JPWO2014171503A1 - Glass laminate, thin film glass with transparent resin layer, liquid crystal display device and organic EL display device - Google Patents

Abstract

A substrate (11) as a glass laminate is configured by laminating a resin layer (21), an adhesive layer (22), a thin film glass (23), an adhesive layer (24), and a polarizing layer (25) in this order. . The resin layers (21) and (24) contain a cocondensate of a reactive metal compound and a hydroxyl group-containing polymer compound. The tensile load per unit strain of the resin layer (21) is 50 N or more. The polarizing layer (25) contains a polyvinyl alcohol resin.

Description

  The present invention relates to a glass laminate in which a resin layer is laminated on a thin film glass and a thin film glass with a transparent resin layer, and a liquid crystal display device and an organic EL (Electro-Luminescence) display device including the same. It is.

  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. As a countermeasure, a method has been proposed in which thin film glass and a film are bonded together to compensate for the flexibility and cracking property of the thin film glass.

  For example, in patent document 1, the reduction | damage at the time of handling a glass film is aimed at by adhere | attaching a resin film on the glass film of thickness 0.1 micrometer-100 micrometers via an adhesive agent. 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.)

  As above-mentioned, the intensity | strength of thin film glass can be supplemented by bonding a film to thin film glass via an adhesive agent. When applying such a thin film glass with a film to a liquid crystal display device, for example, if the film on the thin film glass can have a function as a polarizing plate to form a glass laminate, A liquid crystal cell (in which a liquid crystal layer is sandwiched between two substrates) can be manufactured, and a step of attaching a polarizing plate after manufacturing the liquid crystal cell becomes unnecessary, which is desirable.

  Here, generally the polarizing plate used for a liquid crystal display device is comprised by bonding together a surface protection film and a back surface protection film on the surface and back surface of a polarizing layer (polarizer), respectively. In constructing the glass laminate, the polarizing plate having the above three-layer structure may be laminated as it is on the thin film glass, but the back side of the polarizing layer is protected by the thin film glass, so the back protective film is omitted. And you may comprise a glass laminated body. That is, the polarizing layer may be directly contacted with the adhesive and laminated on the thin film glass to constitute a glass laminate. In this case, it is possible to reduce the thickness and cost of the glass laminate by eliminating the need for the back surface protective film.

  However, as a result of performing a durability test by bringing the polarizing layer into direct contact with the adhesive and laminating it on the thin film glass, it was found that there was a problem in durability and handling properties. This is considered to be due to the following reasons. That is, when a conventional acrylic pressure-sensitive adhesive is used as the adhesive, good adhesion cannot be secured to both the thin film glass and the polarizing layer (resin) of different materials. The adhesion of the polarizing layer is reduced. For this reason, the polarizing layer easily deteriorates due to environmental fluctuations during the durability test, and the degree of polarization is uneven. Moreover, since the bending rigidity (strength with respect to bending) of a glass laminated body falls by the adhesive fall of thin film glass and a polarizing layer, handling property worsens and it becomes easy to break glass at the time of handling.

  Furthermore, considering that the above-described liquid crystal display device is used in various applications such as mobile applications, in-vehicle applications, and digital signage applications, there is a possibility of being placed in various environments. In particular, in digital signage applications, different usage methods are assumed. For example, it may be used as an outdoor advertisement by being affixed to the body of an automobile, or as a guidance display at a construction site.

  In such applications, washing is repeated using water to remove outdoor dust, oil and sebum used in construction. At this time, the polarizing layer of the glass laminate is greatly expanded and contracted, and the stress propagates throughout the glass laminate, which may cause cracks and cracks. Therefore, the glass laminate is also required to have water resistance that does not cause cracking or cracking due to cleaning.

  It is also conceivable to apply the above glass laminate to an organic EL (Electro-Luminescence) display device.

  In addition, when forming a thin film glass with a transparent resin layer by adhering a transparent resin layer to the thin film glass via an adhesive, when using a conventional acrylic pressure-sensitive adhesive or epoxy adhesive as the adhesive, Since favorable adhesiveness cannot be ensured with respect to both the thin film glass and transparent resin layer from which a material differs, the adhesiveness of the transparent resin layer with respect to thin film glass falls. For this reason, the bending rigidity (strength with respect to bending) of thin film glass with a transparent resin layer falls, and it becomes easy to break at the time of handling (impact resistance falls). Therefore, it is desirable to use an adhesive that can ensure good adhesion to both the thin film glass and the transparent resin layer.

  However, using such an adhesive, the transparent resin layers are bonded to both surfaces of the thin film glass to form a thin film glass with a (double-sided) transparent resin layer, so that the adhesion between the thin film glass and the transparent resin layer is high. Therefore, when the transparent resin layer contracts, the influence of the contraction on the warp of the thin film glass becomes large. For this reason, the following problems arise.

  In recent years, the usage environment of display devices using thin glass with a transparent resin layer is changing due to the thinning and weight reduction of the thin glass with a transparent resin layer, and display in an environment that has never been considered before. The number of cases where devices are used is increasing. Specifically, the thin and lightweight display device using thin glass with a transparent resin layer has made it very easy to carry the display device easily and freely because the restrictions on carrying the display device have been greatly reduced. There is a type of usage that has not been envisaged in the past, such as bringing a display device to a facility or home bathroom, and viewing display information (including TV images, information on the Internet, e-mail, etc.) while taking a bath. It is starting to increase.

  Here, there is a correlation between the polymer orientation of the transparent resin layer (presumably the orientation of the polymer main chain) and the tensile elastic modulus of the transparent resin layer, and the transparent resin layer is in the direction of polymer orientation. The tensile modulus is large and therefore tends to shrink in the same direction. Therefore, unless the direction in which the tensile modulus of elasticity is large in each transparent resin layer on both sides (the direction in which shrinkage is likely to occur) is not set appropriately, at room temperature and normal humidity, the transparent resin layer is stretched (shrinked) on both sides of the thin film glass. Even if the balance is achieved, the transparent balance is easily lost when the transparent resin layer absorbs moisture and contracts in an ultra-high humidity environment. As a result, in an ultra-high humidity environment, the thin film glass with a transparent resin layer tends to warp, and a display device using the glass breaks or causes a display defect. In particular, when the moisture permeability (water vapor permeability) of the transparent resin layer is high, the transparent resin layer easily absorbs moisture in the atmosphere, so that the shrinkage balance is more easily lost, and the above problem is more likely to occur.

  In view of the above circumstances, the object of the present invention is to suppress the deterioration of the polarizing layer due to environmental fluctuations and improve the handling property even in the configuration in which the polarizing layer is directly contacted with the adhesive and laminated on the thin film glass. Furthermore, another object of the present invention is to provide a glass laminate that does not crack or break even when repeatedly washed with water, and a liquid crystal display device and an organic EL display device including the glass laminate.

  Another object of the present invention is to improve the adhesion between the thin film glass and the transparent resin layer in view of the circumstances described above, even when used in an ultra-high humidity environment. An object of the present invention is to provide a thin film glass with a transparent resin layer capable of reducing a warp while maintaining a balance of shrinkage in each transparent resin layer, and a liquid crystal display device and an organic EL display device including the same.

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

1. The resin layer, the first adhesive, the thin glass, the second adhesive, and the polarizing layer are laminated in this order,
The first and second adhesives include a cocondensate of a reactive metal compound and a hydroxyl group-containing polymer compound,
The tensile load per unit strain of the resin layer is 50 N or more,
The polarizing layer contains a polyvinyl alcohol-based resin.

  2. 2. The glass laminate according to 1 above, wherein the resin layer contains a cellulose ester.

  3. 3. The glass laminate according to 1 or 2 above, wherein the hydroxyl group-containing polymer compound contains a cellulose derivative or polyvinyl alcohol.

  4). 4. The glass laminate according to 3 above, wherein the cellulose derivative is a cellulose ester resin.

  5). The glass laminate as described in 4 above, wherein the cellulose ester resin has a total acyl group substitution degree of 1.0 to 2.6.

  6). 6. The glass laminate according to any one of 1 to 5, wherein the reactive metal compound is silicon alkoxide.

  7). 7. The glass laminate according to any one of 1 to 6, wherein the thin film glass has a thickness of 5 to 100 μm.

8). A liquid crystal display device in which a liquid crystal layer is sandwiched between a pair of substrates,
At least one of said pair of board | substrates has the glass laminated body in any one of said 1-7, The liquid crystal display device characterized by the above-mentioned.

9. An organic EL display device having a cover glass disposed on the front surface of an organic EL element,
The said cover glass has the glass laminated body in any one of said 1-7, The organic electroluminescence display characterized by the above-mentioned.

10. It is a thin film glass with a transparent resin layer in which a transparent resin layer is laminated on each side of the thin film via an adhesive layer,
The adhesive layer contains a cocondensate of a reactive metal compound and a hydroxyl group-containing polymer compound,
In the transparent resin layer on one side of the thin film glass and the transparent resin layer on the other side, the deviation in the direction in which the tensile elastic modulus is maximum is within 10 °,
A thin film glass with a transparent resin layer, wherein water vapor permeability of at least one transparent resin layer is smaller than 1000 g / m ² · 24 hr.

