルムに滑り性を付与する微粒子(マット剤)、フィルムの劣化を防止する酸化防止剤、フィルムのリタデーションを調整するリタデーション調整剤等を含有させてもよい。 <Additive>
The resin film of the present embodiment includes a plasticizer that imparts processability, flexibility, and moisture resistance to the film, an ultraviolet absorber that imparts an ultraviolet absorbing function, fine particles (matting agent) that impart slipperiness to the film, You may contain the antioxidant which prevents deterioration, the retardation adjusting agent which adjusts the retardation of a film, etc.
本実施形態の樹脂フィルムには、フィルムに加工性・柔軟性・防湿性を付与する可塑剤、紫外線吸収機能を付与する紫外線吸収剤、フィルムに滑り性を付与する微粒子(マット剤)、フィルムの劣化を防止する酸化防止剤、フィルムのリタデーションを調整するリタデーション調整剤等を含有させてもよい。 <Additive>
The resin film of the present embodiment includes a plasticizer that imparts processability, flexibility, and moisture resistance to the film, an ultraviolet absorber that imparts an ultraviolet absorbing function, fine particles (matting agent) that impart slipperiness to the film, You may contain the antioxidant which prevents deterioration, the retardation adjusting agent which adjusts the retardation of a film, etc.
《可塑剤》
用いられる可塑剤しては特に限定はないが、フィルムにヘイズを発生させたり、フィルムからブリードアウトや揮発が生じないように、接着層と相互作用可能である官能基を有していることが好ましい。 《Plasticizer》
There is no particular limitation on the plasticizer used, but it has a functional group capable of interacting with the adhesive layer so as not to cause haze or bleed out or volatilization from the film. preferable.
用いられる可塑剤しては特に限定はないが、フィルムにヘイズを発生させたり、フィルムからブリードアウトや揮発が生じないように、接着層と相互作用可能である官能基を有していることが好ましい。 《Plasticizer》
There is no particular limitation on the plasticizer used, but it has a functional group capable of interacting with the adhesive layer so as not to cause haze or bleed out or volatilization from the film. preferable.
このような官能基としては、水酸基、エーテル基、カルボニル基、エステル基、カルボン酸残基、アミノ基、イミノ基、アミド基、イミド基、シアノ基、ニトロ基、スルホニル基、スルホン酸残基、ホスホニル基、ホスホン酸残基等が挙げられるが、好ましくはカルボニル基、エステル基、ホスホニル基である。
Examples of such functional groups include hydroxyl groups, ether groups, carbonyl groups, ester groups, carboxylic acid residues, amino groups, imino groups, amide groups, imide groups, cyano groups, nitro groups, sulfonyl groups, sulfonic acid residues, Examples thereof include a phosphonyl group and a phosphonic acid residue, and a carbonyl group, an ester group and a phosphonyl group are preferred.
このような可塑剤の例として、リン酸エステル系可塑剤、フタル酸エステル系可塑剤、トリメリット酸エステル系可塑剤、ピロメリット酸系可塑剤、多価アルコールエステル系可塑剤、グリコレート系可塑剤、クエン酸エステル系可塑剤、脂肪酸エステル系可塑剤、カルボン酸エステル系可塑剤、ポリエステル系可塑剤などを好ましく用いることができる。特に好ましくは、多価アルコールエステル系可塑剤、グリコレート系可塑剤、多価カルボン酸エステル系可塑剤等の非リン酸エステル系可塑剤である。
Examples of such plasticizers include phosphate ester plasticizers, phthalate ester plasticizers, trimellitic acid ester plasticizers, pyromellitic acid plasticizers, polyhydric alcohol ester plasticizers, glycolate plasticizers. Agents, citrate plasticizers, fatty acid ester plasticizers, carboxylic acid ester plasticizers, polyester plasticizers, and the like can be preferably used. Particularly preferred are non-phosphate ester plasticizers such as polyhydric alcohol ester plasticizers, glycolate plasticizers, and polycarboxylic acid ester plasticizers.
多価アルコールエステルは、2価以上の脂肪族多価アルコールとモノカルボン酸のエステルよりなり、分子内に芳香環またはシクロアルキル環を有することが好ましい。
The polyhydric alcohol ester is composed of an ester of a dihydric or higher aliphatic polyhydric alcohol and a monocarboxylic acid, and preferably has an aromatic ring or a cycloalkyl ring in the molecule.
《紫外線吸収剤》
樹脂フィルムには、液晶の劣化防止の観点から、紫外線吸収剤を含有させることが望ましい。なお、樹脂フィルム上に紫外線吸収機能を持つ層を形成してもよい。 <Ultraviolet absorber>
The resin film preferably contains an ultraviolet absorber from the viewpoint of preventing deterioration of the liquid crystal. A layer having an ultraviolet absorbing function may be formed on the resin film.
樹脂フィルムには、液晶の劣化防止の観点から、紫外線吸収剤を含有させることが望ましい。なお、樹脂フィルム上に紫外線吸収機能を持つ層を形成してもよい。 <Ultraviolet absorber>
The resin film preferably contains an ultraviolet absorber from the viewpoint of preventing deterioration of the liquid crystal. A layer having an ultraviolet absorbing function may be formed on the resin film.
紫外線吸収機能のある紫外線吸収剤としては、波長370nm以下の紫外線の吸収能に優れ、波長400nm以上の可視光の吸収が少ないものが好ましく用いられる。好ましく用いられる紫外線吸収剤の具体例としては、例えばトリアジン系化合物、オキシベンゾフェノン系化合物、ベンゾトリアゾール系化合物、サリチル酸エステル系化合物、ベンゾフェノン系化合物、シアノアクリレート系化合物、ニッケル錯塩系化合物などが挙げられるが、これらに限定されない。また、特開平6-148430号公報に記載の高分子紫外線吸収剤も好ましく用いられる。
As the ultraviolet absorber having an ultraviolet absorbing function, those having an excellent ability to absorb ultraviolet rays having a wavelength of 370 nm or less and little absorption of visible light having a wavelength of 400 nm or more are preferably used. Specific examples of preferably used ultraviolet absorbers include triazine compounds, oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, nickel complex compounds, and the like. However, it is not limited to these. Further, a polymeric ultraviolet absorber described in JP-A-6-148430 is also preferably used.
《マット剤》
本実施形態の樹脂フィルムには、滑り性を付与するためにマット剤等の微粒子を添加することができる。微粒子としては、無機化合物の微粒子または有機化合物の微粒子が挙げられる。 《Matting agent》
To the resin film of this embodiment, fine particles such as a matting agent can be added in order to impart slipperiness. Examples of the fine particles include fine particles of an inorganic compound or fine particles of an organic compound.
本実施形態の樹脂フィルムには、滑り性を付与するためにマット剤等の微粒子を添加することができる。微粒子としては、無機化合物の微粒子または有機化合物の微粒子が挙げられる。 《Matting agent》
To the resin film of this embodiment, fine particles such as a matting agent can be added in order to impart slipperiness. Examples of the fine particles include fine particles of an inorganic compound or fine particles of an organic compound.
無機化合物の例としては、二酸化ケイ素、二酸化チタン、酸化アルミニウム、酸化ジルコニウム、酸化錫等の微粒子が挙げられる。この中では、ケイ素原子を含有する化合物であることが好ましく、特に二酸化ケイ素微粒子が好ましい。二酸化ケイ素微粒子としては、例えばアエロジル(株)製のAEROSIL 200、200V、300、R972、R972V、R974、R202、R812、R805、OX50、TT600などが挙げられる。
Examples of inorganic compounds include fine particles such as silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, and tin oxide. In this, it is preferable that it is a compound containing a silicon atom, and especially a silicon dioxide fine particle is preferable. Examples of the silicon dioxide fine particles include AEROSIL 200, 200V, 300, R972, R972V, R974, R202, R812, R805, OX50, and TT600 manufactured by Aerosil Co., Ltd.
有機化合物の例としては、アクリル樹脂、シリコーン樹脂、フッ素化合物樹脂、ウレタン樹脂等が挙げられる。
Examples of organic compounds include acrylic resins, silicone resins, fluorine compound resins, and urethane resins.
《酸化防止剤》
酸化防止剤は、劣化防止剤ともいわれる。高湿高温の状態に液晶表示装置が置かれた場合には、光学フィルムの劣化が起こる場合がある。酸化防止剤は、例えば、光学フィルム中の残留溶媒量のハロゲンやリン酸系可塑剤のリン酸等により光学フィルムが分解するのを遅らせたり、防いだりする役割を有するので、光学フィルム中に含有させるのが好ましい。 "Antioxidant"
Antioxidants are also referred to as deterioration inhibitors. When the liquid crystal display device is placed in a high humidity and high temperature state, the optical film may be deteriorated. Antioxidants have the role of delaying or preventing the optical film from being decomposed by, for example, the residual solvent amount of halogen in the optical film or phosphoric acid of the phosphoric acid plasticizer, so it is contained in the optical film. It is preferable to do so.
酸化防止剤は、劣化防止剤ともいわれる。高湿高温の状態に液晶表示装置が置かれた場合には、光学フィルムの劣化が起こる場合がある。酸化防止剤は、例えば、光学フィルム中の残留溶媒量のハロゲンやリン酸系可塑剤のリン酸等により光学フィルムが分解するのを遅らせたり、防いだりする役割を有するので、光学フィルム中に含有させるのが好ましい。 "Antioxidant"
Antioxidants are also referred to as deterioration inhibitors. When the liquid crystal display device is placed in a high humidity and high temperature state, the optical film may be deteriorated. Antioxidants have the role of delaying or preventing the optical film from being decomposed by, for example, the residual solvent amount of halogen in the optical film or phosphoric acid of the phosphoric acid plasticizer, so it is contained in the optical film. It is preferable to do so.
このような酸化防止剤としては、ヒンダードフェノール系の化合物が好ましく用いられ、特に、2,6-ジ-t-ブチル-p-クレゾール、ペンタエリスリチル-テトラキス〔3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート〕、トリエチレングリコール-ビス〔3-(3-t-ブチル-5-メチル-4-ヒドロキシフェニル)プロピオネート〕が好ましい。また、例えば、N,N′-ビス〔3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオニル〕ヒドラジン等のヒドラジン系の金属不活性剤やトリス(2,4-ジ-t-ブチルフェニル)フォスファイト等のリン系加工安定剤を併用してもよい。
As such an antioxidant, a hindered phenol compound is preferably used, and in particular, 2,6-di-t-butyl-p-cresol, pentaerythrityl-tetrakis [3- (3,5-di- -T-butyl-4-hydroxyphenyl) propionate] and triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] are preferred. Further, for example, hydrazine-based metal deactivators such as N, N′-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine and tris (2,4-di- A phosphorus processing stabilizer such as t-butylphenyl) phosphite may be used in combination.
(接着層)
接着層としては、無機系の反応性金属化合物と有機系の水酸基含有高分子化合物との縮合物が用いられる。接着層中に、薄膜ガラスと共有結合可能な金属性水酸基と、偏光層・λ/4位相差層中の有機成分と相溶性・親和性の高い有機系水酸基含有高分子化合物を含有することで、薄膜ガラスと偏光層、薄膜ガラスとλ/4位相差層との接着が可能となる。縮合反応は、一般的に知られている方法で行えばよく、触媒添加による加水分解縮合でもよく、加熱による脱水縮合でもよい。 (Adhesive layer)
As the adhesive layer, a condensate of an inorganic reactive metal compound and an organic hydroxyl group-containing polymer compound is used. In the adhesive layer, by containing a metallic hydroxyl group that can be covalently bonded to the thin film glass, and an organic hydroxyl group-containing polymer compound having high compatibility and affinity with the organic component in the polarizing layer / λ / 4 retardation layer. The thin film glass and the polarizing layer, and the thin film glass and the λ / 4 retardation layer can be bonded. The condensation reaction may be performed by a generally known method, may be hydrolytic condensation by addition of a catalyst, or may be dehydration condensation by heating.
