JPWO2014084046A1 - Glass with retardation function, organic EL display device and liquid crystal display device - Google Patents

Abstract

In the glass with phase difference function (3), a thin film glass (31) and a λ / 4 phase difference layer (33) are laminated via an adhesive layer (32). The adhesive layer (32) contains a condensate of a reactive metal compound and a hydroxyl group-containing polymer compound.

Description

  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.

  In recent years, the size of display devices has been increasing, and mobile devices have also been increasing. Thus, thin and light 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.

  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.

  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.

  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.

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], [0016], FIG. 1, etc.)

  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.

  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.

  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.

  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.

  The above-mentioned glass with retardation function can be applied to a glass substrate of a liquid crystal cell of a liquid crystal display device, for example, but the λ / 4 retardation layer is located on the opposite side of the liquid crystal layer with respect to the thin film glass. 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.

  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 change and suppressing retardation unevenness, and an organic EL display device and a liquid crystal display device including the glass.

  The above object of the present invention is achieved by the following configurations.

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. 2. The glass with retardation function as described in 1 above, wherein the λ / 4 retardation layer contains a cellulose resin.

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). 4. The glass with retardation function as described in 3 above, wherein the resin layer is made of a cellulose-based resin.

  5. The in-plane retardation Ro of the resin layer is 0 to 5 nm, and the retardation Rt in the thickness direction is −10 to 10 nm.

  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). 7. The glass with retardation function according to any one of 1 to 6, wherein the reactive metal compound contains silicon alkoxide.

  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. 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.

  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.

It is sectional drawing which shows the schematic structure of the organic electroluminescence display to which the glass with a phase difference function which concerns on embodiment of this invention is applied. It is sectional drawing which shows the example of a structure different from what was shown in FIG. 1 of the polarizing plate used for the said organic EL display apparatus. It is sectional drawing which shows the structural example different from what was shown in FIG. 1 of the said glass with a phase difference function. It is sectional drawing which shows the structure of the outline of the liquid crystal display device to which the said glass with phase difference function is applied.

  An embodiment of the present invention will be described below with reference to the drawings. In the present 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.

[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 organic 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.

  The organic EL element 2 is a display called OLED (Organic light-Emitting Diode), and in order on a substrate 21 made of glass, polyimide, or the like, for example, a metal electrode 22 made of aluminum, a light emitting layer 23 and a transparent electrode ( For example, an ITO (Indium Tin Oxide) 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.

  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.

  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 the 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 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).

  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.

  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.

[Details of glass with retardation function]
Next, the detail of the above-mentioned glass 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.

  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.

  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.

  In addition, since the polarizing layer 41 is directly bonded to the λ / 4 retardation layer 33, both the polarizing layer 41 and the λ / 4 retardation layer 33 are similarly affected by the environmental variation (for example, temperature change). 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.

  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.

  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.

  The metal component contained in the reactive metal compound tends to be strongly bonded to the material component of the glass 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 type 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.

  The resin layer 35 is laminated on the thin film glass 31 on the side opposite 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.

  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.

  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.

  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 a thermosetting epoxy resin can be used. In this embodiment, the organic-inorganic hybrid adhesive layer similar to the adhesive layer 32 is used. It consists of

  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.

  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.

  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.

[Configuration of liquid crystal display device]
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 phase difference 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.

  On the liquid crystal layer 63 side of the substrate 62, a pixel electrode corresponding to each pixel, a TFT (Thin Film Transistor) which is a switching element for controlling ON / OFF of display in each pixel, and various types of TFTs 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.

  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.

  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.

  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.

  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.

  In a so-called COA (Color filter On Array) type liquid crystal display device in which a color filter is formed on the substrate 62 side on which 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.

  The phase difference function glass 3 of the present 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), and HAN (Hybrid Aligned Nematic) can be used as cell substrates of liquid crystal display devices in various display modes.

  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). From this, 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.

[Details of each layer]
Hereinafter, the detail of each layer which comprises the glass with a phase difference function is demonstrated.

(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.

  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 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.

  The thin film glass is not particularly limited as long as it is a multicomponent 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.

  The surface of the thin film glass is preferably cleaned 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.

(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.

  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 after being dyed and uniaxially stretched, 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.

  In addition, 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 also be used. For example, Japanese Patent Nos. 4279944, 2009-93074, No. 4691205, No. 4751481, No. 4804588, No. 4804589, No. 1701555, No. 2011-248293, etc. A coating-type thin film polarizer can be obtained with reference to FIG.