  11. 11. The thin film glass with a transparent resin layer according to 10, wherein each of the transparent resin layers has a tensile elastic modulus of 1 GPa to 6 GPa.

  12 The thin film glass with a transparent resin layer according to 10 or 11, wherein the in-plane retardation of at least one transparent resin layer is 30 nm to 200 nm.

  13. The thin film glass with a transparent resin layer according to any one of 10 to 12, wherein an average thickness of the thin film glass is 5 to 200 μm.

14 A liquid crystal display device in which a liquid crystal layer is sandwiched between a pair of substrates,
At least one of said pair of board | substrates has the thin film glass with a transparent resin layer in any one of said 10-13, The liquid crystal display device characterized by the above-mentioned.

15. An organic EL display device having a cover glass disposed on the front surface of an organic EL element,
The organic EL display device, wherein the cover glass includes the thin film glass with a transparent resin layer according to any one of 10 to 13 above.

  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. Therefore, the first and second adhesives are cocondensates of a reactive metal compound and a hydroxyl group-containing polymer compound, and have both the characteristics of the reactive metal compound and the hydroxyl group-containing polymer compound. Thus, it is possible to ensure good adhesion to both the thin film glass and the resin layer or the polarizing layer. And the adhesiveness of thin film glass and a resin layer or a polarizing layer can be improved through the 1st or 2nd adhesive agent. As a result, it is possible to suppress the polarization layer from being deteriorated due to environmental fluctuations and causing unevenness in the degree of polarization. Moreover, the bending rigidity of a glass laminated body can be improved and handling property can be improved (breakage of the glass at the time of handling can be reduced).

  Moreover, by using a film having a large tensile load per unit strain as the resin layer, it is possible to suppress warping of the glass laminate due to expansion and contraction of the polarizing layer with respect to water, and to prevent cracks and cracks. Therefore, the glass laminate of the present invention can be used without any problem for a long period of time, even if it is used in such applications as washing repeatedly with water.

  In addition, as described above, the metal component contained in the reactive metal compound can be covalently bonded to the glass component, and the hydroxyl group-containing polymer compound has high affinity with the resin, so that the thin film glass and the transparent resin layer The adhesive layer is a co-condensate of a reactive metal compound and a hydroxyl group-containing polymer compound, and has both the characteristics of the reactive metal compound and the hydroxyl group-containing polymer compound, thereby making it transparent with thin film glass. Good adhesion to both the resin layer can be ensured. Thereby, through the said adhesive layer, the adhesiveness of thin film glass and a transparent resin layer can be improved, and impact resistance can be improved. 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.

  Further, since the deviation in the direction in which the tensile elastic modulus is maximum is within 10 ° between the transparent resin layer on one side of the thin film glass and the transparent resin layer on the other side, the orientation state of each transparent resin layer (Orientation direction) is substantially aligned in one direction, and the direction in which the shrinkage of each transparent resin layer is large is also approximately aligned in one direction (alignment direction). Thereby, the balance of shrinkage can be maintained in each transparent resin layer on both sides of the thin film glass even under an ultra-high humidity environment, and the thin film glass with the transparent resin layer can be reduced from warping. .

Moreover, since the water vapor transmission rate of at least one of the transparent resin layers is smaller than 1000 g / m ² · 24 hr, it is possible to suppress the absorption of moisture in the transparent resin layer and the shrinkage thereof, and to reliably reduce the warpage. it can. Of course, both transparent resin layers have low moisture permeability, and even when only one of them has low moisture permeability, the other transparent resin layer is opposite to the atmosphere side (for example, the liquid crystal layer side). By using the thin glass with a transparent resin layer to suppress the absorption and shrinkage of moisture in the other transparent resin layer, warpage can be reduced.

1 is a cross-sectional view illustrating a schematic configuration of a liquid crystal display device according to an embodiment of the present invention. It is sectional drawing which shows one structural example of the glass laminated body applied to the said liquid crystal display device. 1 is a cross-sectional view showing a schematic configuration of an organic EL display device according to an embodiment of the present invention. It is sectional drawing which shows the schematic structure of the thin film glass with a transparent resin layer applied to the said liquid crystal display device and the said organic EL display device. It is sectional drawing which shows simply the structure of the said organic EL display apparatus.

  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 liquid crystal display device]
FIG. 1 is a cross-sectional view showing a schematic configuration of a liquid crystal display device 1 of the present embodiment. The liquid crystal display device 1 includes a liquid crystal panel 2 and a backlight 3 that illuminates the liquid crystal panel 2. The liquid crystal panel 2 is configured by sandwiching a liquid crystal layer 13 between two substrates 11 and 12. The liquid crystal layer 13 is sealed between the two substrates 11 and 12 by a sealing material 14.

  Of the two substrates 11 and 12, the substrate 11 located on the side opposite to the backlight 3 side with respect to the liquid crystal layer 13 is composed of a glass laminate having a resin layer and a polarizing layer. Will be described later. On the backlight 3 side of the substrate 12, the polarizing layer and a polarizing plate (not shown) in a crossed Nicols state are disposed. In addition, you may comprise the board | substrate 12 with a glass laminated body instead of arrange | positioning the said polarizing plate.

  On the liquid crystal layer 13 side of the substrate 12, 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 kinds 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 substrate 11 on the liquid crystal layer 13 side.

  In the above configuration, of the light emitted from the backlight 3, the light (linearly polarized light) transmitted through the polarizing plate on the back surface side of the liquid crystal panel 2 enters the liquid crystal layer 13 through the substrate 12, and the liquid crystal layer 13 While propagating in the thickness direction, the polarization state changes according to the refractive index anisotropy (birefringence) of the liquid crystal. Of the light incident on the substrate 11 via the liquid crystal layer 13, only the light of the polarization component in a specific direction passes through the polarization layer of the substrate 11 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 13 for each pixel by ON / OFF control of the TFT.

  The display mode of the liquid crystal display device 1 is not particularly limited. Examples of the display mode include 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), any display mode may be adopted.

[About glass laminates]
Next, the substrate 11 as a glass laminate will be described. FIG. 2 is a cross-sectional view illustrating a configuration example of the substrate 11. The substrate 11 is configured by laminating a resin layer 21, an adhesive layer 22 (first adhesive), a thin film glass 23, an adhesive layer 24 (second adhesive), a polarizing layer 25, and a protective layer 26 in this order. ing.

  The case where the adhesive layers 22 and 24 are not clearly present as layers is also included in the scope of the present invention. It is assumed that the components contained in the adhesive layers 22 and 24 are integrated by penetrating and reacting with the resin layer 21 or the polarizing layer 25.

  The resin layer 21 is a layer that improves the strength of the substrate 11 and is not particularly limited as long as it is an optically transparent resin. And the tensile load per unit strain of the resin layer 21 should just be 50 N or more. The reason for this will be described later.

  The polarizing layer 25 is a polarizer that transmits predetermined linearly polarized light, and includes a polyvinyl alcohol resin. For example, it can be obtained by dyeing a polyvinyl alcohol film with a dichroic dye and stretching it at a high magnification. The protective layer 26 is provided for the purpose of protecting the surface of the polarizing layer 25. The protective layer 26 is adhered to the polarizing layer 25 via an ultraviolet curable adhesive, or the polarizing layer 25 using a polyvinyl alcohol aqueous solution as an adhesive (water glue). Are pasted together.

  The adhesive layers 22 and 24 are organic-inorganic hybrid type adhesive layers containing a condensate (co-condensate) of a reactive metal compound (inorganic compound) and a hydroxyl group-containing polymer compound (organic compound) ( HB glue). The co-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 subjected to a condensation reaction. 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 is possible to improve the affinity with the resin layer 21 and the polarizing layer 25 made of a resin, thereby improving the adhesiveness. In addition, the organic compound and the inorganic compound are poorly compatible, but by forming these condensates, the adhesive layers 22 and 24 having both characteristics in a single layer structure can be formed.

  Therefore, by using the organic-inorganic hybrid type adhesive layers 22, 24, adhesion between the thin film glass 23 and the resin layer 21 or the polarizing layer 25 can be improved via the adhesive layers 22, 24. As a result, the polarizing layer 25 is not easily deteriorated due to environmental fluctuations during the durability test, and unevenness in the degree of polarization can be suppressed. Further, by improving the adhesion between the thin film glass 23 and the resin layer 21 or the polarizing layer 25, it is possible to increase the bending rigidity of the substrate 11 as a glass laminate, improve the handling property, and damage the glass during handling. Can be reduced.