接着層としては、無機系の反応性金属化合物と有機系の水酸基含有高分子化合物との縮合物が用いられる。接着層中に、薄膜ガラスと共有結合可能な金属性水酸基と、偏光層・λ/4位相差層中の有機成分と相溶性・親和性の高い有機系水酸基含有高分子化合物を含有することで、薄膜ガラスと偏光層、薄膜ガラスとλ/4位相差層との接着が可能となる。縮合反応は、一般的に知られている方法で行えばよく、触媒添加による加水分解縮合でもよく、加熱による脱水縮合でもよい。 (Adhesive layer)
As the adhesive layer, a condensate of an inorganic reactive metal compound and an organic hydroxyl group-containing polymer compound is used. In the adhesive layer, by containing a metallic hydroxyl group that can be covalently bonded to the thin film glass, and an organic hydroxyl group-containing polymer compound having high compatibility and affinity with the organic component in the polarizing layer / λ / 4 retardation layer. The thin film glass and the polarizing layer, and the thin film glass and the λ / 4 retardation layer can be bonded. The condensation reaction may be performed by a generally known method, may be hydrolytic condensation by addition of a catalyst, or may be dehydration condensation by heating.
<加水分解触媒>
無機化合物である加水分解重縮合可能な反応性金属化合物は、加水分解触媒として塩酸・酢酸・クエン酸などの酸を用いることも可能であるが、固体触媒を用いることが好ましい。更に水と必要に応じて他の触媒を加えて加水分解を起こさせて縮合反応を促進してよい。加水分解は、加水分解可能な基が全て加水分解される完全加水分解であってもよいが、特に好ましくは、一部のみが加水分解される部分加水分解である。 <Hydrolysis catalyst>
The reactive polycondensable reactive metal compound that is an inorganic compound can use an acid such as hydrochloric acid, acetic acid, or citric acid as a hydrolysis catalyst, but a solid catalyst is preferably used. Further, water and another catalyst as required may be added to cause hydrolysis to accelerate the condensation reaction. The hydrolysis may be complete hydrolysis in which all hydrolyzable groups are hydrolyzed, but is particularly preferably partial hydrolysis in which only a part is hydrolyzed.
無機化合物である加水分解重縮合可能な反応性金属化合物は、加水分解触媒として塩酸・酢酸・クエン酸などの酸を用いることも可能であるが、固体触媒を用いることが好ましい。更に水と必要に応じて他の触媒を加えて加水分解を起こさせて縮合反応を促進してよい。加水分解は、加水分解可能な基が全て加水分解される完全加水分解であってもよいが、特に好ましくは、一部のみが加水分解される部分加水分解である。 <Hydrolysis catalyst>
The reactive polycondensable reactive metal compound that is an inorganic compound can use an acid such as hydrochloric acid, acetic acid, or citric acid as a hydrolysis catalyst, but a solid catalyst is preferably used. Further, water and another catalyst as required may be added to cause hydrolysis to accelerate the condensation reaction. The hydrolysis may be complete hydrolysis in which all hydrolyzable groups are hydrolyzed, but is particularly preferably partial hydrolysis in which only a part is hydrolyzed.
加水分解のために添加する水は、反応性金属化合物1モルに対し0.5~10モルの範囲で用い、前記固体触媒で加水分解することが好ましい。加水分解に使用する水の量が少ないと、アルコキシ基の加水分解が不十分となり、わずかしか水酸基が生成しないといった問題が生じる。好ましくは、使用する水の量は、反応性金属化合物1モルに対し0.5~4モルである。
The water added for hydrolysis is preferably used in the range of 0.5 to 10 mol per 1 mol of the reactive metal compound, and hydrolyzed with the solid catalyst. If the amount of water used for the hydrolysis is small, the hydrolysis of the alkoxy group becomes insufficient, resulting in a problem that only a few hydroxyl groups are generated. Preferably, the amount of water used is 0.5-4 moles per mole of reactive metal compound.
また、水としてイオン交換水を用いることも好ましい。イオン交換水は、上記反応性金属化合物の加水分解を行うために好ましく、電気伝導度が1010MΩ以上であるイオン交換水を用いることが好ましい。この電気伝導度よりも低い場合、イオン交換樹脂と加水分解水に含まれているイオンがイオン交換を起こし、加水分解水のpHが大きく変動し、せっかく生成した加水分解重縮合物が安定に存在し得ず、好ましくない。なお、イオン交換水の電気伝導度は1012MΩ以上であることがより好ましく、さらに好ましくは1015MΩ以上である。
It is also preferable to use ion exchange water as water. Ion exchange water is preferable for hydrolyzing the reactive metal compound, and ion exchange water having an electric conductivity of 10 10 MΩ or more is preferably used. If the electrical conductivity is lower than this, the ions contained in the ion exchange resin and the hydrolyzed water will undergo ion exchange, the pH of the hydrolyzed water will fluctuate greatly, and the hydrolyzed polycondensate generated will be present with great stability. This is not preferable. The electric conductivity of the ion exchange water is more preferably 10 12 MΩ or more, and further preferably 10 15 MΩ or more.
また、疎水的な加水分解重縮合可能な反応性金属化合物に水を添加する場合には、加水分解重縮合可能な反応性金属化合物と水が混和し易いように、メタノール、エタノール、アセトニトリルのような親水性の有機溶媒も添加されていることが好ましい。また、水酸基含有高分子化合物(例えばセルロース誘導体)と加水分解重縮合可能な反応性金属化合物とを混合する際に、セルロース誘導体が析出しないよう、セルロース誘導体の良溶媒も添加されていることが好ましい。なお、良溶媒とは、セルロース誘導体に対して良好な溶解性を有する有機溶媒を言う。
In addition, when water is added to a hydrophobic hydrolytic polycondensable reactive metal compound, methanol, ethanol, acetonitrile, etc. are used so that the hydrolytic polycondensable reactive metal compound and water can be easily mixed. It is preferable that a hydrophilic organic solvent is also added. In addition, when a hydroxyl group-containing polymer compound (for example, a cellulose derivative) and a reactive metal compound capable of hydrolysis polycondensation are mixed, a good solvent for the cellulose derivative is preferably added so that the cellulose derivative does not precipitate. . In addition, a good solvent means the organic solvent which has favorable solubility with respect to a cellulose derivative.
加水分解触媒としての固体触媒は、特に限定されるものではなく、以下に挙げるものを使用することができる。
The solid catalyst as the hydrolysis catalyst is not particularly limited, and those listed below can be used.
(1)陽イオン交換樹脂:
アンバーライト15、アンバーライト200C、アンバーリスト15(以上、ローム・アンド・ハース社製);ダウエックスMWC-1-H、ダウエックス88、ダウエックスHCR-W2(以上、ダウ・ケミカル社製);レバチットSPC-108、レバチットSPC-118(以上、バイエル社製);ダイヤイオンRCP-150H(三菱化成社製);スミカイオンKC-470、デュオライトC26-C、デュオライトC-433、デュオライト-464(以上、住友化学工業社製);ナフィオン-H(デュポン社製)など。 (1) Cation exchange resin:
Amberlite 15, Amberlite 200C, Amberlist 15 (above, Rohm &Haas); Dowex MWC-1-H, Dowex 88, Dowex HCR-W2 (above, Dow Chemical); Levacit SPC-108, Levacit SPC-118 (manufactured by Bayer); Diaion RCP-150H (Mitsubishi Kasei); Sumikaion KC-470, Duolite C26-C, Duolite C-433, Duolite-464 (The above is manufactured by Sumitomo Chemical Co., Ltd.); Nafion-H (manufactured by DuPont) and the like.
アンバーライト15、アンバーライト200C、アンバーリスト15(以上、ローム・アンド・ハース社製);ダウエックスMWC-1-H、ダウエックス88、ダウエックスHCR-W2(以上、ダウ・ケミカル社製);レバチットSPC-108、レバチットSPC-118(以上、バイエル社製);ダイヤイオンRCP-150H(三菱化成社製);スミカイオンKC-470、デュオライトC26-C、デュオライトC-433、デュオライト-464(以上、住友化学工業社製);ナフィオン-H(デュポン社製)など。 (1) Cation exchange resin:
Amberlite 15, Amberlite 200C, Amberlist 15 (above, Rohm &Haas); Dowex MWC-1-H, Dowex 88, Dowex HCR-W2 (above, Dow Chemical); Levacit SPC-108, Levacit SPC-118 (manufactured by Bayer); Diaion RCP-150H (Mitsubishi Kasei); Sumikaion KC-470, Duolite C26-C, Duolite C-433, Duolite-464 (The above is manufactured by Sumitomo Chemical Co., Ltd.); Nafion-H (manufactured by DuPont) and the like.
(2)陰イオン交換樹脂:
アンバーライトIRA-400、アンバーライトIRA-45(以上、ローム・アンド・ハース社製)など。 (2) Anion exchange resin:
Amberlite IRA-400, Amberlite IRA-45 (above, manufactured by Rohm and Haas), etc.
アンバーライトIRA-400、アンバーライトIRA-45(以上、ローム・アンド・ハース社製)など。 (2) Anion exchange resin:
Amberlite IRA-400, Amberlite IRA-45 (above, manufactured by Rohm and Haas), etc.
(3)プロトン酸基を含有する基が表面に結合されている無機固体:
Zr(O3PCH2CH2SO3H)2、Th(O3PCH2CH2COOH)2など。 (3) Inorganic solid in which a group containing a protonic acid group is bonded to the surface:
Such as Zr (O 3 PCH 2 CH 2 SO 3 H) 2, Th (O 3 PCH 2 CH 2 COOH) 2.
Zr(O3PCH2CH2SO3H)2、Th(O3PCH2CH2COOH)2など。 (3) Inorganic solid in which a group containing a protonic acid group is bonded to the surface:
Such as Zr (O 3 PCH 2 CH 2 SO 3 H) 2, Th (
(4)プロトン酸基を含有するポリオルガノシロキサン:
スルホン酸基を有するポリオルガノシロキサンなど。 (4) Polyorganosiloxane containing protonic acid groups:
Polyorganosiloxane having a sulfonic acid group.
スルホン酸基を有するポリオルガノシロキサンなど。 (4) Polyorganosiloxane containing protonic acid groups:
Polyorganosiloxane having a sulfonic acid group.
(5)ヘテロポリ酸:
コバルトタングステン酸、リンモリブデン酸など。 (5) Heteropoly acid:
Cobalt tungstic acid, phosphomolybdic acid, etc.
コバルトタングステン酸、リンモリブデン酸など。 (5) Heteropoly acid:
Cobalt tungstic acid, phosphomolybdic acid, etc.
(6)イソポリ酸:
ニオブ酸、タンタル酸、モリブデン酸など。 (6) Isopolyacid:
Niobic acid, tantalum acid, molybdic acid, etc.
ニオブ酸、タンタル酸、モリブデン酸など。 (6) Isopolyacid:
Niobic acid, tantalum acid, molybdic acid, etc.
(7)単元系金属酸化物:
アルミナ、クロミア、ジルコニア、CaO、MgOなど。 (7) Unitary metal oxide:
Alumina, chromia, zirconia, CaO, MgO, etc.
アルミナ、クロミア、ジルコニア、CaO、MgOなど。 (7) Unitary metal oxide:
Alumina, chromia, zirconia, CaO, MgO, etc.