  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.

  Further, a protective layer may be separately formed on the surface of the polarizing layer opposite to the adhesion side with 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

  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 retardation layer)
The λ / 4 retardation layer refers to a film in which the in-plane retardation of the film is 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.

  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
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). ).

  The in-plane retardation Ro of the λ / 4 retardation layer may be 115 to 160 nm, preferably 120 to 160 nm, and 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. When a long circular polarizing plate is produced using such a film and applied to, for example, an organic EL display In addition, 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 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, the hue when viewed obliquely on a large screen tends to deteriorate.

  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.

  Among them, as the λ / 4 retardation layer, it is preferable to use a cellulose resin in consideration of heat resistance during the durability test.

(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.

  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.

  The resin layer preferably has a small in-plane direction retardation (retardation) Ro and a thickness direction retardation (retardation) Rt, 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 (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.

  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 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.

  Although there is no limitation in particular as a cellulose of the raw material of the cellulose resin used for the resin layer of this embodiment, Cotton linter, wood pulp, kenaf etc. can be mentioned. 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.

  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 cellulose ester solution becomes too high, so that 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.

  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.

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 Corporation) Mw = 1,000,000-500 calibration curves with 13 samples were used. The 13 samples are preferably used at approximately equal intervals.

  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 acyl group substitution degree can be measured according to ASTM-D817-96.

<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.

《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.

  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.

  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.

<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.

  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. Moreover, the polymeric ultraviolet absorber described in JP-A-6-148430 is also preferably used.

《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.

  Examples of the inorganic compound 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.

  Examples of the organic compound include acrylic resin, silicone resin, fluorine compound resin, and urethane resin.

"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.

  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.

(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.

<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.

  The water added for the 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.

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.

  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.

  The solid catalyst as the hydrolysis catalyst is not particularly limited, and those listed below can be used.

(1) Cation exchange resin:
Amberlite 15, Amberlite 200C, Amberlist 15 (above, manufactured by Rohm and Haas); Dowex MWC-1-H, Dowex 88, Dowex HCR-W2 (above, Dow Chemical Co.); Levacit SPC-108, Levacit SPC-118 (above, Bayer); Diaion RCP-150H (Mitsubishi Kasei); Sumikaion KC-470, Duolite C26-C, Duolite C-433, Duolite-464 (The above, manufactured by Sumitomo Chemical Co., Ltd.); Nafion-H (manufactured by DuPont) and the like.

(2) Anion exchange resin:
Amberlite IRA-400, Amberlite IRA-45 (above, manufactured by Rohm and Haas) and the like.

(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.

(4) Polyorganosiloxane containing protonic acid groups:
Polyorganosiloxane having a sulfonic acid group.

(5) Heteropoly acid:
Cobalt tungstic acid, phosphomolybdic acid, etc.

(6) Isopolyacid:
Niobic acid, tantalum acid, molybdic acid, etc.

(7) Unitary metal oxide:
Alumina, chromia, zirconia, CaO, MgO, etc.

(8) Composite metal oxide:
Silica-alumina, silica-magnesia, silica-zirconia, zeolites and the like.

(9) Clay mineral:
Acid clay, activated clay, montmorillonite, kaolinite, etc.

(10) Metal sulfate:
LiSO ₄ , MgSO _{4 and the} like.

(11) Metal phosphate:
Zirconia phosphate, lanthanum phosphate, etc.

(12) Metal nitrate:
Such as _{LiNO 3, Mn (NO 3)} 2.

(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) Polyorganosiloxane containing amino groups:
Amino-modified silicone resin.

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. Among these, Burolite CT-175 (manufactured by Burolite) is particularly preferable.

  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.

  Although there is no restriction | limiting in particular as a particle size of the cation exchange resin used by this embodiment, The range whose average particle diameter is 10-2000 micrometers is preferable. When the average particle size is less than 10 μm, filterability and liquid breakage may be deteriorated during resin separation after 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.

  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.

  In this 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 mass%. 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.

  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.

<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.

  Examples of the reactive metal compound capable of hydrolysis polycondensation used in this embodiment include metal alkoxide, metal diketonate, metal alkyl acetoacetate, metal isocyanate, and reactive metal halide. Preferably, the metal species is an alkoxide of Si, Ti, Zr or Al, and particularly preferably an alkoxide of Si.

