JPWO2014084045A1 - Glass with polarization function and liquid crystal display device having the same - Google Patents

Abstract

A thin film glass (21) and a polarizing layer (23) are laminated via an adhesive layer (22) to constitute a substrate (11) as a glass with a polarizing function. The adhesive layer (22) contains a condensate of a reactive metal compound and a hydroxyl group-containing polymer compound.

Description

  The present invention relates to a glass with a polarizing function obtained by imparting a polarizing function to glass, and a liquid crystal display device including the glass.

  In recent years, the size of display devices has been increasing, and mobile devices have also been increasing. Thus, thin and light display devices are required. A glass substrate is generally used for the display device, and the display device can be made thin and light by thinning the glass substrate. However, when the glass substrate is thinned, the glass substrate is easily broken and the handling property is deteriorated.

  Therefore, in Patent Document 1, a resin film is bonded to a glass film having a thickness of 0.1 μm to 100 μm via an adhesive to reduce damage when the glass film is handled. As described above, Patent Document 2 also proposes a method of attaching a film to a thin film glass via an adhesive.

  On the other hand, in Patent Document 3, an ultrathin glass with a thickness of 50 μm is sandwiched and laminated between PET (polyethylene terephthalate) films with an adhesive to increase the strength while giving flexibility to the entire film. I am doing so.

  In addition, as an example of the adhesive to be used, Patent Document 1 mentions an acrylic pressure-sensitive adhesive, and Patent Document 2 mentions a thermosetting epoxy resin, but Patent Document 3 discloses a specific example thereof. It has not been.

JP 2001-97733 A (see claim 1, paragraphs [0017], [0059], etc.) JP 2009-94050 A (refer to claim 1, paragraph [0008], FIG. 1, etc.) JP 2002-299041 A (refer to claim 1, paragraphs [0013], [0016], FIG. 1, etc.)

  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 such a thin film glass with a film is applied to a liquid crystal display device, for example, if the film on the thin film glass has a function as a polarizing plate and a glass with a polarization function can be configured, this polarizing function is provided. A liquid crystal cell (a liquid crystal layer sandwiched between two substrates) can be manufactured using glass, 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 with a polarizing function, the polarizing plate having the above three-layer structure may be laminated as a film on the thin film glass as it is. However, since the back side of the polarizing layer is protected by the thin film glass, You may abbreviate | omit and comprise glass with a polarization function. That is, the polarizing layer may be directly contacted with the adhesive and laminated on the thin film glass to constitute a glass with a polarizing function. In this case, it is possible to reduce the thickness of the glass with a polarizing function and reduce the cost 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 or epoxy-based adhesive is used as the adhesive, good adhesion to both the thin film glass and the polarizing layer (resin) of different materials cannot be ensured. For this reason, the adhesion of the polarizing layer to the thin film glass is lowered. 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 glass with a polarization function falls by the adhesive fall of thin film glass and a polarizing layer, handling property worsens and it becomes easy to damage glass at the time of handling.

  In view of the circumstances described above, the object of the present invention is to suppress the deterioration of the polarizing layer due to environmental fluctuations during a durability test and handle it even when the polarizing layer is directly contacted with an adhesive and laminated on a thin film glass. It is in providing the glass with a polarization function which can improve property, and a liquid crystal display device provided with the same.

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

1. A thin glass and a polarizing layer are laminated via an adhesive layer,
The glass with polarizing function, wherein the adhesive layer contains a condensate of a reactive metal compound and a hydroxyl group-containing polymer compound.

  2. 2. The glass with a polarizing function according to 1 above, wherein the polarizing layer contains polyvinyl alcohol.

  3. 3. The glass with a polarizing function according to 1 or 2, wherein the polarizing layer has a thickness of 10 μm or less.

  4). 4. The glass with polarizing function according to any one of 1 to 3, wherein the hydroxyl group-containing polymer compound is a cellulose ester having a total acyl group substitution degree of 1.0 to 2.6.

5. When the adhesive layer is a first adhesive layer,
5. The glass with a polarizing function according to any one of 1 to 4, wherein a resin layer is laminated on a side opposite to the polarizing layer with respect to the thin film glass via a second adhesive layer.

  6). 6. The glass with a polarizing function according to 5, wherein the resin layer is made of a cellulose-based resin.

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

8. A liquid crystal display device in which a liquid crystal layer is sandwiched between two substrates,
One substrate is comprised with the glass with a polarization function in any one of said 1-7, The liquid crystal display device characterized by the above-mentioned.

  The metal component contained in the reactive metal compound can be covalently bonded to the glass component. Further, since the hydroxyl group-containing polymer compound contains a hydroxyl group, the affinity with the polarizing layer can be improved. Therefore, the adhesive layer that bonds the thin film glass and the polarizing layer is a condensate of the reactive metal compound and the hydroxyl group-containing polymer compound, and has both the characteristics of the reactive metal compound and the hydroxyl group-containing polymer compound. Thereby, favorable adhesiveness can be ensured with respect to both the thin film glass and the polarizing layer, and the adhesiveness between the thin film glass and the polarizing layer can be improved via the adhesive layer. Thereby, it can suppress that a polarizing layer deteriorates by the environmental fluctuation | variation at the time of an endurance test, and a nonuniformity arises in a polarization degree. Further, by improving the adhesion between the thin film glass and the polarizing layer, the bending rigidity of the glass with a polarizing function can be increased and the handling property can be improved (breakage of the glass during handling 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 with a polarization function applied to the said liquid crystal display device. It is sectional drawing which shows the other structural example of the said glass with a polarization function.