(8)複合系金属酸化物:
シリカ-アルミナ、シリカ-マグネシア、シリカ-ジルコニア、ゼオライト類など。 (8) Composite metal oxide:
Silica-alumina, silica-magnesia, silica-zirconia, zeolites, etc.
シリカ-アルミナ、シリカ-マグネシア、シリカ-ジルコニア、ゼオライト類など。 (8) Composite metal oxide:
Silica-alumina, silica-magnesia, silica-zirconia, zeolites, etc.
(9)粘土鉱物:
酸性白土、活性白土、モンモリロナイト、カオリナイトなど。 (9) Clay mineral:
Acid clay, activated clay, montmorillonite, kaolinite, etc.
酸性白土、活性白土、モンモリロナイト、カオリナイトなど。 (9) Clay mineral:
Acid clay, activated clay, montmorillonite, kaolinite, etc.
(10)金属硫酸塩:
LiSO4、MgSO4など。 (10) Metal sulfate:
LiSO 4 , MgSO 4 and the like.
LiSO4、MgSO4など。 (10) Metal sulfate:
LiSO 4 , MgSO 4 and the like.
(11)金属リン酸塩:
リン酸ジルコニア、リン酸ランタンなど。 (11) Metal phosphate:
Zirconia phosphate, lanthanum phosphate, etc.
リン酸ジルコニア、リン酸ランタンなど。 (11) Metal phosphate:
Zirconia phosphate, lanthanum phosphate, etc.
(12)金属硝酸塩:
LiNO3、Mn(NO3)2など。 (12) Metal nitrate:
Such as LiNO 3, Mn (NO 3) 2.
LiNO3、Mn(NO3)2など。 (12) Metal nitrate:
Such as LiNO 3, Mn (NO 3) 2.
(13)アミノ基を含有する基が表面に結合されている無機固体:
シリカゲル上にアミノプロピルトリエトキシシランを反応させて得られた固体など。 (13) Inorganic solid in which a group containing an amino group is bonded to the surface:
Solids obtained by reacting aminopropyltriethoxysilane on silica gel.
シリカゲル上にアミノプロピルトリエトキシシランを反応させて得られた固体など。 (13) Inorganic solid in which a group containing an amino group is bonded to the surface:
Solids obtained by reacting aminopropyltriethoxysilane on silica gel.
(14)アミノ基を含有するポリオルガノシロキサン:
アミノ変性シリコーン樹脂など。 (14) Polyorganosiloxane containing amino groups:
Amino-modified silicone resin.
アミノ変性シリコーン樹脂など。 (14) Polyorganosiloxane containing amino groups:
Amino-modified silicone resin.
これらの中で、本実施形態では、特に陽イオン交換樹脂が好ましい。陽イオン交換樹脂の種類としては、まず、骨格はポリスチレン又はジビニルベンゼンの懸濁重合高分子体が好ましい。イオン交換樹脂のタイプは、ゲル型とマクロポーラス型に分かれるが、ゲル型樹脂は空孔を有さず、反応に関与する物質が樹脂内部に進入しにくく、活性点が有効に利用され難い。マクロポーラス型樹脂は大きな空孔を有しており、反応に関与する物質が容易に活性点に到達することができ、活性点が有効に利用される。このため、本実施形態で用いる陽イオン交換樹脂としては、空孔体積が水銀注入法による測定で0.1ml/g以上を示すマクロポーラスであることが好ましい。また、樹脂についている酸性基としてはスルホン基、アクリル基等で、H+型であることが好ましく、スルホン基がより好ましい。これらを満たすイオン交換樹脂の例としては、アンバーリスト15(ローム・アンド・ハーズ社製)、ダイアイオンPK-208H,PK-216H,PK-228H(以上三菱化成製)、ビュロライトCT-175,CT-171,CT-169(以上ビュロライト社製)等を例示することができる。これらの中で、特にビュロライトCT-175(ビュロライト社製)が好ましい。
Among these, in the present embodiment, a cation exchange resin is particularly preferable. As a kind of cation exchange resin, first, a suspension polymer of polystyrene or divinylbenzene as a skeleton is preferable. The types of ion exchange resins are classified into a gel type and a macroporous type. However, the gel type resin does not have pores, and it is difficult for a substance involved in the reaction to enter the inside of the resin, so that the active sites are not effectively used. The macroporous resin has large pores, and a substance involved in the reaction can easily reach the active site, and the active site is effectively used. For this reason, it is preferable that the cation exchange resin used in this embodiment is a macroporous material whose pore volume is 0.1 ml / g or more as measured by a mercury injection method. The acidic group attached to the resin is a sulfone group, an acrylic group or the like, preferably an H + type, and more preferably a sulfone group. Examples of ion exchange resins that satisfy these requirements include Amberlyst 15 (manufactured by Rohm and Hers), Diaion PK-208H, PK-216H, PK-228H (manufactured by Mitsubishi Kasei), Burolite CT-175, CT -171, CT-169 (manufactured by Burolite) and the like. Of these, Burolite CT-175 (manufactured by Burolite) is particularly preferable.
本実施形態おいては、上記イオン交換樹脂の添加後、撹拌し、上記反応性金属化合物を加水分解させて加水分解物またはその縮合物を得るものであるが、この場合、撹拌時間(反応時間)は3分以上、特に5分以上とすることが好ましい。また、反応温度は0℃以上とすることが好ましい。しかし、反応時間は長過ぎると縮合物の分子量が大きく成り過ぎヘイズ上昇の可能性があるため、3時間以内の反応時間が好ましい。また、反応温度が高い場合においても、同様であり、反応温度としては0~50℃での実施が好ましい。
In this embodiment, after the addition of the ion exchange resin, stirring is performed to hydrolyze the reactive metal compound to obtain a hydrolyzate or a condensate thereof. In this case, the stirring time (reaction time) ) Is preferably 3 minutes or more, particularly preferably 5 minutes or more. Moreover, it is preferable that reaction temperature shall be 0 degreeC or more. However, if the reaction time is too long, the molecular weight of the condensate becomes so large that haze may be increased. The same applies to the case where the reaction temperature is high, and the reaction temperature is preferably 0 to 50 ° C.
本実施形態で用いる陽イオン交換樹脂の粒径としては、特に制限はないが、平均粒径が10~2000μmの範囲が好ましい。平均粒径が10μm未満の場合は、処理後の樹脂分離の際濾過性や液切れが劣化することがあり、また平均粒径が2000μmを超えると、質量当たりの表面積が低下し、加水分解効率が低いという問題がある。粒径は揃っていたほうが好ましいが、欠けたり割れたりした粒子が一部混入していてもよい。
The particle size of the cation exchange resin used in the present embodiment is not particularly limited, but the average particle size is preferably in the range of 10 to 2000 μm. When the average particle size is less than 10 μm, filterability and liquid breakage may be deteriorated during the resin separation after the treatment. When the average particle size exceeds 2000 μm, the surface area per mass decreases, and the hydrolysis efficiency There is a problem that is low. Although it is preferable that the particle diameters are uniform, a chipped or cracked particle may be partially mixed.
また、イオン交換樹脂のイオン交換容量は、0.1ミリ等量/ml以上が好ましい。0.1ミリ等量/ml未満では、加水分解効率が低下し、生産性の低下を来たすことがある。
The ion exchange capacity of the ion exchange resin is preferably 0.1 milliequivalent / ml or more. If it is less than 0.1 milliequivalent / ml, the hydrolysis efficiency is lowered and productivity may be lowered.
本実施形態において、固体触媒であるイオン交換樹脂の添加量は、加水分解重縮合可能な反応性金属化合物に対して、0.00001~30質量%であることが好ましく、より好ましくは0.001~20質量%である。イオン交換樹脂の量が多過ぎると、縮合が優先的に進行してしまい、縮合物の分子量が大きく成り過ぎる。また、イオン交換樹脂の量が少な過ぎると、加水分解に必要な十分な活性が得られず、加水分解物またはその縮合物を十分得ることができない。
In the present embodiment, the addition amount of the ion exchange resin as a solid catalyst is preferably 0.00001 to 30% by mass, more preferably 0.001 based on the reactive metal compound capable of hydrolysis polycondensation. ~ 20% by weight. If the amount of the ion exchange resin is too large, the condensation proceeds preferentially, and the molecular weight of the condensate becomes too large. Moreover, when there is too little quantity of an ion exchange resin, sufficient activity required for a hydrolysis cannot be obtained, and a hydrolyzate or its condensate cannot fully be obtained.
本実施形態における固体触媒を用いた加水分解の方法は、予め水とアルコールを混合しておき、ここに反応性金属化合物を添加混合した後、固体触媒を添加して攪拌して加水分解を進めることが好ましい。また、予め水とアルコールを混合し、ここに固体触媒を添加した後、更にここに反応性金属化合物を攪拌しながら添加して加水分解を進めることも好ましい。
In the hydrolysis method using the solid catalyst in the present embodiment, water and alcohol are mixed in advance, a reactive metal compound is added and mixed therein, and then the solid catalyst is added and stirred to proceed the hydrolysis. It is preferable. In addition, it is also preferable that water and alcohol are mixed in advance and the solid catalyst is added thereto, and then the reactive metal compound is further added with stirring to proceed the hydrolysis.
<反応性金属化合物>
本実施形態において、金属とは、「周期表の化学」岩波書店 斎藤一夫著 p.71記載の金属、すなわち、半金属性原子を含む金属である。 <Reactive metal compound>
In the present embodiment, the term “metal” refers to “Chemistry of the Periodic Table” by Iwanami Shoten, Kazuo Saito, p. 71. A metal according to 71, that is, a metal containing a semimetallic atom.
本実施形態において、金属とは、「周期表の化学」岩波書店 斎藤一夫著 p.71記載の金属、すなわち、半金属性原子を含む金属である。 <Reactive metal compound>
In the present embodiment, the term “metal” refers to “Chemistry of the Periodic Table” by Iwanami Shoten, Kazuo Saito, p. 71. A metal according to 71, that is, a metal containing a semimetallic atom.
本実施形態で用いられる加水分解重縮合が可能な反応性金属化合物としては、例えば金属アルコキシド、金属ジケトネート、金属アルキルアセトアセテート、金属イソシアネート、反応性の金属ハロゲン化物が挙げられる。好ましくは、金属種が、Si、Ti、ZrまたはAlのアルコキシドであり、特に好ましくは、Siのアルコキシドである。
Examples of reactive metal compounds capable of hydrolytic polycondensation used in this embodiment include metal alkoxides, metal diketonates, metal alkyl acetoacetates, metal isocyanates, and reactive metal halides. Preferably, the metal species is an alkoxide of Si, Ti, Zr or Al, and particularly preferably an alkoxide of Si.
このような加水分解重縮合可能な反応性金属化合物は、中心金属をM、その原子数をq、加水分解されない置換基をA、その置換基数をp、加水分解可能な置換基をB、その置換基数をrとすると、理想的には下記の式(1)のように反応が完結し、金属酸化物が得られる。
Such a reactive metal compound capable of hydrolytic polycondensation has M as the central metal, q as the number of atoms, A as the non-hydrolyzed substituent, p as the number of substituents, B as the hydrolyzable substituent, When r is the number of substituents, the reaction is ideally completed as shown in the following formula (1), and a metal oxide is obtained.