  Such a reactive polycondensable reactive metal compound 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.

Equation _{(1) A p M q B} r → A p M q O r / 2

The hydrolyzable polycondensable reactive metal compounds, 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.

  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.

  Examples of the reactive metal compound 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.

  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, ethyltriiso Lopoxysilane, 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, (3,3,3 (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) trichlorosilane Methyl triisocyanate silane, phenyl triisocyanate silane, vinyl triisocyanate silane, and the like. 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.

  In addition, as titanium compounds, 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 triethanolamate, butyl titanate dimer, etc. Can be mentioned.

  Further, as the zirconium compound, zirconium-n-propoxide, zirconium-n-butoxide, zirconium tri-n-butoxide acetylacetonate, zirconium di-n-butoxide bisacetylacetonate, zirconium acetylacetonate, zirconium acetate, etc. Is mentioned.

  Examples of the aluminum compound include aluminum ethoxide, aluminum isopropoxide, aluminum n-butoxide, aluminum s-butoxide, aluminum di-s-butoxide ethylacetylacetonate, aluminum tert-butoxide, almatrane, aluminum phenoxide. , Aluminum acetylacetonate, aluminum ethylacetylacetonate and the like.

  Examples of the compound composed of other metals 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, tetra Toxigermane, 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.

  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.

<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.

  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.

  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 acrylamide, an acrylamide resin having a hydroxyl group such as N- (4- (4-hydroxyphenylsulfonyl) phenoxycarbonyl) methacrylamide, and the like can 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 Propylmethylcellulose, carboxymethylcellulose, methylcellulose Scan, ethylcellulose, and the like of these cationic products can be mentioned.

  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.

〔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.

<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.

<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

<Composition of dope solution>
Methylene chloride 340 parts by mass 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 mass Particulate 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.

  Then, 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 becomes 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.

  Next, drying was terminated 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.

  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.

<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.

<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

<Composition of dope solution>
Methylene chloride 340 parts by mass 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 weight Sugar ester compound A 5 parts by weight Polyester B 5 parts by weight TINUVIN 928 (manufactured by BASF Japan Ltd.) 2 parts by weight Particulate additive solution 2 parts by weight A dope solution was prepared.

  In addition, the sugar ester compound A and the polyester B are shown by the following structural formulas.

  Then, 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 becomes 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.

  Next, drying was terminated 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.

  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 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.

<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

<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

<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.

<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. The glass with retardation function of Comparative Example 1 is referred to as glass 5 with retardation function.

<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.

<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. doing.

  The method and evaluation criteria for evaluating the phase difference unevenness are as follows. Glasses 1 to 6 with retardation function are 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 is 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.

(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.

  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 in which the raw material of the adhesive layer includes TMOS (or TEOS) and DAC, 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.

  In particular, 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.

[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.

  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 a 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 a retardation function and the polarizing plate.

  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.

  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.

  In the organic EL display device or the liquid crystal display device, the polarizing plate is configured such that a polarizing layer that transmits linearly polarized light is sandwiched between two protective layers from one side, and the other protective layer is a λ / 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.

DESCRIPTION OF SYMBOLS 1 Organic EL display device 2 Organic EL element 3 Glass with phase difference function 31 Thin film glass 32 Adhesive layer (1st adhesive layer)
33 λ / 4 retardation layer 34 adhesive layer (second adhesive layer)
35 Resin layer 51 Liquid crystal display device 61 Substrate 62 Substrate 63 Liquid crystal layer

Claims (9)

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.   The glass with a retardation function according to claim 1, wherein the λ / 4 retardation layer contains a cellulose-based resin. 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.   The said resin layer consists of cellulose resin, Glass with a phase difference function of Claim 3 characterized by the above-mentioned.   The in-plane retardation Ro of the resin layer is 0 to 5 nm, and the retardation Rt in the thickness direction is −10 to 10 nm. The glass with a retardation function according to claim 3 or 4.   The glass with a polarizing function according to any one of claims 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.   The said reactive metal compound contains silicon alkoxide, Glass with phase difference function in any one of Claim 1 to 6 characterized by the above-mentioned.   An organic EL display device comprising the glass with a retardation function according to claim 1 on an organic EL element. A liquid crystal display device having a liquid crystal layer sandwiched between two substrates,
A liquid crystal display device, wherein at least one of the two substrates is made of the glass with a retardation function according to claim 1.

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