  In addition, since the polyvinyl alcohol resin contained in the polarizing layer 25 has strong hydrophilicity, the affinity between the adhesive layer 22 containing a hydroxyl group and the polarizing layer 25 is further improved, and the adhesion between the thin film glass 23 and the polarizing layer 25 is improved. Is further improved. Therefore, when the polarizing layer 25 includes a polyvinyl alcohol-based resin, a configuration using the adhesive layer 24 containing a hydroxyl group is very effective.

  The thickness of the polarizing layer 25 is preferably 10 μm or less. In this case, the above-described effects can be obtained with the thin configuration of the polarizing layer 25.

  On the other hand, since the polyvinyl alcohol resin contained in the polarizing layer 25 has strong hydrophilicity, the polarizing layer 25 has a large expansion and contraction with respect to water. Therefore, when it is repeatedly washed with water in order to remove outdoor dust, oil or sebum used in construction, the polarizing layer 25 greatly expands and contracts, and the stress propagates throughout the substrate 11. At this time, if the substrate 11 is warped, cracks and cracks may occur. However, if the resin layer 21 is laminated as in the present embodiment, the strength of the substrate 11 is increased and warping is suppressed, and cracks and cracks are generated. Can be prevented.

  The hydroxyl group-containing polymer compound is preferably a cellulose ester having a total acyl group substitution degree of 1.0 to 2.6. As such a cellulose ester, for example, diacetyl cellulose (DAC) or cellulose acetate propionate (CAP) can be used. Such a cellulose ester contains a hydroxyl group and improves the affinity with the resin layer 21 and the polarizing layer 25 made of a resin. Therefore, the cellulose ester is very effective as a material for improving the adhesiveness with the resin layer 21 or the polarizing layer 25. It is.

  By the way, when forming a color filter on the board | substrate 11, there exists the method of forming a color filter by an inkjet system, for example using a latent pigment as an 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 21.

  In the so-called COA (Color filter On Array) type liquid crystal display device in which a color filter is formed on the substrate 12 side on which the TFT is formed, the resin layer 21 of the substrate 11 does not need heat resistance when the color filter is formed. Therefore, the resin layer 26 can be made of a resin other than the cellulose resin.

  Further, in the liquid crystal display device, as described above, there are IPS method, TN method, VA method, and the like as the driving method of the liquid crystal, but the IPS method has better viewing angle performance than the TN method and VA method. There is a feature that. For this reason, in the case of the IPS system, it is desirable that the phase difference in the resin layer 21 is almost zero (the visibility can be improved when the phase difference is close to zero). Therefore, it is desirable that the in-plane retardation Ro of the resin layer 21 is 0 to 5 nm and the thickness direction retardation Rt is −10 to 10 nm.

[Configuration of organic EL display device]
FIG. 3 is a cross-sectional view showing a schematic configuration of the organic EL display device 31 of the present embodiment. The substrate 11 that is the glass laminate described above can also be applied to the organic EL display device 31. In this case, the resin layer 21 is provided with a retardation function to form a λ / 4 retardation layer.

  The organic EL display device 31 includes an organic EL element 32 and a substrate 11 as a cover glass. In the figure, in order to clearly distinguish the organic EL element 32 and the substrate 11, they are shown separated from each other, but they are actually in close contact with each other.

  The organic EL element 32 is a display called OLED (Organic light-Emitting Diode), and in order on a substrate 33 using glass, polyimide, or the like, for example, a metal electrode 34 made of aluminum, a light emitting layer 35 and a transparent electrode ( For example, an ITO (Indium Tin Oxide) 36 is included. Originally, a sealing glass for protecting the surface is provided on the transparent electrode 36, but in this embodiment, the substrate 11 is used as a substitute for the sealing glass.

  When a voltage is applied to the metal electrode 34 and the transparent electrode 36, electrons are injected from the electrode serving as the cathode of the metal electrode 34 and the transparent electrode 36 into the light emitting layer 35, and holes are injected from the electrode serving as the anode. Then, when the two recombine in the light emitting layer 35, visible light emission corresponding to the light emission characteristics of the light emitting layer 35 occurs. The light generated in the light emitting layer 35 is taken out through the transparent electrode 36 and the substrate 11 directly or after being reflected by the metal electrode 34.

  The substrate 11 is provided to protect the surface of the transparent electrode 36 and prevent reflection of external light incident on the organic EL element 2.

  Of the external light incident on the substrate 11, the light transmitted through the polarizing layer 25 (linearly polarized light) is converted into circularly polarized light by the λ / 4 phase difference layer (resin layer 21), and is transmitted by the metal electrode 34 of the organic EL element 32. When reflected, the phase is inverted by 180 ° and reflected as a reverse circularly polarized light. The reflected light again enters the λ / 4 retardation layer, is converted into linearly polarized light perpendicular to the transmission axis of the polarizing layer 25, and is all absorbed by the polarizing layer 25.

  In the case where the light emitting layer 35 of the organic EL element 32 is configured to emit white light, for example, color filters for R (red), G (green), and B (blue) are used to support color display. Is required. In this case, for example, there is a method of forming a color filter on the λ / 4 retardation layer side of the substrate 11 by an inkjet 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 heat-resistant cellulose resin such as triacetyl cellulose (TAC) as the λ / 4 retardation layer.

  When the light emitting layer 35 is configured to emit RGB light, the λ / 4 retardation layer does not need the heat resistance when the color filter is formed, and thus the λ / 4 retardation layer. Can be comprised with resin (for example, polycarbonate resin) other than a cellulose resin.

  Further, when the angle formed between the slow axis of the λ / 4 retardation layer and the absorption axis of the polarizing layer 25 is set to 30 to 60 °, the linearly polarized light transmitted through the polarizing layer 25 is circularly polarized or elliptically polarized. And converted to the metal electrode 34, the reflected light from the metal electrode 34 (circularly polarized light or elliptically polarized light reverse to the above) is converted into linearly polarized light in a direction perpendicular to the transmission axis of the polarizing layer 25, Light reflection can be prevented.

[About thin film glass with transparent resin layer]
Next, the thin film glass with a transparent resin layer of this embodiment applicable to the above-described display device will be described. FIG. 4 is a cross-sectional view illustrating a schematic configuration of the thin film glass with a transparent resin layer 40 of the present embodiment.

  At least one of the substrates 11 and 12 of the liquid crystal display device 1 shown in FIG. 1 may be constituted by the thin film glass 40 with a transparent resin layer shown in FIG. The thin film glass 40 with a transparent resin layer does not have the polarizing layer 25 like the glass laminated body mentioned above. For this reason, a polarizing plate (not shown) is arranged in a crossed Nicol state outside the substrates 11 and 12 (on the side opposite to the liquid crystal layer 13). In the case of a polymer dispersion type liquid crystal display device, the above polarizing plate is not necessary. Further, as shown in FIG. 5, a thin film glass 40 with a transparent resin layer may be used as the cover glass 37 of the organic EL display device 31. Hereinafter, the thin film glass 40 with a transparent resin layer will be described.

  The thin film glass 40 with a transparent resin layer is formed by laminating an adhesive layer 42 and a transparent resin layer 43 in this order on one surface side of the thin film glass 41, and an adhesive layer 44 and a transparent resin layer 45 on the other surface side. It is constructed by stacking in order.

  The case where the adhesive layers 42 and 44 are not clearly present as layers is also included in the scope of the present invention. It is assumed that the components contained in the adhesive layers 42 and 44 are integrated by penetrating and reacting with the transparent resin layers 43 and 45.

  The transparent resin layer 43 includes a cellulose resin or a polycarbonate resin (PC). From the viewpoint of heat resistance during a heat resistance test, the transparent resin layer 43 preferably includes a heat resistant cellulose resin. As such a cellulose resin, for example, diacetyl cellulose (DAC) or cellulose acetate propionate (CAP) can be used.

  The transparent resin layer 45 is laminated on the opposite side of the thin film glass 41 from the transparent resin layer 43 with an adhesive layer 44 for the purpose of further improving the strength of the thin film glass 40 with a transparent resin layer. That is, by providing the transparent resin layer 45, the thin film glass 41 is sandwiched between the resin layers (transparent resin layer 43, transparent resin layer 45) from both sides, so that the resin layer (transparent resin layer 43) is provided only on one side of the thin film glass 41. Compared with the structure which provides, the intensity | strength of the thin film glass 40 with a transparent resin layer whole can further be improved.

  Here, when the color filter is formed by the inkjet method on the transparent resin layer 45 side of the thin film glass 40 with the transparent resin layer using the latent pigment as the ink, the heating for fixing the latent pigment is necessary as described above. This is the same as in the case of the laminated glass. In the case where heat resistance is required for the transparent resin layer 45, it is desirable to use a cellulose resin having heat resistance such as triacetyl cellulose (TAC) as the transparent resin layer 45. When such heat resistance is not required, the transparent resin layer 45 can be composed of a resin (for example, polycarbonate resin) other than the cellulose resin.