式(1) ApMqBr → ApMqOr/2
Equation (1) A p M q B r → A p M q O r / 2
加水分解重縮合可能な反応性金属化合物としては、式(1)で示されているApMqBrにおいて、p=0であるような、全てが加水分解可能な置換基で置換されていることが好ましいが、基材フィルムの透湿度を低減する観点から、加水分解されない置換基によって該金属1原子当たり1つまたは2つ、或いは3つ置換されている化合物が含まれていても良い。このような加水分解されない置換基を有する金属化合物の添加量としては、添加される金属化合物の50モル%以下が好ましい。また、上記添加量の範囲で2種以上の異なる種類の金属アルコキシドを併用しても良い。
The hydrolyzable polycondensable reactive metal compound, in A p M q B r shown in equation (1), such that p = 0, all being substituted with hydrolyzable substituents However, from the viewpoint of reducing the moisture permeability of the base film, a compound substituted with one, two, or three per atom of the metal by a non-hydrolyzed substituent may be included. . The amount of the metal compound having a substituent that is not hydrolyzed is preferably 50 mol% or less of the metal compound to be added. Moreover, you may use together 2 or more types of different types of metal alkoxide in the range of the said addition amount.
このような加水分解されない置換基としては、置換または無置換のアルキル基、または置換または無置換のアリール基が好ましく、該アルキル基またはアリール基の置換基としては、アルキル基(例えばメチル基、エチル基等)、シクロアルキル基(例えばシクロペンチル基、シクロヘキシル基等)、アラルキル基(例えばベンジル基、2-フェネチル基等)、アリール基(例えばフェニル基、ナフチル基等)、複素環基(例えばフラン、チオフェン、ピリジン等)、アルコキシ基(例えばメトキシ基、エトキシ基等)、アリールオキシ基(例えばフェノキシ基等)、アシル基、ハロゲン原子、シアノ基、アミノ基、アルキルチオ基、グリシジル基、ビニル基、フッ素原子含有アルキル基またはフッ素原子含有アリール基等が挙げられる。
As such a non-hydrolyzed substituent, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group is preferable. As the substituent of the alkyl group or aryl group, an alkyl group (for example, methyl group, ethyl group) Group), cycloalkyl group (eg cyclopentyl group, cyclohexyl group etc.), aralkyl group (eg benzyl group, 2-phenethyl group etc.), aryl group (eg phenyl group, naphthyl group etc.), heterocyclic group (eg furan, Thiophene, pyridine etc.), alkoxy group (eg methoxy group, ethoxy group etc.), aryloxy group (eg phenoxy group etc.), acyl group, halogen atom, cyano group, amino group, alkylthio group, glycidyl group, vinyl group, fluorine Examples thereof include an atom-containing alkyl group and a fluorine atom-containing aryl group.
本実施形態で用いられる重縮合が可能な反応性金属化合物としては、ケイ素化合物として、例えば、テトラメトキシシラン、テトラエトキシシラン、テトライソプロポキシシラン、テトラ-n-ブトキシシラン、テトラ-t-ブトキシシラン、テトラキス(メトキシエトキシ)シラン、テトラキス(メトキシプロポキシ)シラン、テトラクロロシラン、テトライソシアナートシラン等が挙げられる。
Examples of reactive metal compounds capable of polycondensation used in this embodiment include silicon compounds such as tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, and tetra-t-butoxysilane. , Tetrakis (methoxyethoxy) silane, tetrakis (methoxypropoxy) silane, tetrachlorosilane, tetraisocyanatosilane and the like.
また、加水分解されない置換基を有するケイ素化合物として、ジメチルジメトキシシラン、ジメチルジエトキシシラン、ジメチルジイソプロポキシシラン、ジメチルジブトキシシラン、ジエチルジメトキシシラン、ジエチルジエトキシシラン、ジエチルジイソプロポキシシラン、ジエチルジブトキシシラン、ジフェニルジメトキシシラン、ジフェニルジエトキシシラン、ジフェニルジイソプロポキシシラン、ジフェニルジブトキシシラン、3-グリシドキシプロピルメチルジメトキシシラン、ジクロロジメチルシラン、ジクロロジエチルシラン、メチルトリメトキシシラン、メチルトリエトキシシラン、メチルトリイソプロポキシシラン、メチルトリブトキシシラン、エチルトリメトキシシラン、エチルトリエトキシシラン、エチルトリイソプロポキシシラン、エチルトリブトキシシラン、フェニルトリメトキシシラン、フェニルトリエトキシシラン、フェニルトリイソプロポキシシラン、フェニルトリブトキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリイソプロポキシシラン、ビニルトリブトキシシラン、3-グリシドキシプロピルトリメトキシシラン、3-アミノプロピルトリエトキシシラン、2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン、3-クロロプロピルトリメトキシシラン、3-メルカプトプロピルトリメトキシシラン、(3-アクリロキシプロピル)トリメトキシシラン、アセトキシトリエトキシシラン、(ヘプタデカフルオロ-1,1,2,2-テトラヒドロデシル)トリメトキシシラン、(3,3,3-トリフルオロプロピル)トリメトキシシラン、メチルトリクロロシラン、エチルトリクロロシラン、フェニルトリクロロシラン、(3,3,3-トリフルオロプロピル)トリエトキシシラン、ペンタフルオロフェニルプロピルトリメトキシシラン、(ヘプタデカフルオロ-1,1,2,2-テトラヒドロデシル)トリエトキシシラン、(3,3,3-トリフルオロプロピル)トリクロロシラン、ペンタフルオロフェニルプロピルトリクロロシラン、(ヘプタデカフルオロ-1,1,2,2-テトラヒドロデシル)トリクロロシラン、メチルトリイソシアナートシラン、フェニルトリイソシアナートシラン、ビニルトリイソシアナートシラン等が挙げられる。また、これらの化合物が部分的に縮合した、多摩化学製シリケート40、シリケート45、シリケート48、Mシリケート51のような、数量体のケイ素化合物でもよい。
Examples of silicon compounds having substituent groups that are not hydrolyzed include dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiisopropoxysilane, dimethyldibutoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldiisopropoxysilane, and diethyldiisosilane. Butoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldiisopropoxysilane, diphenyldibutoxysilane, 3-glycidoxypropylmethyldimethoxysilane, dichlorodimethylsilane, dichlorodiethylsilane, methyltrimethoxysilane, methyltriethoxysilane , Methyltriisopropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri Propoxysilane, ethyltributoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriisopropoxysilane, phenyltributoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltributoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, ( 3-acryloxypropyl) trimethoxysilane, acetoxytriethoxysilane, (heptadecafluoro-1,1,2,2-tetrahydrodecyl) trimethoxysilane, (3,3, -Trifluoropropyl) trimethoxysilane, methyltrichlorosilane, ethyltrichlorosilane, phenyltrichlorosilane, (3,3,3-trifluoropropyl) triethoxysilane, pentafluorophenylpropyltrimethoxysilane, (heptadecafluoro-1, 1,2,2-tetrahydrodecyl) triethoxysilane, (3,3,3-trifluoropropyl) trichlorosilane, pentafluorophenylpropyltrichlorosilane, (heptadecafluoro-1,1,2,2-tetrahydrodecyl) tri Examples include chlorosilane, methyl triisocyanate silane, phenyl triisocyanate silane, and vinyl triisocyanate silane. In addition, quantified silicon compounds such as silicate 40, silicate 45, silicate 48, and M silicate 51 manufactured by Tama Chemical, which are partially condensed with these compounds, may be used.
また、チタン化合物としては、チタンメトキシド、チタンエトキシド、チタンイソプロポキシド、チタン-n-ブトキシド、テトラクロロチタン、チタンジイソプロポキシド(ビス-2,4-ペンタンジオネート)、チタンジイソプロポキシド(ビス-2,4-エチルアセトアセテート)、チタンジ-n-ブトキシド(ビス-2,4-ペンタンジオネート)、チタンアセチルアセトネート、チタンラクテート、チタントリエタノールアミネート、ブチルチタネートダイマー等が挙げられる。
Examples of titanium compounds include titanium methoxide, titanium ethoxide, titanium isopropoxide, titanium-n-butoxide, tetrachlorotitanium, titanium diisopropoxide (bis-2,4-pentanedionate), titanium diiso Propoxide (bis-2,4-ethylacetoacetate), titanium di-n-butoxide (bis-2,4-pentanedionate), titanium acetylacetonate, titanium lactate, titanium triethanolaminate, butyl titanate dimer, etc. Can be mentioned.
また、ジルコニウム化合物としては、ジルコニウム-n-プロポキシド、ジルコニウム-n-ブトキシド、ジルコニウムトリ-n-ブトキシドアセチルアセトネート、ジルコニウムジ-n-ブトキシドビスアセチルアセトネート、ジルコニウムアセチルアセトネート、ジルコニウムアセテート、等が挙げられる。
Zirconium compounds include zirconium-n-propoxide, zirconium-n-butoxide, zirconium tri-n-butoxide acetylacetonate, zirconium di-n-butoxide bisacetylacetonate, zirconium acetylacetonate, zirconium acetate, etc. Is mentioned.
また、アルミニウム化合物としては、アルミニウムエトキシド、アルミニウムイソプロポキシド、アルミニウム-n-ブトキシド、アルミニウム-s-ブトキシド、アルミニウム-ジ-s-ブトキシドエチルアセチルアセトナート、アルミニウム-t-ブトキシド、アルマトラン、アルミニウムフェノキシド、アルミニウムアセチルアセトナート、アルミニウムエチルアセチルアセトナート等が挙げられる。
Aluminum compounds include aluminum ethoxide, aluminum isopropoxide, aluminum-n-butoxide, aluminum-s-butoxide, aluminum-di-s-butoxide ethylacetylacetonate, aluminum-t-butoxide, almatrane, aluminum phenoxide. , Aluminum acetylacetonate, aluminum ethylacetylacetonate and the like.
また、その他の金属からなる化合物としては、例えば、バリウムイソプロポキシド、カルシウムエトキシド、銅エトキシド、マグネシウムエトキシド、マンガンメトキシド、ストロンチウムイソプロポキシド、錫エトキシド、亜鉛メトキシエトキシド、トリメトキシボラン、トリエトキシボラン、アンチモンエトキシド、ヒ素トリエトキシド、ビスマスt-ペントキシド、クロムイソプロポキシド、エルビウムメトキシエトキシド、ガリウムエトキシド、インジウムメトキシエトキシド、鉄エトキシド、ランタンイソプロポキシド、ネオジウムメトキシエトキシド、プラセオジムメトキシエトキシド、サマリウムイソプロポキシド、バナジウムトリイソブトキシドオキシド、イットリウムイソプロポキシド、テトラメトキシゲルマン、テトラエトキシゲルマン、テトライソプロポキシゲルマン、テトラ-n-ブトキシゲルマン、セリウム-t-ブトキシド、ハフニウムエトキシド、ハフニウム-n-ブトキシド、テルルエトキシド、モリブデンエトキシド、ニオブエトキシド、ニオブ-n-ブトキシド、タンタルメトキシド、タンタルエトキシド、タンタル-n-ブトキシド、タングステン(V)エトキシド、タングステン(VI)エトキシド、タングステン(VI)フェノキシド等が挙げられる。
Examples of the other metal compound include barium isopropoxide, calcium ethoxide, copper ethoxide, magnesium ethoxide, manganese methoxide, strontium isopropoxide, tin ethoxide, zinc methoxyethoxide, trimethoxyborane, Triethoxyborane, antimony ethoxide, arsenic triethoxide, bismuth t-pentoxide, chromium isopropoxide, erbium methoxyethoxide, gallium ethoxide, indium methoxyethoxide, iron ethoxide, lanthanum isopropoxide, neodymium methoxyethoxide, praseodymium methoxy Ethoxide, samarium isopropoxide, vanadium triisobutoxide oxide, yttrium isopropoxide, tetramethoxygermane, teto Ethoxygermane, tetraisopropoxygermane, tetra-n-butoxygermane, cerium-t-butoxide, hafnium ethoxide, hafnium-n-butoxide, tellurium ethoxide, molybdenum ethoxide, niobium ethoxide, niobium-n-butoxide, tantalum Examples thereof include methoxide, tantalum ethoxide, tantalum-n-butoxide, tungsten (V) ethoxide, tungsten (VI) ethoxide, tungsten (VI) phenoxide and the like.