  The adhesive layers 42 and 44 are, like the adhesive layers 22 and 24 of the glass laminate described above, a condensate (co-polymer) of a reactive metal compound (inorganic compound) and a hydroxyl group-containing polymer compound (organic compound). An organic-inorganic hybrid adhesive layer (HB glue) containing a condensate). As the reactive metal compound, for example, silicon alkoxide such as TEOS or TMOS can be used. Further, as the hydroxyl group-containing polymer compound, for example, DAC or CAP can be used.

  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 layers 42 and 44, the adhesion between the thin film glass 41 and the transparent resin layer 43 can be improved via the adhesive layer 42. Thus, the adhesion between the thin film glass 41 and the transparent resin layer 45 can be improved. Thereby, the bending rigidity of the thin film glass 40 with a transparent resin layer can be improved, and damage can be reduced (impact resistance can be improved). In general, organic compounds and inorganic compounds are poorly compatible, but by forming these condensates, the adhesive layers 42 and 44 having both characteristics in a single layer structure can be easily formed. Can be realized.

  In particular, 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 the affinity with the transparent resin layer 43 or the transparent resin layer 45 made of resin is improved. Therefore, the adhesion between the thin film glass 41 and the transparent resin layer 43 and the thin film glass 41 are improved. It is very effective as a material for improving the adhesion between the transparent resin layer 45 and the transparent resin layer 45.

Moreover, in this embodiment, the deviation in the direction in which the tensile elastic modulus is maximum is within 10 ° between the transparent resin layer 43 on one side of the thin film glass 41 and the transparent resin layer 45 on the other side. The water vapor permeability (moisture permeability) in the transparent resin layers 43 and 45 is smaller than 1000 g / m ² · 24 hr.

The direction in which the tensile elastic modulus is maximized can be obtained as follows. With respect to the resin film (single unit) constituting each transparent resin layer 43 and 45, 3 to 4 directions (in 45 ° increments with respect to a reference direction (for example, a conveyance direction during film formation) in a plane by a tensile tester ( For example, each direction of 0 °, 45 °, 90 °, and 135 ° is measured, and the elastic modulus in each direction is measured to perform an ellipse approximation, and the major axis direction of the approximated ellipse is set as the maximum direction of the tensile elastic modulus. . That is, the elastic modulus in the 0 ° direction is a value in the 0 ° direction and the 180 ° direction, the elastic modulus in the 45 ° direction is a value in the 45 ° direction and the 225 ° direction, and the elastic modulus in the 90 ° direction is the 90 ° direction and 270 °. As the value in the ° direction, the elastic modulus in the 135 ° direction is plotted on the coordinate axes as the values in the 135 ° direction and the 315 ° direction to create an ellipse, and the major axis direction of the ellipse is the direction of the maximum tensile elastic modulus. And Further, an elliptical equation (x ² + Axy + By ² + C = 0) is obtained based on the values of the tensile modulus in four directions, and from this equation, the rotation angle θ = {tan ⁻¹ (A / (B−1))} / 2 may be obtained, and the direction of the rotation angle θ may be the direction with the maximum tensile elastic modulus.

  The tensile elastic modulus is also called Young's modulus, and is represented by a ratio between tensile stress per unit area and elongation generated in the stress direction. For example, the larger the value of the tensile modulus, the smaller the elongation (stress strain) in the stress direction when the tensile stress is constant, and the larger the tensile stress when the stress strain is constant. Shrinkage can be considered in the same way. The larger the value of the tensile modulus, the smaller the shrinkage when the stress during shrinkage is constant, and the larger the contraction stress (shrinking force) when the shrinkage is constant. Means that. The direction in which the tensile elastic modulus is large, that is, the direction in which the shrinkage force acts greatly coincides with the resin orientation direction (stretching direction).

  Therefore, when the deviation in the direction in which the tensile modulus of elasticity in the transparent resin layers 43 and 45 is maximum is within 10 ° as described above, the orientation state (orientation direction) of the transparent resin layers 43 and 45 is substantially aligned in one direction. I can say that. In this case, since the direction in which the shrinkage of the transparent resin layers 43 and 45 is large is aligned in almost one direction (orientation direction), even if the transparent resin layers 43 and 45 shrink by absorbing moisture in the air, the thin film glass 41 The transparent resin layers 43 and 45 shrink on both sides with good balance, and the balance of shrinkage is maintained on both sides of the thin film glass 41. As a result, even in an ultra-high humidity environment such as when bathing, the thin film glass 41 sandwiched between the transparent resin layers 43 and 45 is contracted by the transparent resin layers 43 and 45 due to moisture absorption. It is possible to reduce the warpage to either one of 43 and 45, and to reduce the warpage of the thin film glass 40 with a transparent resin layer, and the display device (the liquid crystal display device 1, the organic EL display device 31) to which the thin glass 40 is applied. can do. As a result, it is possible to reduce cracks and display defects of the display device due to use in an ultra-high humidity environment.

Moreover, since the water vapor transmission rate of the transparent resin layers 43 and 45 is less than 1000 g / m ² · 24 hr and has low moisture permeability, moisture absorption in the transparent resin layers 43 and 45 and the resulting shrinkage itself are suppressed, The warpage can be surely reduced.

  Further, since both of the transparent resin layers 43 and 45 have low moisture permeability, when the thin film glass 40 with the transparent resin layer is applied to the substrate 11 of the liquid crystal display device 1 or the cover glass of the organic EL display device 31, the transparent resin layer. Regardless of which of 43 and 45 is located on the atmosphere side, absorption of moisture in the atmosphere can be suppressed. Therefore, in disposing the thin film glass 40 with the transparent resin layer, there is no need to hesitate which of the transparent resin layers 43 and 45 is on the air side or on the liquid crystal layer side (or on the organic EL element side).

  Only one of the transparent resin layers 43 and 45 (for example, only the transparent resin layer 43) may have low moisture permeability. In this case, when applied to a display device, the low moisture-permeable transparent resin layer 43 is positioned on the atmosphere side, and the high moisture-permeable transparent resin layer 45 is on the liquid crystal layer side (or the organic EL element side). By disposing the thin film glass 40 with the transparent resin layer, the transparent resin layer 45 does not come into contact with the air, so that the absorption of moisture in the ultra-high humidity environment and the shrinkage of the shrinkage balance are reduced. Thus, the warpage can be reduced. Therefore, it can be said that at least one of the transparent resin layers 43 and 45 only needs to have low moisture permeability in order to obtain the above-described effect in the present embodiment.

  In particular, in the configuration in which the adhesion between the thin film glass 41 and the transparent resin layers 43 and 45 is improved by using the organic-inorganic hybrid adhesive layers 42 and 44 as in the present embodiment, the transparent resin layer 43 is used. Since the influence of 45 shrinkage on the warp of the thin film glass 41 becomes large, the deviation in the direction in which the tensile elastic modulus is maximized and the water vapor transmission rate of the transparent resin layers 43 and 45 are defined as described above. It is very effective to reduce the warp of the layered thin film glass 40.

  In addition, if the deviation in the direction in which the tensile elastic modulus is maximum in the transparent resin layers 43 and 45 is 0 °, that is, if the direction in which the tensile elastic modulus is maximum is completely parallel, the transparent resin layers 43 and 45 Since the orientation direction and the direction of large shrinkage are also completely aligned in one direction, the balance of shrinkage of the transparent resin layers 43 and 45 can be maintained best. Therefore, in this case, the effect of reducing the warpage of the thin film glass with a transparent resin layer 40 and thus the display device can be obtained to the maximum in an ultra-high humidity environment.

  In the present embodiment, the tensile elastic modulus of the transparent resin layers 43 and 45 is desirably 1 GPa to 6 GPa. If the tensile elastic modulus is less than 1 GPa, the rigidity of the transparent resin layers 43 and 45 is low, and there is a possibility that the stability of the applied film thickness cannot be ensured when an adhesive is applied to the transparent resin layers 43 and 45. Although the thin film glass 40 with a transparent resin layer of this embodiment can suppress curvature by the balance of the film of the both sides of glass, when a tensile elasticity modulus exceeds 6 GPa, adjustment with respect to curvature will become very difficult. In addition, the stiffness of the film is too strong, and there is a possibility that peeling occurs in the transporting process immediately after the adhesive is applied and bonded to the glass. From the viewpoint of the occurrence of wrinkles and distortion during film conveyance and the risk of breakage, a more preferable range of the tensile elastic modulus of the transparent resin layers 43 and 45 is 2 GPa to 5 GPa.

  In the present embodiment, the in-plane retardation of at least one of the transparent resin layers 43 and 45 is desirably 30 nm to 200 nm. In this case, the thin film glass 40 with a transparent resin layer according to the present embodiment can have an optical function for imparting a phase difference. In particular, when the thin film glass 40 with a transparent resin layer is applied to the liquid crystal display device 1. It becomes effective.

  The transparent resin layers 43 and 45 are desirably a polymer containing a hydroxyl group from the viewpoint of the wettability and adhesion of the organic-inorganic hybrid adhesive layer. The film thickness of the transparent resin layers 43 and 45 is preferably 5 μm to 65 μm. When the film thickness of the transparent resin layers 43 and 45 is less than the lower limit, it is difficult to suppress scratches generated on the glass due to external impact or the like, and it is difficult to protect the glass. The shrinkage force (shrinkage stress due to glass) due to the dimensional change of the resin layer is increased, and the birefringence generated by the photoelastic effect is increased.

[Details of each layer]
(Thin glass)
As thin film glass which comprises a glass laminated body and thin film glass with a transparent resin layer, 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 preferably treated with a silicon alkoxide such as TEOS or TMOS, or a silane coupling agent.

(Polarizing layer)
The polarizing layer of the glass laminate is an element (polarizer) that passes only light having a polarization plane 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 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.

  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 base material onto the thin film glass, the stretching film base material may be peeled off or may be utilized as it is as a protective layer without being peeled off. A coating-type thin film polarizer is preferably used because it can be made thinner than a polarizer using an original film.

  Moreover, you may form a protective layer separately in the surface on the opposite side to the adhesion | attachment side with the glass in a polarizing 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.

(Resin layer)
The resin layer formed on the side opposite to the polarizing layer with respect to the thin film glass and the resin layer used for the thin film glass with a transparent resin layer are not particularly limited as long as they are optically transparent resins. For example, acrylic resin, polycarbonate resin, cycloolefin resin, polyester resin, polylactic acid resin, polyvinyl alcohol resin, cellulose resin, and the like 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 plays a role of preventing cracks and cracks by increasing the strength of the glass laminate and suppressing warpage. Therefore, a resin layer having a tensile load per unit strain of 50 N or more is used.

In addition, the tensile load M per unit strain of the resin layer is represented by the following formula.
M [N] = E [MPa] × 10 [mm] × d [μm] × 10 ⁻³
In the formula, E represents the elastic modulus of the resin layer, and d represents the film thickness of the resin layer.

  The elastic modulus E and the film thickness d can be obtained by the following method, for example. That is, a film (resin layer) conditioned for 24 hours in an air-conditioned room at 23 ° C. and 55% RH was cut out at 120 mm (length) × 10 mm (width) under the same conditions, and Tensilon tester (produced by ORIENTEC, RTC- 1225A) is used, a tensile test is performed 5 times at a pulling speed of 50 mm / min, this measurement is performed in two orthogonal directions, and an average value is defined as an elastic modulus E. On the other hand, the film thickness d of the film is measured with a contact-type film thickness meter manufactured by Mitutoyo Corporation.

  The resin layer preferably has both an in-plane direction retardation (retardation) Ro and a thickness direction retardation (retardation) Rt, more preferably, the retardation Ro is in the range of 0 to 5 nm, and the retardation Rt is It is in the range of −10 to 10 nm.

In addition, retardation Ro and Rt are represented by the following formula | equation.
Ro = (nx−ny) × d
Rt = {(nx + ny) / 2−nz} × d
In the formula, nx represents the refractive index in the slow axis direction in the plane of the resin layer, ny represents the refractive index in the direction perpendicular to the slow axis in the plane of the resin layer, and nz represents the thickness of the resin layer. The refractive index of a direction is shown, d shows the thickness (nm) of a film. The measurement wavelength of the refractive index is 590 nm.

Moreover, retardation Ro and Rt can be calculated | required also with 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 when the 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 is KOBRA 21ADH (manufactured by Oji Scientific Instruments) or KOBRA 31WPR (Oji Scientific Instruments (stock) )).
3) Using KOBRA 21ADH or the like, measure the 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. θ can be preferably 30 ° to 50 °.
4) nx, ny and nz are calculated from the measured Ro and R (θ) and the above-mentioned average refractive index and film thickness by KOBRA 21ADH or the like, and Rt at a measurement wavelength of 590 nm 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>
Cellulose resins used in 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 propionate ( CAP), cellulose acetate butyrate (CAB), cellulose acetate phthalate, cellulose acetate trimellitate, cellulose ester such as cellulose nitrate, and the like, preferably cellulose esters. 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 a cellulose resin, Cotton linter, a 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 is preferably 1.0 to 2.9, more preferably 1.5 to 2.9. The total acyl group substitution degree can be measured according to ASTM-D817-96.

<Total light transmittance>
The total light transmittance of the resin layer is preferably 80% or more. A practical upper limit of the total light transmittance is about 99%. In order to achieve excellent transparency expressed by such total light transmittance, it is necessary not to introduce additives and copolymerization components that absorb visible light, or to remove foreign substances in the polymer by high-precision filtration. It is effective to reduce the diffusion and absorption of light inside the film (resin layer). Also, reduce the surface roughness of the film surface by reducing the surface roughness of the film contact part (cooling roll, calender roll, drum, belt, coating substrate in solution casting, transport roll, etc.) during film formation. It is effective to reduce the diffusion and reflection of light on the film surface.

<Additive>
The resin layer of the present embodiment includes a plasticizer that imparts processability, flexibility, and moisture resistance to the film, an ultraviolet absorber that imparts an ultraviolet absorption function, fine particles (matting agent) that imparts 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 layer 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》
Fine particles such as a matting agent can be added to the resin layer of this embodiment 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 (co-condensate) of an inorganic reactive metal compound and an organic hydroxyl group-containing polymer compound is used. The adhesive layer contains a metallic hydroxyl group that can be covalently bonded to the thin film glass, and an organic hydroxyl group-containing polymer compound that has high compatibility and affinity with the organic component in the polarizing layer and the resin layer. And a resin layer (including a polarizing 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 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.

  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.

  As polysaccharides, 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 film A>
<Silicon dioxide dispersion diluent>
Aerosil R812 (manufactured by Nippon Aerosil Co., Ltd.) 10 parts by mass Ethanol 90 parts by mass The above was stirred and mixed with a dissolver for 30 minutes, and then dispersed with Manton Gorin to obtain a silicon dioxide dispersion. 88 parts by mass of methylene chloride was added to this silicon dioxide dispersion with stirring, and the mixture was stirred and mixed with a dissolver for 30 minutes. Subsequently, a fine particle dispersion dilution filter (Advantech Toyo Co., Ltd .: Polypropylene Wind Cartridge Filter TCW-PPS- 1N) to prepare a silicon dioxide dispersion dilution.

<Preparation of dope solution>
TAC: Triacetyl cellulose (acetyl group substitution degree 2.89, Mw = 19000, Ca content 25 ppm)
100 parts by mass Tinuvin 928 (manufactured by BASF Japan Ltd.) 2.5 parts by mass Polycondensed ester compound P2 7.0 parts by mass Polycondensed ester compound P5 1.6 parts by mass Methylene chloride 540 parts by mass Ethanol 35 parts by mass The solution was put into a container, completely dissolved with heating and stirring, and filtered. To this, 4 parts by mass of a silicon dioxide dispersion diluted solution was added with stirring, and the mixture was further stirred for 30 minutes to prepare a dope solution.

<Synthesis of Polycondensed Ester Compound P2>
Said polycondensation ester compound P2 was synthesize | combined as follows. 251 g of 1,2-propylene glycol, 244 g of phthalic anhydride, 103 g of adipic acid, 610 g of benzoic acid, 0.191 g of tetraisopropyl titanate as an esterification catalyst, 2 L four-neck equipped with thermometer, stirrer, and slow cooling tube The flask was charged and gradually heated with stirring until it reached 230 ° C. in a nitrogen stream. Then, a dehydration condensation reaction was carried out while observing the degree of polymerization. After completion of the reaction, unreacted 1,2-propylene glycol was distilled off under reduced pressure at 200 ° C. to obtain a polycondensed ester compound P2. The acid value was 0.10 and the number average molecular weight was 450.

<Synthesis of polycondensed ester compound P5>
Said polycondensation ester compound P5 was synthesize | combined as follows. 251 g of 1,2-propylene glycol, 354 g of terephthalic acid, 680 g of p-troyl acid and 0.191 g of tetraisopropyl titanate as an esterification catalyst are charged into a 2 L four-necked flask equipped with a thermometer, a stirrer and a slow cooling tube. The temperature was gradually raised with stirring until it reached 230 ° C. in a nitrogen stream. Then, a dehydration condensation reaction was carried out while observing the degree of polymerization. After completion of the reaction, unreacted 1,2-propylene glycol was distilled off under reduced pressure at 200 ° C. to obtain a polycondensed ester compound P5. The acid value was 0.30 and the number average molecular weight was 400.

<Film formation / stretching / drying>
Next, using the belt casting apparatus, the above cellulose acylate dope solution was cast uniformly on a stainless steel belt support at a temperature of 35 ° C. and a width of 2 m. With the stainless steel belt support, the solvent was evaporated until the residual solvent amount reached 100% by mass, and it was peeled off from the stainless steel belt support. The peeled film web was conveyed while being dried at 50 ° C., slitted, and then stretched by a tenter in a TD direction (direction perpendicular to the film conveying direction) at a temperature of 160 ° C. and a stretching ratio of 26%. . At this time, the residual solvent amount when starting stretching with a tenter was 5.0%. Then, after being dried for 15 minutes while being transported in a drying apparatus at 120 ° C. with a number of rolls, slitting is performed, and both ends of the film are subjected to a knurling process having a width of 15 mm and a height of 5 μm. Obtained. The residual solvent amount of the film was less than 0.1%, the film thickness was 10 μm, the width was 2 m, and the winding length was 6000 m. The draw ratio in the MD direction (film transport direction) calculated from the rotational speed of the stainless steel belt support and the operating speed of the tenter was 1.05.