また、本実施形態で用いられる重縮合が可能な反応性金属化合物としては、分子種内に2つの金属原子を持つダブル金属アルコキシドと呼ばれる化合物でも良い。このようなダブル金属アルコキシドとしては、例えば、ゲレスト社製のアルミニウム銅アルコキシド、アルミニウムチタンアルコキシド、アルミニウムイットリウムアルコキシド、アルミニウムジルコニウムアルコキシド、バリウムチタンアルコキシド、バリウムイットリウムアルコキシド、バリウムジルコニウムアルコキシド、インジウム錫アルコキシド、リチウムニッケルアルコキシド、リチウムニオブアルコキシド、リチウムタンタルアルコキシド、マグネシウムアルミニウムアルコキシド、マグネシウムチタンアルコキシド、マグネシウムジルコニウムアルコキシド、ストロンチウムチタンアルコキシド、ストロンチウムジルコニウムアルコキシド等が挙げられるが、少なくとも、ケイ素、アルミニウム、チタニウム、ジルコニウムのいずれかの金属が含まれているものが好ましい。
The reactive metal compound capable of polycondensation used in this embodiment may be a compound called double metal alkoxide having two metal atoms in the molecular species. Examples of such double metal alkoxides include aluminum copper alkoxide, aluminum titanium alkoxide, aluminum yttrium alkoxide, aluminum zirconium alkoxide, barium titanium alkoxide, barium yttrium alkoxide, barium zirconium alkoxide, indium tin alkoxide, lithium nickel alkoxide manufactured by Gerest Co., Ltd. Lithium niobium alkoxide, lithium tantalum alkoxide, magnesium aluminum alkoxide, magnesium titanium alkoxide, magnesium zirconium alkoxide, strontium titanium alkoxide, strontium zirconium alkoxide, etc., but at least silicon, aluminum, titanium, zirconium Preferably one that contains any metal.
<水酸基含有高分子化合物>
水酸基含有高分子化合物は、分子内に水酸基を含有していればよく、例えば、ポリビニルアルコール等の合成高分子や、デンプン、セルロース、カルボキシメチルセルロース、アルギン酸ナトリウムなどの多糖類とそれらの誘導体などが挙げられる。これらの水酸基含有高分子化合物は、1種単独で又は2種以上を適宜組み合わせて用いることができる。 <Hydroxyl-containing polymer compound>
The hydroxyl group-containing polymer compound only needs to contain a hydroxyl group in the molecule, and examples thereof include synthetic polymers such as polyvinyl alcohol, polysaccharides such as starch, cellulose, carboxymethyl cellulose, sodium alginate, and derivatives thereof. It is done. These hydroxyl group-containing polymer compounds can be used singly or in appropriate combination of two or more.
水酸基含有高分子化合物は、分子内に水酸基を含有していればよく、例えば、ポリビニルアルコール等の合成高分子や、デンプン、セルロース、カルボキシメチルセルロース、アルギン酸ナトリウムなどの多糖類とそれらの誘導体などが挙げられる。これらの水酸基含有高分子化合物は、1種単独で又は2種以上を適宜組み合わせて用いることができる。 <Hydroxyl-containing polymer compound>
The hydroxyl group-containing polymer compound only needs to contain a hydroxyl group in the molecule, and examples thereof include synthetic polymers such as polyvinyl alcohol, polysaccharides such as starch, cellulose, carboxymethyl cellulose, sodium alginate, and derivatives thereof. It is done. These hydroxyl group-containing polymer compounds can be used singly or in appropriate combination of two or more.
合成高分子には、例えば、水酸基を有するビニル系、ポリスチレン系、ポリアクリル系、ポリウレタン系、アルキド系、メラミン系、尿素系、フェノール系、ポリエステル系、ポリグリセリン系高分子化合物、また多分岐形状を有する水酸基を有する高分子化合物を用いることができる。また、水酸基を有する高分子は、水酸基をもつ単量体を導入した重合体であってもよい。この場合、高分子の有する水酸基の量や導入位置が調整可能となる。
Synthetic polymers include, for example, vinyl-based, polystyrene-based, polyacrylic-based, polyurethane-based, alkyd-based, melamine-based, urea-based, phenol-based, polyester-based, polyglycerol-based polymer compounds having a hydroxyl group, and multi-branched shapes. A high molecular compound having a hydroxyl group having can be used. Further, the polymer having a hydroxyl group may be a polymer into which a monomer having a hydroxyl group is introduced. In this case, the amount of hydroxyl groups and the introduction position of the polymer can be adjusted.
水酸基を有する単量体としては、3-ビニルフェノール、ヒドロキシメチルスチレン、4-ビニルベンジル-4-ヒドロキシブチルエーテル、4-(ヒドロキシメチルシリルフェニル)スチレン、などの水酸基を有するスチレン類や、ヒドロキシエチルメタクリレートなどの水酸基を有するアクリル樹脂や、N-(4-(4-ヒドロキシフェニルスルホニル)フェノキシカルボニル)メタクリルアミドなどの水酸基を有するアクリルアミド樹脂などが使用でき、好ましくはビニル系モノマーである。これらの水酸基を有する単量体は、2種類以上を混合して用いてもよい。
Examples of the monomer having a hydroxyl group include styrenes having a hydroxyl group such as 3-vinylphenol, hydroxymethylstyrene, 4-vinylbenzyl-4-hydroxybutyl ether, 4- (hydroxymethylsilylphenyl) styrene, and hydroxyethyl methacrylate. An acrylic resin having a hydroxyl group such as N- (4- (4-hydroxyphenylsulfonyl) phenoxycarbonyl) methacrylamide may be used, and a vinyl monomer is preferable. Two or more kinds of these monomers having a hydroxyl group may be mixed and used.
多糖類としては、デンプン、ヒドロキシメチルデンプン、ヒドロキシエチルデンプン、ヒドロキシプロピルデンプン、グリコーゲン、イヌリン、リケニン、セルロース、ヘミセルロース、アミロペクチン、ヘパリン、ヘパリチン硫酸、コンドロイチン硫酸、ヒアルロン酸、ケラト硫酸、キチン、キトサン、寒天、カラギーナン、アルギン酸、ファーセレラン、ローカストビーンガム、ガラクトマンナン、グアガム、サイリュウガム、タマリンドガム、アラビアガム、トラガカントガム、カラヤガム、ペクチン、アラビノガラクタン、キサンタンガム、ジェランガム、プルラン、デキストラン、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、ヒドロキシプロピルメチルセルロース、カルボキシメチルセルロース、メチルセルロース、エチルセルロース、及びこれらのカチオン化物等が挙げられる。
Polysaccharides include starch, hydroxymethyl starch, hydroxyethyl starch, hydroxypropyl starch, glycogen, inulin, lichenin, cellulose, hemicellulose, amylopectin, heparin, heparitin sulfate, chondroitin sulfate, hyaluronic acid, keratosulfate, chitin, chitosan, agar , Carrageenan, alginic acid, fur celerane, locust bean gum, galactomannan, guar gum, syrup gum, tamarind gum, gum arabic, tragacanth gum, caraya gum, pectin, arabinogalactan, xanthan gum, gellan gum, pullulan, dextran, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxy Propyl methyl cellulose, carboxymethyl cellulose, methyl cell Over scan, ethyl cellulose, and the cationic compound, and the like.
本実施形態で用いられる水酸基含有高分子化合物としては、セルロース誘導体が好ましく用いられ、中でもジアセチルセルロース(DAC)、セルロースアセテートプロピオネート(CAP)、セルロースアセテートブチレート(CAB)、セルロースアセテートフタレート、セルロースアセテートトリメリテート、硝酸セルロース等のセルロースエステル類が好ましい。更に好ましくは、アシル基置換度が0.5~2.9であり、より好ましくは、アシル基置換度が1.0~2.6である。
As the hydroxyl group-containing polymer compound used in the present embodiment, cellulose derivatives are preferably used. Among them, diacetyl cellulose (DAC), cellulose acetate propionate (CAP), cellulose acetate butyrate (CAB), cellulose acetate phthalate, cellulose Cellulose esters such as acetate trimellitate and cellulose nitrate are preferred. More preferably, the acyl group substitution degree is 0.5 to 2.9, and more preferably, the acyl group substitution degree is 1.0 to 2.6.
〔実施例〕
以下、本発明の具体例を実施例として説明する。また、本発明との比較のため、比較例についても併せて説明する。なお、本発明は、以下の実施例に限定されるものではない。なお、以下での説明において、「部」あるいは「%」の表示は、特に断りがない限り、「質量部」あるいは「質量%」を表すものとする。 〔Example〕
Hereinafter, specific examples of the present invention will be described as examples. For comparison with the present invention, comparative examples will also be described. The present invention is not limited to the following examples. In the following description, “parts” or “%” indicates “parts by mass” or “mass%” unless otherwise specified.
以下、本発明の具体例を実施例として説明する。また、本発明との比較のため、比較例についても併せて説明する。なお、本発明は、以下の実施例に限定されるものではない。なお、以下での説明において、「部」あるいは「%」の表示は、特に断りがない限り、「質量部」あるいは「質量%」を表すものとする。 〔Example〕
Hereinafter, specific examples of the present invention will be described as examples. For comparison with the present invention, comparative examples will also be described. The present invention is not limited to the following examples. In the following description, “parts” or “%” indicates “parts by mass” or “mass%” unless otherwise specified.
<λ/4位相差フィルムAの製造>
〈微粒子分散液〉
微粒子(アエロジル R812 日本アエロジル(株)製)
11質量部
エタノール 89質量部
以上をディゾルバーで50分間攪拌混合した後、マントンゴーリンで分散を行い、微粒子分散液を調製した。 <Manufacture of λ / 4 retardation film A>
<Fine particle dispersion>
Fine particles (Aerosil R812 manufactured by Nippon Aerosil Co., Ltd.)
11 parts by mass Ethanol 89 parts by mass The above was stirred and mixed with a dissolver for 50 minutes, and then dispersed with Manton Gorin to prepare a fine particle dispersion.
〈微粒子分散液〉
微粒子(アエロジル R812 日本アエロジル(株)製)
11質量部
エタノール 89質量部
以上をディゾルバーで50分間攪拌混合した後、マントンゴーリンで分散を行い、微粒子分散液を調製した。 <Manufacture of λ / 4 retardation film A>
<Fine particle dispersion>
Fine particles (Aerosil R812 manufactured by Nippon Aerosil Co., Ltd.)
11 parts by mass Ethanol 89 parts by mass The above was stirred and mixed with a dissolver for 50 minutes, and then dispersed with Manton Gorin to prepare a fine particle dispersion.
〈微粒子添加液〉
メチレンクロライドを入れた溶解タンクに十分攪拌しながら、微粒子分散液をゆっくりと添加した。更に、二次粒子の粒径が所定の大きさとなるようにアトライターにて分散を行った。これを日本精線(株)製のファインメットNFで濾過し、微粒子添加液を調製した。
メチレンクロライド 5質量部
微粒子分散液 5質量部 <Fine particle additive solution>
The fine particle dispersion was slowly added to the dissolution tank containing methylene chloride with sufficient stirring. Further, the particles were dispersed by an attritor so that the secondary particles had a predetermined particle size. This was filtered through Finemet NF manufactured by Nippon Seisen Co., Ltd. to prepare a fine particle additive solution.