<Manufacture of film B>
Similarly to the production of the film A, the dope casting amount was appropriately adjusted to produce a film B having a thickness of 60 μm.

<Manufacture of film C>
Similarly to the production of the film A, the casting amount of the dope was appropriately adjusted to produce a film C having a thickness of 20 μm.

  <Evaluation of films A to C>

Each film A to C conditioned for 24 hours in an air conditioning room at 23 ° C. and 55% RH was cut out at 120 mm (length) × 10 mm (width) under the same conditions, and a Tensilon tester (ORITC), RTC-1225A The tensile test was performed 5 times at a pulling speed of 50 mm / min, and this measurement was performed in two orthogonal directions. Moreover, the film thickness d of the film was measured with a contact-type film thickness meter manufactured by Mitutoyo Corporation. And the tensile load M per unit strain of each film AC was computed by the following formula.
M [N] = E [MPa] × 10 [mm] × d [μm] × 10 ⁻³
Table 1 shows the tensile load M per unit strain of the films A to C.

<Manufacture of polarizing layer A>
Prepare a 4-5% PVA aqueous solution in which polyvinyl alcohol (PVA) powder having a polymerization degree of 1000 or more and a saponification degree of 99% or more is dissolved in water, and apply the PVA aqueous solution on a 200 μm thick amorphous PET substrate. By drying at a temperature of 50 to 60 ° C., a laminate in which a PVA layer having a thickness of 7 μm was laminated on an amorphous PET base material was produced.

<Extension processing>
The laminate obtained above was subjected to free end stretching at 140 ° C. in the transport direction (MD direction) at a stretch ratio of 5 to obtain a stretched laminate.

<Dyeing treatment>
The stretched laminate produced above was immersed in an iodine solution (mass ratio: iodine / potassium iodide / water = 1/10/100) at 30 ° C. for 60 seconds while maintaining the tension. Thereafter, drying was performed at 60 ° C. for 4 minutes.

  Through the above steps, a laminate in which an amorphous PET base material and a 5 μm polarizing layer A were laminated was obtained. The following adhesive M was applied to the surface of the PVA layer of the laminate, and then KC2UA manufactured by Konica Minolta Advanced Layer was bonded with a laminator and cured and adhered by ultraviolet irradiation. The thickness of the cured layer was 0.05 μm. By peeling the amorphous PET substrate from this laminate, a laminate R including the polarizing layer A was obtained.

<Adhesive M>
An adhesive M was obtained by blending 3 parts by weight of a photopolymerization initiator (manufactured by Ciba Japan, trade name: Irgacure 127) with 100 parts by weight of N-hydroxyethylacrylamide.

<Manufacture of polarizing layer B>
A material obtained by impregnating 100 parts by mass of PVA having a saponification degree of 99.95 mol% and a polymerization degree of 2400 with 10 parts by mass of glycerin and 170 parts by mass of water is dissolved in an aqueous solution. Cast and film-form. Then, it dried and heat-processed and obtained the PVA film. This PVA film had an average thickness of 25 μm, a moisture content of 4.4%, and a film width of 3 m.

  Next, this PVA film was continuously treated in the order of pre-swelling, dyeing, uniaxial stretching by a wet method, fixing treatment, drying, and heat treatment to prepare a polarizing layer B.

  That is, the PVA film was preliminarily swollen in water at a temperature of 30 ° C. for 30 seconds, and immersed in an aqueous solution having an iodine concentration of 0.4 g / liter and a potassium iodide concentration of 40 g / liter at a temperature of 35 ° C. for 3 minutes. Subsequently, the film was uniaxially stretched 6 times in a 50% aqueous solution with a boric acid concentration of 4% under the condition that the tension applied to the film was 700 N / m, and the potassium iodide concentration was 40 g / liter and the boric acid concentration was 40 g / liter. Then, it was immersed in an aqueous solution having a zinc chloride concentration of 10 g / liter and a temperature of 30 ° C. for 5 minutes for fixing.

  Thereafter, the PVA film was taken out, dried with hot air at a temperature of 40 ° C., and further heat-treated at a temperature of 100 ° C. for 5 minutes. The obtained polarizing layer B had an average thickness of 13 μm, a polarizing performance of 43.0% transmittance, a polarization degree of 99.5%, and a dichroic ratio of 40.1.

  And after apply | coating the adhesive agent M to the single side | surface of a polarizing layer, Konica Minolta Advanced Layer KC2UA was bonded together with the laminator, and it hardened | cured and adhered by ultraviolet irradiation, and the laminated body S containing the polarizing layer B was obtained.

<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 cocondensate 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

<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 cocondensate of a reactive metal compound and a hydroxyl group-containing polymer compound.
Water 100 parts by mass Tetraethoxysilane (TEOS) 10 parts by mass Amberlyst 15 (solid catalyst) 2 parts by mass Polyvinyl alcohol 10 parts by mass

<Manufacture of adhesive C>
After mixing the materials in the following ratio and stirring at room temperature, the solid catalyst was separated by filtration to prepare an adhesive C containing a cocondensate of a reactive metal compound and a hydroxyl group-containing polymer compound.
Water 100 parts by mass Tetramethoxysilane (TMOS) 10 parts by mass Amberlyst 15 (solid catalyst) 2 parts by mass Polyvinyl alcohol 10 parts by mass

<Example 1-1>
A thin film glass having a thickness of 50 μm manufactured by Nippon Electric Glass Co., Ltd. is prepared, and film A is formed using adhesive A on one side, and laminate R is formed using adhesive B on the other side. The glass laminated body of Example 1-1 was obtained by heat-bonding so that it might adhere | attach on glass.

<Example 1-2>
Except having used the film B instead of the film A, it carried out similarly to Example 1-1, and obtained the glass laminated body of Example 1-2.

<Example 1-3>
A glass laminate of Example 1-3 was obtained in the same manner as Example 1-1 except that film B was used instead of film A and adhesive C was used instead of adhesive B.

<Example 1-4>
Example similar to Example 1-1, except that adhesive C was used instead of adhesive B, and laminate S was used instead of laminate R so that the polarizing layer B side was adhered to the thin film glass. A glass laminate of 1-4 was obtained.

<Comparative Example 1-1>
Except having used the film C instead of the film A, it carried out similarly to Example 1-1, and obtained the glass laminated body of the comparative example 1-1.

<Evaluation of Examples and Comparative Examples>
Table 2 shows the results of evaluating the resistance to washing with water for the glass laminates of Examples 1-1 to 1-4 and Comparative Example 1-1.

  The water washing test and evaluation criteria are as follows. Ten glass laminates of each Example and Comparative Example were prepared, immersed in water for 30 minutes, then taken out from water and dried by applying 50 ° C. wind for 30 minutes. This was defined as one cycle and repeated 500 cycles. And the state of the glass laminated body after a test was judged visually according to the following evaluation criteria.

(Evaluation criteria)
○: No cracks or cracks in all 10 sheets.
(Triangle | delta): Although 1 to 2 sheets among 10 sheets have a crack and a crack, there is no problem in actual use.
X: There are cracks and cracks in 3 or more of 10 sheets, which is a problem in actual use.

  From Table 2, in Comparative Example 1-1 in which the film C was used for the resin layer, three or more of 10 glass laminates were cracked or cracked in the water washing test, whereas the film was formed on the resin layer. In Example 1-1 using A and Example 1-2 using the film B as the resin layer, no cracks or cracks occurred in all 10 glass laminates in the water washing test. This is because the polarizing layer A made of PVA expands when immersed in water and contracts when dried, whereas the film C used in Comparative Example 1-1 has a tensile load per unit strain of 40 N. Therefore, it is considered that the expansion and contraction could not be suppressed, and as a result, the glass laminate was repeatedly warped and cracked or cracked.

  On the other hand, the films A and B used in the examples have large tensile loads per unit strain of 60 and 100 N, so that the expansion and contraction of the PVA can be suppressed, and as a result, the glass laminate is repeatedly warped. No cracks or cracks are considered to have occurred.

  Further, from Table 2, the adhesive for bonding the polarizing layer A is different between Example 1-2 and Example 1-3, but the evaluation results of the washing test with water are the same. It is considered that there is no superior difference between the adhesive and the adhesive C.

  Moreover, from Example 2, in Example 1-4 using the polarizing layer B, cracks and cracks occurred in 1 to 2 of 10 glass laminates in a water washing test. This is because the polarizing layer B is stronger in stretching force than the polarizing layer A, so that the film A has to be restrained from further stretching, and as a result, it is considered that the glass laminate is repeatedly slightly warped. .