Methylene chloride 5 parts by weight Fine particle dispersion 5 parts by weight
メチレンクロライドを入れた溶解タンクに十分攪拌しながら、微粒子分散液をゆっくりと添加した。更に、二次粒子の粒径が所定の大きさとなるようにアトライターにて分散を行った。これを日本精線(株)製のファインメットNFで濾過し、微粒子添加液を調製した。
メチレンクロライド 5質量部
微粒子分散液 5質量部 <Fine particle additive solution>
The fine particle dispersion was slowly added to the dissolution tank containing methylene chloride with sufficient stirring. Further, the particles were dispersed by an attritor so that the secondary particles had a predetermined particle size. This was filtered through Finemet NF manufactured by Nippon Seisen Co., Ltd. to prepare a fine particle additive solution.
Methylene chloride 5 parts by weight Fine particle dispersion 5 parts by weight
〈ドープ液の組成〉
メチレンクロライド 340質量部
エタノール 64質量部
セルロースアセテート(DAC、アセチル基置換度2.45)
100質量部
糖エステル化合物(平均置換度5.5のスクロースベンゾエート)
12質量部
微粒子添加液 2質量部
以上を密閉されている主溶解釜に投入し、攪拌しながら溶解してドープ液を調製した。 <Composition of dope solution>
Methylene chloride 340 parts bymass Ethanol 64 parts by mass Cellulose acetate (DAC, acetyl group substitution degree 2.45)
100 parts by mass Sugar ester compound (sucrose benzoate having an average substitution degree of 5.5)
12 parts by massParticulate additive solution 2 parts by mass The above was put into a sealed main dissolution vessel and dissolved with stirring to prepare a dope solution.
メチレンクロライド 340質量部
エタノール 64質量部
セルロースアセテート(DAC、アセチル基置換度2.45)
100質量部
糖エステル化合物(平均置換度5.5のスクロースベンゾエート)
12質量部
微粒子添加液 2質量部
以上を密閉されている主溶解釜に投入し、攪拌しながら溶解してドープ液を調製した。 <Composition of dope solution>
Methylene chloride 340 parts by
100 parts by mass Sugar ester compound (sucrose benzoate having an average substitution degree of 5.5)
12 parts by mass
そして、上記のように調製したドープ液をステンレスベルト支持体上に流延し、ステンレスベルト支持体上で、流延(キャスト)したフィルム中の残留溶媒量が75質量%になるまで溶媒を蒸発させ、次いで剥離張力130N/mで、ステンレスベルト支持体上から剥離した。その後、剥離したフィルムを、160℃の熱をかけながらテンターを用いて幅方向に1%延伸した。延伸開始時の残留溶媒は15質量%であった。
The dope solution prepared as described above is cast on a stainless steel belt support, and the solvent is evaporated on the stainless steel belt support until the amount of residual solvent in the cast (cast) film reaches 75% by mass. And then peeled off from the stainless steel belt support with a peeling tension of 130 N / m. Thereafter, the peeled film was stretched by 1% in the width direction using a tenter while applying heat at 160 ° C. The residual solvent at the start of stretching was 15% by mass.
次いで、乾燥ゾーンを多数のロールで搬送させながら乾燥を終了させた。乾燥温度は130℃で、搬送張力は100N/mとした。以上のようにして、乾燥膜厚102μmのロール状の原反フィルムAを得た。
Next, drying was completed while the drying zone was conveyed by a number of rolls. The drying temperature was 130 ° C. and the transport tension was 100 N / m. As described above, a roll-shaped raw film A having a dry film thickness of 102 μm was obtained.
ロール状の原反フィルムAを、スライド可能な繰出装置にセットし、斜め延伸テンター装置に供給した。テンターで延伸温度190℃、延伸倍率80%で幅手方向に延伸を行い、その後、レールが45°屈曲する際に延伸と垂直方向に0.71倍に収縮した。その後、フィルム両端をトリミングして、エアーフローロールからなる搬送方向変更装置で搬送方向を変更し、巻取装置で巻き取り、2000mm幅のロール状のλ/4位相差フィルムAを得た。λ/4位相差フィルムAの膜厚は40μmであり、面内位相差Roは140nmであり、厚み方向の位相差Rtは90nmであった。
The roll-shaped raw film A was set in a slidable feeding device and supplied to an oblique stretching tenter device. The tenter was stretched in the width direction at a stretching temperature of 190 ° C. and a stretching ratio of 80%, and then contracted 0.71 times in the direction perpendicular to the stretching when the rail was bent 45 °. Thereafter, both ends of the film were trimmed, the transport direction was changed with a transport direction changing device composed of an airflow roll, and the film was wound up with a winder to obtain a roll-like λ / 4 retardation film A having a width of 2000 mm. The film thickness of the λ / 4 retardation film A was 40 μm, the in-plane retardation Ro was 140 nm, and the thickness direction retardation Rt was 90 nm.
<λ/4位相差フィルムBの製造>
〈微粒子分散液〉
微粒子(アエロジル R812 日本アエロジル(株)製)
11質量部
エタノール 89質量部
以上をディゾルバーで50分間攪拌混合した後、マントンゴーリンで分散を行い、微粒子分散液を調製した。 <Manufacture of λ / 4 retardation film B>
<Fine particle dispersion>
Fine particles (Aerosil R812 manufactured by Nippon Aerosil Co., Ltd.)
11 parts by mass Ethanol 89 parts by mass The above was stirred and mixed with a dissolver for 50 minutes, and then dispersed with Manton Gorin to prepare a fine particle dispersion.
〈微粒子分散液〉
微粒子(アエロジル R812 日本アエロジル(株)製)
11質量部
エタノール 89質量部
以上をディゾルバーで50分間攪拌混合した後、マントンゴーリンで分散を行い、微粒子分散液を調製した。 <Manufacture of λ / 4 retardation film B>
<Fine particle dispersion>
Fine particles (Aerosil R812 manufactured by Nippon Aerosil Co., Ltd.)
11 parts by mass Ethanol 89 parts by mass The above was stirred and mixed with a dissolver for 50 minutes, and then dispersed with Manton Gorin to prepare a fine particle dispersion.
〈微粒子添加液〉
メチレンクロライドを入れた溶解タンクに十分攪拌しながら、微粒子分散液をゆっくりと添加した。更に、二次粒子の粒径が所定の大きさとなるようにアトライターにて分散を行った。これを日本精線(株)製のファインメットNFで濾過し、微粒子添加液を調製した。
メチレンクロライド 5質量部
微粒子分散液 5質量部 <Fine particle additive solution>
The fine particle dispersion was slowly added to the dissolution tank containing methylene chloride with sufficient stirring. Further, the particles were dispersed by an attritor so that the secondary particles had a predetermined particle size. This was filtered through Finemet NF manufactured by Nippon Seisen Co., Ltd. to prepare a fine particle additive solution.
Methylene chloride 5 parts by weight Fine particle dispersion 5 parts by weight
メチレンクロライドを入れた溶解タンクに十分攪拌しながら、微粒子分散液をゆっくりと添加した。更に、二次粒子の粒径が所定の大きさとなるようにアトライターにて分散を行った。これを日本精線(株)製のファインメットNFで濾過し、微粒子添加液を調製した。
メチレンクロライド 5質量部
微粒子分散液 5質量部 <Fine particle additive solution>
The fine particle dispersion was slowly added to the dissolution tank containing methylene chloride with sufficient stirring. Further, the particles were dispersed by an attritor so that the secondary particles had a predetermined particle size. This was filtered through Finemet NF manufactured by Nippon Seisen Co., Ltd. to prepare a fine particle additive solution.
Methylene chloride 5 parts by weight Fine particle dispersion 5 parts by weight
〈ドープ液の組成〉
メチレンクロライド 340質量部
エタノール 64質量部
セルロースアセテートプロピオネート(CAP、アセチル基置換度1.53、プロピオニル基置換度0.91、総置換度2.44、重量平均分子量Mw220000)
100質量部
糖エステル化合物A 5質量部
ポリエステルB 5質量部
TINUVIN928(BASFジャパン社製) 2質量部
微粒子添加液 2質量部
以上を密閉されている主溶解釜1に投入し、攪拌しながら溶解してドープ液を調製した。 <Composition of dope solution>
Methylene chloride 340 parts bymass Ethanol 64 parts by mass Cellulose acetate propionate (CAP, acetyl group substitution degree 1.53, propionyl group substitution degree 0.91, total substitution degree 2.44, weight average molecular weight Mw220,000)
100 parts by mass Sugar ester compound A 5 parts by mass Polyester B 5 parts by mass TINUVIN 928 (manufactured by BASF Japan Ltd.) 2 parts by massParticulate additive solution 2 parts by mass The above is charged into the sealed main dissolution kettle 1 and dissolved while stirring. A dope solution was prepared.
メチレンクロライド 340質量部
エタノール 64質量部
セルロースアセテートプロピオネート(CAP、アセチル基置換度1.53、プロピオニル基置換度0.91、総置換度2.44、重量平均分子量Mw220000)
100質量部
糖エステル化合物A 5質量部
ポリエステルB 5質量部
TINUVIN928(BASFジャパン社製) 2質量部
微粒子添加液 2質量部
以上を密閉されている主溶解釜1に投入し、攪拌しながら溶解してドープ液を調製した。 <Composition of dope solution>
Methylene chloride 340 parts by
100 parts by mass Sugar ester compound A 5 parts by mass Polyester B 5 parts by mass TINUVIN 928 (manufactured by BASF Japan Ltd.) 2 parts by mass
なお、糖エステル化合物AおよびポリエステルBは、以下の構造式で示されるものである。
The sugar ester compound A and the polyester B are represented by the following structural formula.
そして、上記のように調製したドープ液をステンレスベルト支持体上に流延し、ステンレスベルト支持体上で、流延(キャスト)したフィルム中の残留溶媒量が75質量%になるまで溶媒を蒸発させ、次いで剥離張力130N/mで、ステンレスベルト支持体上から剥離した。その後、剥離したフィルムを、160℃の熱をかけながらテンターを用いて幅方向に1%延伸した。延伸開始時の残留溶媒は15質量%であった。
The dope solution prepared as described above is cast on a stainless steel belt support, and the solvent is evaporated on the stainless steel belt support until the amount of residual solvent in the cast (cast) film reaches 75% by mass. And then peeled off from the stainless steel belt support with a peeling tension of 130 N / m. Thereafter, the peeled film was stretched by 1% in the width direction using a tenter while applying heat at 160 ° C. The residual solvent at the start of stretching was 15% by mass.
次いで、乾燥ゾーンを多数のロールで搬送させながら乾燥を終了させた。乾燥温度は130℃で、搬送張力は100N/mとした。以上のようにして、乾燥膜厚73μmのロール状の原反フィルムBを得た。
Next, drying was completed while the drying zone was conveyed by a number of rolls. The drying temperature was 130 ° C. and the transport tension was 100 N / m. As described above, a roll-shaped raw film B having a dry film thickness of 73 μm was obtained.
ロール状の原反フィルムBを、スライド可能な繰出装置にセットし、斜め延伸テンター装置の斜め延伸機に供給した。テンターで延伸温度190℃、延伸倍率1.74倍で幅手方向に延伸を行い、その後、レールが45°屈曲する際に延伸と垂直方向に0.71倍に収縮した。その後、フィルム両端をトリミングして、エアーフローロールからなる搬送方向変更装置で搬送方向を変更し、スライド可能な巻取装置で巻き取り、2000mm幅のλ/4位相差フィルムBを得た。λ/4位相差フィルムBの膜厚は55μmであり、面内位相差Roは140nmであり、厚み方向の位相差Rtは90nmであった。
The roll-shaped raw film B was set in a slidable feeding device and supplied to an oblique stretching machine of an oblique stretching tenter device. The tenter was stretched in the width direction at a stretching temperature of 190 ° C. and a stretching ratio of 1.74 times, and then contracted 0.71 times in the direction perpendicular to the stretching when the rail was bent 45 °. Then, both ends of the film were trimmed, the transport direction was changed with a transport direction changing device composed of an airflow roll, and the film was wound up with a slidable winding device to obtain a λ / 4 retardation film B having a width of 2000 mm. The film thickness of the λ / 4 retardation film B was 55 μm, the in-plane retardation Ro was 140 nm, and the thickness direction retardation Rt was 90 nm.