  Therefore, it can be said that it is resistant to a water washing test by using a film having a tensile load per unit strain of the resin layer of 50 N or more.

  From the above, when the glass laminates of Examples 1-1 to 1-4 are used in a display device, they should be used without problems over a long period of time, even if they are used in applications where they are repeatedly washed with water. Can do.

<Preparation of transparent resin film>
Cellulose acetate (acetyl substitution degree 2.86) 100 parts by weight Sugar ester 1 9 parts by weight Sugar ester 2 3 parts by weight Methylene chloride 365.8 parts by weight Methanol 92.6 parts by weight Butanol 4.6 parts by weight Mixing the above composition The dope was prepared by charging into a tank and stirring. As sugar ester 1 and sugar ester 2, the following were used.

  Next, the dope is cast and formed with a metal belt, the web is peeled off from the metal belt, stretched 1.3 times in the conveying direction while drying, and then 1.25 times in the direction perpendicular to the conveying direction with a tenter. The film was stretched and dried to obtain a transparent resin film No. 80 having a thickness of 80 μm. 1 was produced.

  Using the same dope, the web was stretched 1.45 times in the conveying direction, followed by a 1.4-fold stretching treatment in a direction perpendicular to the conveying direction with a tenter, dried, and dried to obtain a transparent resin film No. 80 μm thick. 3 was produced.

  Using the same dope, the web was stretched 1.3 times in the transport direction, and then the web was clipped so that the clip positions on both sides of the tenter were shifted by 1% in the transport direction, and 1.25 in the direction perpendicular to the transport direction. A double-stretching treatment was performed, followed by drying. 5 was produced.

  Using the same dope, the web was stretched 1.3 times in the transport direction, and then the web was clipped so that the clip positions on both sides of the tenter were shifted by 2% in the transport direction, and 1.25 in the direction perpendicular to the transport direction. A double-stretching treatment was performed, followed by drying. 6 was produced.

  The same dope was cast with a metal belt, the web was peeled off from the metal belt and cut, and after 30 minutes without stretching, the film was dried to obtain a transparent resin film No. 80 μm thick. 2 was produced.

  Using the same dope, after cutting the web, it was dried immediately without performing a stretching treatment, and a transparent resin film No. 60 μm thick was obtained. 4 was produced.

  Using the same dope, the web was stretched 1.25 times in the transport direction, and then the web was clipped so that the clip positions on both sides of the tenter were shifted by 2% in the transport direction, and 1.2 in the direction perpendicular to the transport direction. A double-stretching treatment was performed, followed by drying. 7 was produced.

  Further, two types of dopes were produced by the method of Example 11 described in JP 2012-225994 A, and cast and formed on a metal belt by a co-casting method. The film was stretched 1.1 times in the direction, dried, and transparent resin film No. 70 having a film thickness of 70 μm. 8 was produced.

  Also, using the same two types of dopes as described above, the web was stretched 1.6 times in the conveying direction, and a transparent resin film No. 7 having a thickness of 70 μm was used. 9 was produced.

  Here, the above-mentioned two types of dopes (referred to as dope 1 and dope 2) were specifically produced as follows.

(Preparation of dope 1)
The following composition was put into a mixing tank and stirred to dissolve each component to prepare a cellulose acylate solution for a core layer (low substitution degree layer). At this time, the amount of the solvent (methylene chloride and methanol) was appropriately adjusted so that the solid content concentration of each cellulose acylate solution had a value described in 22%. In addition, S3 shown in Table 3 was used as an additive.
Cellulose acetate (substitution degree 2.43) 100.0 parts by mass Additive 15.0 parts by mass Methylene chloride 365.5 parts by mass Methanol 54.6 parts by mass

(Preparation of dope 2)
The following composition was put into a mixing tank and stirred to dissolve each component to prepare a cellulose acylate solution for the outer layer (high substitution degree layer). At this time, the amount of the solvent (methylene chloride and methanol) was appropriately adjusted so that the solid content concentration of each cellulose acylate solution was 19.7%.
Cellulose acetate (substitution degree 2.81) 100.0 parts by mass Silica fine particles R972 (manufactured by Nippon Aerosil Co., Ltd.) 0.15 parts by mass Methylene chloride 395.0 parts by mass Methanol 59.0 parts by mass

<Measurement of moisture permeability>
The moisture permeability (water vapor permeability) of the transparent resin film, than the method described in JIS Z 0208, measured at 40 ° C. 90% RH conditions, the value of the moisture permeation amount of 1 m ² per 24 hours (g / m ² -It calculated | required as 24h).

<Measurement of tensile modulus>
A 10 mm x 150 mm sample is cut out from the produced transparent resin film so that each direction of 0 °, 45 °, 90 °, and 135 ° is the longitudinal direction with respect to the reference direction (corresponding to the transport direction during film formation). Was conditioned at 23 ° C. and 55% relative humidity for 12 hours. Then, using a universal tensile tester STM T50BP manufactured by Toyo Baldwin, stress strain curves were obtained by stretching each sample in the longitudinal direction at an initial sample length of 50 mm and 10% / min in an atmosphere at 23 ° C. and a relative humidity of 55%. Was measured, and the tensile modulus of the film was measured. Thereafter, the tensile modulus of elasticity in four directions was plotted in eight directions around the center of the origin and elliptical approximation was performed, and the direction in which the tensile modulus of elasticity of each transparent resin film was maximized and the value of the maximum tensile modulus of elasticity were calculated.

<Measurement of in-plane retardation>
After adjusting the humidity of each transparent resin film at 23 ° C. and 55% RH, the in-plane retardation (retardation) Ro when light with a measurement wavelength of 590 nm is incident from the normal direction of the film surface is expressed as KOBRA 31WPR (Oji Measurement) Measured with a device manufactured by K.K.

  Table 4 shows the measurement results of the moisture permeability, the direction of maximum tensile elastic modulus, and the maximum tensile elastic modulus of each transparent resin film.

<Preparation of adhesive>
Next, the materials are mixed at the following ratios, stirred at room temperature for 2 hours, and then the solid catalyst is separated by filtration. An organic-inorganic hybrid type containing a condensate of a reactive metal compound and a hydroxyl group-containing polymer compound An adhesive was prepared.
Acetone 100 parts by mass M silicate 51 (manufactured by Tama Chemical Co., Ltd.) 10 parts by mass Amberlyst 15 (solid catalyst) 2 parts by mass Cellulose ester (DAC) 10 parts by mass M silicate 51 is methyl polysilicate (Si _n O _(n-1) (OCH ₃ ) _{2 (n + 1)} , n = 3 to 5 (average), 50 to 53% as silica), methyl silicate (normal methyl silicate (Si (OCH) ₄ )), It is a mixture with methanol (methyl alcohol (CH ₃ OH)).

<Production of thin film glass with transparent resin layer>
A thin film glass having a thickness of 30 μm and a size of 4.5 inches manufactured by Nippon Electric Glass Co., Ltd. was prepared, and the above-mentioned adhesive was applied to both sides thereof and dried. The thickness of the adhesive layer after drying was 5 μm. On both sides of this thin glass, transparent resin film No. 1 is heated and bonded so that the maximum direction of the tensile elastic modulus is parallel (the deviation in the above direction is 0 °). 11 was obtained.

  In the same manner as described above, the transparent resin films were bonded to both surfaces of the thin film glass according to the combinations shown in Table 5 below. 12-20 were produced. At this time, the transparent resin films were bonded on both sides of the thin film glass so that the reference directions of the transparent resin films were parallel to each other.

  Table 5 shows a thin film glass No. with a transparent resin layer. 11 to 20 and the combination of the transparent resin films on both sides and the deviation (°) in the direction of the maximum tensile elastic modulus, and the thin film glass with a transparent resin layer No. The correspondence of 11-20 and an Example or a comparative example is shown.

<Production of liquid crystal display device (part 1)>
The thin film glass with a transparent resin layer was provided with an ITO layer by a sputtering process to form an electrode and connected to a driving wiring. Further, a rubbing treatment was performed by providing a PVA layer as an alignment film on the ITO layer. A liquid crystal cell was produced using the thin film glass with a transparent resin layer subjected to the rubbing treatment so as to have the combinations shown in Table 6. In addition, the thin film glass with transparent resin layer No. When using No. 17, the transparent resin film No. 7 was placed so as to be on the liquid crystal cell side (inside the liquid crystal display device).

  As the liquid crystal, 5CB (4-cyano-4'-pentylbiphenyl; manufactured by Merck & Co., Inc.), which is a liquid crystal substance often used for TN liquid crystal, was used. Then, a cell gap was secured using a spherical spacer having a diameter of 6 μm, and a rubbing direction was orthogonalized to produce a TN-oriented 4.5 inch size liquid crystal cell.