<λ/4位相差フィルムC>
λ/4位相差フィルムCとして、帝人(株)製のポリカーボネートフィルムであるピュアエース(登録商標)WRを用意した。 <Λ / 4 retardation film C>
As λ / 4 retardation film C, Pure Ace (registered trademark) WR, which is a polycarbonate film manufactured by Teijin Ltd., was prepared.
λ/4位相差フィルムCとして、帝人(株)製のポリカーボネートフィルムであるピュアエース(登録商標)WRを用意した。 <Λ / 4 retardation film C>
As λ / 4 retardation film C, Pure Ace (registered trademark) WR, which is a polycarbonate film manufactured by Teijin Ltd., was prepared.
<接着剤Aの製造>
下記の比率で材料を混合し、室温で攪拌した後、濾過によって固体触媒を分離して、反応性金属化合物と水酸基含有高分子化合物との縮合物を含む接着剤Aを調製した。
アセトン 100質量部
テトラメトキシシラン(TMOS) 10質量部
アンバーリスト15(固体触媒) 2質量部
セルロースエステル(DAC、アセチル基置換度2.45)
10質量部 <Manufacture of adhesive A>
After mixing the materials in the following ratio and stirring at room temperature, the solid catalyst was separated by filtration to prepare an adhesive A containing a condensate of a reactive metal compound and a hydroxyl group-containing polymer compound.
Acetone 100 parts by mass Tetramethoxysilane (TMOS) 10 parts by mass Amberlyst 15 (solid catalyst) 2 parts by mass Cellulose ester (DAC, acetyl group substitution degree 2.45)
10 parts by mass
下記の比率で材料を混合し、室温で攪拌した後、濾過によって固体触媒を分離して、反応性金属化合物と水酸基含有高分子化合物との縮合物を含む接着剤Aを調製した。
アセトン 100質量部
テトラメトキシシラン(TMOS) 10質量部
アンバーリスト15(固体触媒) 2質量部
セルロースエステル(DAC、アセチル基置換度2.45)
10質量部 <Manufacture of adhesive A>
After mixing the materials in the following ratio and stirring at room temperature, the solid catalyst was separated by filtration to prepare an adhesive A containing a condensate of a reactive metal compound and a hydroxyl group-containing polymer compound.
Acetone 100 parts by mass Tetramethoxysilane (TMOS) 10 parts by mass Amberlyst 15 (solid catalyst) 2 parts by mass Cellulose ester (DAC, acetyl group substitution degree 2.45)
10 parts by mass
<接着剤Bの製造>
下記の比率で材料を混合し、室温で攪拌した後、濾過によって固体触媒を分離して、反応性金属化合物と水酸基含有高分子化合物との縮合物を含む接着剤Bを調製した。
アセトン 100質量部
テトラエトキシシラン(TEOS) 10質量部
アンバーリスト15(固体触媒) 2質量部
セルロースエステル(DAC、アセチル基置換度2.45)
10質量部 <Manufacture of adhesive B>
After mixing the materials in the following ratio and stirring at room temperature, the solid catalyst was separated by filtration to prepare an adhesive B containing a condensate of a reactive metal compound and a hydroxyl group-containing polymer compound.
Acetone 100 parts by mass Tetraethoxysilane (TEOS) 10 parts by mass Amberlyst 15 (solid catalyst) 2 parts by mass Cellulose ester (DAC, acetyl group substitution degree 2.45)
10 parts by mass
下記の比率で材料を混合し、室温で攪拌した後、濾過によって固体触媒を分離して、反応性金属化合物と水酸基含有高分子化合物との縮合物を含む接着剤Bを調製した。
アセトン 100質量部
テトラエトキシシラン(TEOS) 10質量部
アンバーリスト15(固体触媒) 2質量部
セルロースエステル(DAC、アセチル基置換度2.45)
10質量部 <Manufacture of adhesive B>
After mixing the materials in the following ratio and stirring at room temperature, the solid catalyst was separated by filtration to prepare an adhesive B containing a condensate of a reactive metal compound and a hydroxyl group-containing polymer compound.
Acetone 100 parts by mass Tetraethoxysilane (TEOS) 10 parts by mass Amberlyst 15 (solid catalyst) 2 parts by mass Cellulose ester (DAC, acetyl group substitution degree 2.45)
10 parts by mass
<実施例1>
日本電気硝子(株)製の厚さ50μmの薄膜ガラスを準備し、その両面に接着剤Aを塗布し、一方の面にλ/4位相差フィルムAを積層し、他方の面にコニカミノルタアドバンストレイヤー(株)製のセルローストリアセテートフィルム(KC2UA)を積層し、加熱貼合することで位相差機能付きガラスを得た。実施例1の位相差機能付きガラスを、位相差機能付きガラス1とする。 <Example 1>
Prepare a thin glass with a thickness of 50μm made by Nippon Electric Glass Co., Ltd., apply adhesive A on both sides, laminate λ / 4 retardation film A on one side, and Konica Minolta Advanced on the other side A cellulose triacetate film (KC2UA) manufactured by Layer Co., Ltd. was laminated and heated and bonded to obtain glass with a retardation function. The glass with retardation function of Example 1 is referred to as glass 1 with retardation function.
日本電気硝子(株)製の厚さ50μmの薄膜ガラスを準備し、その両面に接着剤Aを塗布し、一方の面にλ/4位相差フィルムAを積層し、他方の面にコニカミノルタアドバンストレイヤー(株)製のセルローストリアセテートフィルム(KC2UA)を積層し、加熱貼合することで位相差機能付きガラスを得た。実施例1の位相差機能付きガラスを、位相差機能付きガラス1とする。 <Example 1>
Prepare a thin glass with a thickness of 50μm made by Nippon Electric Glass Co., Ltd., apply adhesive A on both sides, laminate λ / 4 retardation film A on one side, and Konica Minolta Advanced on the other side A cellulose triacetate film (KC2UA) manufactured by Layer Co., Ltd. was laminated and heated and bonded to obtain glass with a retardation function. The glass with retardation function of Example 1 is referred to as glass 1 with retardation function.
<実施例2>
接着剤Aの代わりに接着剤Bを用いた以外は、実施例1と同様にして位相差機能付きガラスを得た。実施例2の位相差機能付きガラスを、位相差機能付きガラス2とする。 <Example 2>
A glass with a retardation function was obtained in the same manner as in Example 1 except that the adhesive B was used in place of the adhesive A. Let the glass with phase difference function of Example 2 be theglass 2 with phase difference function.
接着剤Aの代わりに接着剤Bを用いた以外は、実施例1と同様にして位相差機能付きガラスを得た。実施例2の位相差機能付きガラスを、位相差機能付きガラス2とする。 <Example 2>
A glass with a retardation function was obtained in the same manner as in Example 1 except that the adhesive B was used in place of the adhesive A. Let the glass with phase difference function of Example 2 be the
<実施例3>
位相差フィルムAの代わりに位相差フィルムBを用いた以外は、実施例1と同様にして位相差機能付きガラスを得た。実施例3の位相差機能付きガラスを、位相差機能付きガラス3とする。 <Example 3>
A glass with a retardation function was obtained in the same manner as in Example 1 except that the retardation film B was used instead of the retardation film A. The glass with retardation function of Example 3 is referred to asglass 3 with retardation function.
位相差フィルムAの代わりに位相差フィルムBを用いた以外は、実施例1と同様にして位相差機能付きガラスを得た。実施例3の位相差機能付きガラスを、位相差機能付きガラス3とする。 <Example 3>
A glass with a retardation function was obtained in the same manner as in Example 1 except that the retardation film B was used instead of the retardation film A. The glass with retardation function of Example 3 is referred to as
<実施例4>
位相差フィルムAの代わりに位相差フィルムCを用いた以外は、実施例1と同様にして位相差機能付きガラスを得た。実施例4の位相差機能付きガラスを、位相差機能付きガラス4とする。 <Example 4>
A glass with a retardation function was obtained in the same manner as in Example 1 except that the retardation film C was used instead of the retardation film A. The glass with retardation function of Example 4 is referred to asglass 4 with retardation function.
位相差フィルムAの代わりに位相差フィルムCを用いた以外は、実施例1と同様にして位相差機能付きガラスを得た。実施例4の位相差機能付きガラスを、位相差機能付きガラス4とする。 <Example 4>
A glass with a retardation function was obtained in the same manner as in Example 1 except that the retardation film C was used instead of the retardation film A. The glass with retardation function of Example 4 is referred to as
<比較例1>
接着剤Aの代わりにアクリル系粘着剤(PSA)を用いた以外は、実施例1と同様にして位相差機能付きガラスを得た。比較例1の位相差機能付きガラスを、位相差機能付きガラス5とする。 <Comparative Example 1>
A glass with a retardation function was obtained in the same manner as in Example 1 except that an acrylic pressure-sensitive adhesive (PSA) was used instead of the adhesive A. The glass with retardation function of Comparative Example 1 is referred to as glass 5 with retardation function.
接着剤Aの代わりにアクリル系粘着剤(PSA)を用いた以外は、実施例1と同様にして位相差機能付きガラスを得た。比較例1の位相差機能付きガラスを、位相差機能付きガラス5とする。 <Comparative Example 1>
A glass with a retardation function was obtained in the same manner as in Example 1 except that an acrylic pressure-sensitive adhesive (PSA) was used instead of the adhesive A. The glass with retardation function of Comparative Example 1 is referred to as glass 5 with retardation function.
<比較例2>
接着剤Aの代わりに熱硬化性のエポキシ系接着剤(ダイゾーニチモリ(株)製のエポテック310)を用いた以外は、実施例1と同様にして位相差機能付きガラスを得た。比較例2の位相差機能付きガラスを、位相差機能付きガラス6とする。 <Comparative Example 2>
A glass with a retardation function was obtained in the same manner as in Example 1 except that a thermosetting epoxy adhesive (Epotech 310 manufactured by Daizonichi Mori Co., Ltd.) was used instead of the adhesive A. The glass with retardation function of Comparative Example 2 is referred to as glass 6 with retardation function.
接着剤Aの代わりに熱硬化性のエポキシ系接着剤(ダイゾーニチモリ(株)製のエポテック310)を用いた以外は、実施例1と同様にして位相差機能付きガラスを得た。比較例2の位相差機能付きガラスを、位相差機能付きガラス6とする。 <Comparative Example 2>
A glass with a retardation function was obtained in the same manner as in Example 1 except that a thermosetting epoxy adhesive (Epotech 310 manufactured by Daizonichi Mori Co., Ltd.) was used instead of the adhesive A. The glass with retardation function of Comparative Example 2 is referred to as glass 6 with retardation function.
<評価>
上記で作製した位相差機能付きガラス1~6について、湿熱耐久試験による位相差ムラについて評価した結果を表1に示す。なお、表1において、接着層AおよびBは、上記した接着剤AおよびBに対応しており、λ/4位相差層A~Cは、上記したλ/4位相差フィルムA~Cに対応している。 <Evaluation>
Table 1 shows the results of evaluating the retardation unevenness by the wet heat durability test for the glasses 1 to 6 with retardation function produced above. In Table 1, the adhesive layers A and B correspond to the adhesives A and B described above, and the λ / 4 retardation layers A to C correspond to the λ / 4 retardation films A to C described above. is doing.
上記で作製した位相差機能付きガラス1~6について、湿熱耐久試験による位相差ムラについて評価した結果を表1に示す。なお、表1において、接着層AおよびBは、上記した接着剤AおよびBに対応しており、λ/4位相差層A~Cは、上記したλ/4位相差フィルムA~Cに対応している。 <Evaluation>
Table 1 shows the results of evaluating the retardation unevenness by the wet heat durability test for the glasses 1 to 6 with retardation function produced above. In Table 1, the adhesive layers A and B correspond to the adhesives A and B described above, and the λ / 4 retardation layers A to C correspond to the λ / 4 retardation films A to C described above. is doing.
位相差ムラの評価の手法および評価基準は以下の通りである。位相差機能付きガラス1~6をそれぞれ、λ/4位相差層が外側になるように、アクリル系粘着剤を用いて厚さ0.7mmの旭硝子(株)製AN100ガラスに貼合し、80℃90%RHで500時間湿熱処理した後、23℃55%RHで24時間調湿し、クロスニコルに配置した偏光板の間に配置した。そして、正面方向から見た場合と斜め方向から見た場合とで位相差機能付きガラスを回転させながら位相差ムラの有無を、5人のモニターによる目視で判断した。なお、位相差ムラの評価結果については、△以上であれば実用上問題ない。
The evaluation method and evaluation criteria for phase difference unevenness are as follows. Glasses 1 to 6 with retardation function were each bonded to AN100 glass manufactured by Asahi Glass Co., Ltd. with a thickness of 0.7 mm using an acrylic pressure-sensitive adhesive so that the λ / 4 retardation layer was on the outside. After heat-moisture treatment at 90 ° C. for 90 hours and humidity control at 23 ° C. and 55% RH for 24 hours, it was placed between polarizing plates arranged in crossed Nicols. And the presence or absence of phase difference nonuniformity was judged by visual observation with five monitors while rotating the glass with a phase difference function between the case of viewing from the front direction and the case of viewing from the oblique direction. The evaluation result of the phase difference unevenness is practically satisfactory if it is Δ or more.
(評価基準)
◎:5人全員が位相差ムラを確認できなかった。
○:5人中1人が位相差ムラを確認できた。
△:5人中2人が位相差ムラを確認できた。
×:5人中3人以上が位相差ムラを確認できた。 (Evaluation criteria)
A: All five people could not confirm the phase difference unevenness.
○: One out of five people confirmed phase difference unevenness.
Δ: Two out of five people were able to confirm phase difference unevenness.
X: 3 or more out of 5 people confirmed phase difference unevenness.
◎:5人全員が位相差ムラを確認できなかった。
○:5人中1人が位相差ムラを確認できた。
△:5人中2人が位相差ムラを確認できた。
×:5人中3人以上が位相差ムラを確認できた。 (Evaluation criteria)
A: All five people could not confirm the phase difference unevenness.
○: One out of five people confirmed phase difference unevenness.
Δ: Two out of five people were able to confirm phase difference unevenness.
X: 3 or more out of 5 people confirmed phase difference unevenness.
表1より、薄膜ガラスとλ/4位相差層との接着層が、PSAまたはエポキシ樹脂である比較例1および2では、半数以上のモニターが位相差ムラを確認しているのに対して、上記接着層の原料にTMOS(またはTEOS)とDACとを含む実施例1~4では、半数以上のモニターが位相差ムラを確認できない結果となっている。これは、薄膜ガラスとλ/4位相差層との接着層が、反応性金属化合物と水酸基含有高分子化合物との縮合物を含んでいることにより、薄膜ガラスとλ/4位相差層との密着性が向上し、これによって耐久試験時の環境変動によるλ/4位相差層の寸法変化が抑えられているためと考えられる。
From Table 1, in Comparative Examples 1 and 2 in which the adhesive layer between the thin film glass and the λ / 4 retardation layer is PSA or epoxy resin, more than half of the monitors confirmed the retardation unevenness, In Examples 1 to 4 where TMOS (or TEOS) and DAC are included in the material for the adhesive layer, more than half of the monitors cannot confirm phase difference unevenness. This is because the adhesive layer between the thin film glass and the λ / 4 retardation layer contains a condensate of a reactive metal compound and a hydroxyl group-containing polymer compound, so that the thin film glass and the λ / 4 retardation layer are This is considered to be because the adhesiveness was improved, and the dimensional change of the λ / 4 retardation layer due to environmental fluctuation during the durability test was suppressed.
特に、λ/4位相差層がセルロース樹脂である実施例1~3では、λ/4位相差層がPC(ポリカーボネート)である実施例4に比べて、位相差ムラを抑える効果が高い。これは、セルロース樹脂は、PCに比べて耐熱性の点で優れており、耐久試験時の温度変化によるλ/4位相差層の寸法変化が元々少ないため、位相差ムラを抑える効果を得やすいためと考えられる。
Particularly, in Examples 1 to 3 in which the λ / 4 retardation layer is a cellulose resin, the effect of suppressing retardation unevenness is higher than in Example 4 in which the λ / 4 retardation layer is PC (polycarbonate). This is because the cellulose resin is superior in heat resistance compared to PC, and the dimensional change of the λ / 4 retardation layer due to the temperature change during the durability test is originally small, so that the effect of suppressing the retardation unevenness is easily obtained. This is probably because of this.
〔補足〕
本実施形態で説明した有機EL表示装置および液晶表示装置は、以下の構成であってもよいと言える。 [Supplement]
It can be said that the organic EL display device and the liquid crystal display device described in the present embodiment may have the following configurations.
本実施形態で説明した有機EL表示装置および液晶表示装置は、以下の構成であってもよいと言える。 [Supplement]
It can be said that the organic EL display device and the liquid crystal display device described in the present embodiment may have the following configurations.
本実施形態の有機EL表示装置は、直線偏光を透過する偏光板を含み、上述した位相差機能付きフィルムと上記偏光板とで円偏光板が構成されていてもよい。
The organic EL display device of this embodiment includes a polarizing plate that transmits linearly polarized light, and a circularly polarizing plate may be configured by the above-described film with retardation function and the polarizing plate.
本実施形態の液晶表示装置は、直線偏光を透過する偏光板を含み、上述した位相差機能付きフィルムと上記偏光板とで円偏光板が構成されていてもよい。
The liquid crystal display device of this embodiment includes a polarizing plate that transmits linearly polarized light, and a circularly polarizing plate may be configured by the above-described film with retardation function and the polarizing plate.
上記有機EL表示装置または上記液晶表示装置において、上記の偏光板は、上記位相差機能付きフィルムのλ/4位相差層に貼り合わされていてもよい。
In the organic EL display device or the liquid crystal display device, the polarizing plate may be bonded to the λ / 4 retardation layer of the film having a retardation function.
上記の偏光板は、直線偏光を透過する偏光層と、上記偏光層の一方の面を保護する保護層とを含み、上記偏光層がλ/4位相差層に貼り合わされていてもよい。
The polarizing plate includes a polarizing layer that transmits linearly polarized light and a protective layer that protects one surface of the polarizing layer, and the polarizing layer may be bonded to the λ / 4 retardation layer.
上記有機EL表示装置または上記液晶表示装置において、上記の偏光板は、直線偏光を透過する偏光層を2つの保護層で両側から挟んで構成され、一方の保護層がλ/4位相差層に貼り合わされていてもよい。
In the organic EL display device or the liquid crystal display device, the polarizing plate is configured by sandwiching a polarizing layer that transmits linearly polarized light from both sides with two protective layers, and one protective layer is a λ / 4 retardation layer. It may be pasted.
本発明の位相差機能付きガラスは、有機EL表示装置や液晶表示装置に利用可能である。
The glass with a retardation function of the present invention can be used for an organic EL display device and a liquid crystal display device.
1 有機EL表示装置
2 有機EL素子
3 位相差機能付きガラス
31 薄膜ガラス
32 接着層(第1の接着層)
33 λ/4位相差層
34 接着層(第2の接着層)
35 樹脂層
51 液晶表示装置
61 基板
62 基板
63 液晶層 DESCRIPTION OF SYMBOLS 1 OrganicEL display device 2 Organic EL element 3 Glass with phase difference function 31 Thin film glass 32 Adhesive layer (1st adhesive layer)
33 λ / 4retardation layer 34 adhesive layer (second adhesive layer)
35Resin layer 51 Liquid crystal display device 61 Substrate 62 Substrate 63 Liquid crystal layer
2 有機EL素子
3 位相差機能付きガラス
31 薄膜ガラス
32 接着層(第1の接着層)
33 λ/4位相差層
34 接着層(第2の接着層)
35 樹脂層
51 液晶表示装置
61 基板
62 基板
63 液晶層 DESCRIPTION OF SYMBOLS 1 Organic
33 λ / 4
35
Claims (9)
- 薄膜ガラスとλ/4位相差層とが接着層を介して積層されており、
前記接着層は、反応性金属化合物と水酸基含有高分子化合物との縮合物を含んでいることを特徴とする位相差機能付きガラス。 A thin film glass and a λ / 4 retardation layer are laminated via an adhesive layer,
The adhesive layer contains a condensate of a reactive metal compound and a hydroxyl group-containing polymer compound. - 前記λ/4位相差層は、セルロース系樹脂を含んでいることを特徴とする請求項1に記載の位相差機能付きガラス。 The glass with a retardation function according to claim 1, wherein the λ / 4 retardation layer contains a cellulose resin.
- 前記接着層を第1の接着層とすると、
前記薄膜ガラスに対して前記λ/4位相差層とは反対側に、第2の接着層を介して樹脂層が積層されていることを特徴とする請求項1または2に記載の位相差機能付きガラス。 When the adhesive layer is a first adhesive layer,
3. The retardation function according to claim 1, wherein a resin layer is laminated on a side opposite to the λ / 4 retardation layer with respect to the thin film glass via a second adhesive layer. With glass. - 前記樹脂層は、セルロース系樹脂からなることを特徴とする請求項3に記載の位相差機能付きガラス。 The glass with a retardation function according to claim 3, wherein the resin layer is made of a cellulose-based resin.
- 前記樹脂層の面内位相差Roが0~5nmであり、厚み方向の位相差Rtが-10~10nmであることを特徴とする請求項3または4に記載の位相差機能付きガラス。 The glass with a retardation function according to claim 3 or 4, wherein an in-plane retardation Ro of the resin layer is 0 to 5 nm and a retardation Rt in the thickness direction is -10 to 10 nm.
- 前記水酸基含有高分子化合物が、総アシル基置換度が1.0~2.6のセルロースエステルであることを特徴とする請求項1から5のいずれかに記載の偏光機能付きガラス。 6. The polarizing glass according to claim 1, wherein the hydroxyl group-containing polymer compound is a cellulose ester having a total acyl group substitution degree of 1.0 to 2.6.
- 前記反応性金属化合物が、シリコンアルコキシドを含むことを特徴とする請求項1から6のいずれかに記載の位相差機能付きガラス。 The glass with retardation function according to any one of claims 1 to 6, wherein the reactive metal compound contains silicon alkoxide.
- 請求項1から7のいずれかに記載の位相差機能付きガラスを有機EL素子上に備えていることを特徴とする有機EL表示装置。 An organic EL display device comprising the glass with a retardation function according to any one of claims 1 to 7 on an organic EL element.
- 2つの基板で液晶層を挟持してなる液晶表示装置であって、
前記2つの基板の少なくとも一方が、請求項1から7のいずれかに記載の位相差機能付きガラスで構成されていることを特徴とする液晶表示装置。 A liquid crystal display device having a liquid crystal layer sandwiched between two substrates,
8. A liquid crystal display device, wherein at least one of the two substrates is composed of the glass with a retardation function according to claim 1.
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