  Then, a polarizing plate is bonded to both sides of each liquid crystal cell so that the absorption axis of the polarizing plate and the rubbing direction of the liquid crystal cell are parallel, and a liquid crystal cell for driving that is shielded from light at 7V and transmitted at 0V is manufactured. As shown in Table 6, a 4.5-inch TN alignment display device No. 101-109.

<Production of liquid crystal display device (part 2)>
The thin film glass with a transparent resin layer was provided with an ITO layer by a sputtering process to form an electrode and connected to a driving wiring. This electrode-attached thin film glass with a transparent resin layer was used in the combination shown in Table 7 and bonded through a liquid crystal layer in which liquid crystals were dispersed in a polymer. At this time, a cell gap was secured using a spacer having a diameter of 12 μm. As a result, the polymer dispersion type display device No. 201-206 were produced. In these display devices, it was confirmed that the white turbidity was obtained when no voltage was applied, and the transparency increased (the haze decreased) when a voltage of 12 V was applied. In addition, the thin film glass with transparent resin layer No. When using No. 17, the transparent resin film No. 7 was placed so as to be on the liquid crystal cell side (inside the liquid crystal display device).

In addition, as a liquid crystal composition which comprises a liquid-crystal layer, the same thing as Example 1 of Unexamined-Japanese-Patent No. 2011-105908 was used. That is, composition (A) is 74%, urethane acrylate oligomer UN-6300 (manufactured by Negami Kogyo Co., Ltd., molecular weight 13000) is 7.72%, compound (B) is morpholine acrylate, 18.02%, light A liquid crystal composition for a polymer dispersion type liquid crystal element in which a polymerization initiator Irgacure 651 (manufactured by Ciba Japan) was 0.26% was used. These are prepared to moderately control the temperature. As a UV cut filter, 10 mm thick blue plate glass is used, and a high pressure mercury lamp adjusted to have an irradiation intensity of 10 mw / cm ² is irradiated for 60 seconds to polymerize. A polymer dispersion type display device was obtained by polymerizing the compound to induce phase separation from the liquid crystal composition.

<Evaluation of liquid crystal display device>
Each display device shown in Table 6 and Table 7 was left standing for 30 minutes in an environment of 40 ° C. and 90% RH, and then the amount of warping at the four corners was measured and averaged over four points. Then, the same thing was fixed to the backlight unit with the bezel, and was left on the same conditions as the above. The warpage amount and the evaluation results at that time are shown in Tables 6 and 7. Each display device was evaluated based on the following criteria.
(Evaluation criteria)
○: No cracks occurred in the display device (particularly the thin film glass with a transparent resin layer), and no display defect was confirmed.
X: Display device (particularly thin film glass with a transparent resin layer) was cracked or display failure was confirmed.

  No. 106, no. 107, no. 205, no. About display apparatuses other than 206, the curvature amount of the thin film glass with a transparent resin layer was 4 mm or less, and a crack and display defect were not confirmed but the favorable result was obtained as evaluation.

In contrast, no. About the display apparatus of 107, the crack of the thin film glass with a transparent resin layer was confirmed. This is because the moisture permeability of the transparent resin film used exceeds 1000 g / m ² · 24 h, and the amount of shrinkage due to moisture absorption is too large under ultra-high humidity, so the maximum tensile elastic modulus of the transparent resin film is Even if the direction is aligned (even if the deviation in the above direction is 0 °), the balance of shrinkage of the transparent resin film easily breaks on both sides of the thin glass, and as a result, the amount of warpage becomes as large as 10 mm, This is probably because the thin film glass with a transparent resin layer was cracked.

No. 106, no. 205, no. For each of the display devices 206, no crack was observed in the thin film glass with a transparent resin layer, but white / black display or white / transparent display was not properly performed, and display defects were confirmed. This is because the displacement in the maximum direction of the tensile modulus in each transparent resin film exceeds 10 °, or the moisture permeability of the transparent resin film exceeds 1000 g / m ² · 24 h. Below, the balance of the shrinkage of the transparent resin film tends to be lost on both sides of the thin glass, and the amount of warpage becomes as large as 7 mm. As a result, the orientation control of the liquid crystal layer by voltage application cannot be performed properly, resulting in poor display. Is considered to have occurred.

From the above, the organic-inorganic hybrid adhesive improves the adhesion between the thin film glass and the transparent resin film, and the shift in the direction in which the tensile elastic modulus of the transparent resin film on both sides of the thin film glass is maximized is eliminated. If it is within 10 ° and the moisture permeability of at least one transparent resin film is smaller than 1000 g / m ² · 24 hr, the balance of shrinkage is maintained in each transparent resin layer on both sides of the thin film glass even in an ultra-high humidity environment. Thus, it can be said that the thin film glass with a transparent resin layer, and thus the warpage of the display device can be reduced, whereby the destruction of the display device and display defects can be reduced. In particular, if the moisture permeability of at least one transparent resin film is 600 g / m ² · 24 hr or less shown in Table 4, the absorption of moisture in the transparent resin film can be further suppressed, and thus the above effect can be obtained with certainty. I think that the.

  In addition, No. No. 101 TN alignment display device and No. 101. No. 201 polymer dispersion type display device, No. 201. No. 102 TN alignment display device and No. 102. No. 203 polymer dispersion type display device, no. No. 107 TN alignment display device and No. The amount of warpage is different from the polymer dispersion type display device 206 in spite of using the same thin film glass with a transparent resin layer. This is considered to be due to the difference in thickness of the liquid crystal cell.

  In the above examples, a liquid crystal display device is taken as an example of the display device, but it was confirmed that the same result as described above was obtained even with an organic EL display device.

  The glass laminate and the thin film glass with a transparent resin layer of the present invention can be used for organic EL display devices and liquid crystal display devices.

1 Liquid crystal display device 11 Substrate (glass laminate, cover glass)
12 Substrate 13 Liquid crystal layer 21 Resin layer 22 Adhesive layer (first adhesive)
23 Thin film glass 24 Adhesive layer (second adhesive)
25 Polarizing layer 31 Organic EL display device 32 Organic EL element 37 Cover glass 40 Thin film glass with transparent resin layer 41 Thin film glass 42 Adhesive layer 43 Transparent resin layer 44 Adhesive layer 45 Transparent resin layer

Claims (15)

The resin layer, the first adhesive, the thin glass, the second adhesive, and the polarizing layer are laminated in this order,
The first and second adhesives include a cocondensate of a reactive metal compound and a hydroxyl group-containing polymer compound,
The tensile load per unit strain of the resin layer is 50 N or more,
The polarizing layer contains a polyvinyl alcohol-based resin.   The glass laminate according to claim 1, wherein the resin layer contains a cellulose ester.   The glass laminate according to claim 1, wherein the hydroxyl group-containing polymer compound contains a cellulose derivative or polyvinyl alcohol.   The glass laminate according to claim 3, wherein the cellulose derivative is a cellulose ester resin.   The glass laminate according to claim 4, wherein the cellulose ester resin has a total acyl group substitution degree of 1.0 to 2.6.   The glass laminate according to any one of claims 1 to 5, wherein the reactive metal compound is silicon alkoxide.   The glass laminate according to claim 1, wherein the thin film glass has a thickness of 5 to 100 μm. A liquid crystal display device in which a liquid crystal layer is sandwiched between a pair of substrates,
At least one of said pair of board | substrates has the glass laminated body in any one of Claims 1-7, The liquid crystal display device characterized by the above-mentioned. An organic EL display device having a cover glass disposed on the front surface of an organic EL element,
The said cover glass has the glass laminated body in any one of Claims 1-7, The organic electroluminescence display characterized by the above-mentioned. It is a thin film glass with a transparent resin layer in which a transparent resin layer is laminated on each side of the thin film via an adhesive layer,
The adhesive layer contains a cocondensate of a reactive metal compound and a hydroxyl group-containing polymer compound,
In the transparent resin layer on one side of the thin film glass and the transparent resin layer on the other side, the deviation in the direction in which the tensile elastic modulus is maximum is within 10 °,
A thin film glass with a transparent resin layer, wherein water vapor permeability of at least one transparent resin layer is smaller than 1000 g / m ² · 24 hr.   The tensile elastic modulus of each said transparent resin layer is 1 GPa-6GPa, The thin film glass with a transparent resin layer of Claim 10 characterized by the above-mentioned.   The thin film glass with a transparent resin layer according to claim 10 or 11, wherein an in-plane retardation of at least one transparent resin layer is 30 nm to 200 nm.   The thin film glass with a transparent resin layer according to claim 10, wherein an average thickness of the thin film glass is 5 to 200 μm. A liquid crystal display device in which a liquid crystal layer is sandwiched between a pair of substrates,
A liquid crystal display device, wherein at least one of the pair of substrates has the thin film glass with a transparent resin layer according to any one of claims 10 to 13. An organic EL display device having a cover glass disposed on the front surface of an organic EL element,
The said cover glass has the thin film glass with a transparent resin layer in any one of Claims 10-13, The organic electroluminescence display characterized by the above-mentioned.

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