  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 made of a polarizing glass having a polarizing layer 23 (see FIG. 2). The details will be described later. A polarizing layer 23 and a polarizing plate (not shown) in a crossed Nicols state are disposed on the backlight 3 side of the substrate 12. In addition, you may comprise the board | substrate 12 with glass with a polarization function 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 23 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.

[About glass with polarization function]
Next, the board | substrate 11 as glass with a polarization function is demonstrated. FIG. 2 is a cross-sectional view illustrating a configuration example of the substrate 11. The substrate 11 is configured by laminating an adhesive layer 22, a polarizing layer 23, and a protective layer 24 in this order on a thin film glass 21.

  The polarizing layer 23 is a polarizer that transmits predetermined linearly polarized light, and is obtained, for example, by dyeing a polyvinyl alcohol film with a dichroic dye and stretching the film at a high magnification. The protective layer 24 is provided for the purpose of protecting the surface of the polarizing layer 23. The protective layer 24 is adhered to the polarizing layer 23 via an ultraviolet curable adhesive, or an aqueous polyvinyl alcohol solution as an adhesive (water glue). Are pasted together.

  The adhesive layer 22 is an organic-inorganic hybrid adhesive layer (HB glue) including a condensate of a reactive metal compound (inorganic compound) and a hydroxyl group-containing polymer compound (organic compound). The condensate of a reactive metal compound and a hydroxyl group-containing polymer compound means that it includes a structure in which a hydroxyl group generated from the reactive metal compound and a hydroxyl group in the hydroxyl group-containing polymer compound are condensed. The 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, the affinity with the polarizing layer 23 made of a resin can be improved and the adhesiveness can be improved. In addition, the organic compound and the inorganic compound are poorly compatible, but by forming these condensates, the adhesive layer 22 having both characteristics in a single layer structure can be formed.

  Therefore, by using the organic-inorganic hybrid adhesive layer 22, the adhesion between the thin film glass 21 and the polarizing layer 23 can be improved via the adhesive layer 22. Thereby, the polarizing layer 23 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 21 and the polarizing layer 23, it is possible to increase the bending rigidity of the substrate 11 as a glass with a polarizing function, improve handling, and reduce breakage of the glass during handling. Can do.

  Moreover, since the polyvinyl alcohol contained in the polarizing layer 23 has strong hydrophilicity, the affinity between the adhesive layer 22 containing a hydroxyl group and the polarizing layer 23 is further improved, and the adhesion between the thin film glass 21 and the polarizing layer 23 is further increased. improves. Therefore, when the polarizing layer 23 contains polyvinyl alcohol, the configuration using the adhesive layer 22 containing a hydroxyl group is very effective.

  The thickness of the polarizing layer 23 is preferably 10 μm or less. In this case, the above-described effects can be obtained with the thin configuration of the polarizing layer 23.

  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 polarizing layer 23 made of a resin, so that it is very effective as a material for improving the adhesiveness with the polarizing layer 23.

  FIG. 3 is a cross-sectional view showing another configuration example of the substrate 11 as a glass with a polarizing function. In the substrate 11, an adhesive layer 22 (first adhesive layer), a polarizing layer 23, and a protective layer 24 are laminated in this order on a thin film glass 21, and further on the opposite side of the thin film glass 21 from the polarizing layer 23. The resin layer 26 may be laminated via the adhesive layer 25 (second adhesive layer).

  As described above, by bonding the resin layers (the polarizing layer 23, the protective layer 24, and the resin layer 26) on both sides of the thin film glass 21, the strength of the substrate 11 can be further improved, and it can be made difficult to break.

  The adhesive layer 25 may be composed of an acrylic adhesive or an epoxy adhesive, but it can improve the adhesion between the thin film glass 21 and the resin layer 26 and further improve the strength of the substrate 11. In terms of the capability, it is desirable that the adhesive layer is the same as the adhesive layer 22 described above, that is, an organic-inorganic hybrid adhesive layer.

  The case where the adhesive layers 22 and 25 are not clearly present as layers is also included in the scope of the present invention. That is, the component contained in the adhesive layer 22 penetrates into and reacts with the polarizing layer 23 or the protective layer 24, so that the integrated state or the component contained in the adhesive layer 25 penetrates into the resin layer 26 and reacts. Therefore, an integrated state is also included in the scope of the present invention.

  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. Accordingly, 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 26.

  In addition, in a 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, heat resistance when forming the color filter on the resin layer 26 of the substrate 11 is not necessary. Therefore, the resin layer 26 can be made of a resin other than the cellulose resin.

  In a liquid crystal display device, there are an IPS (In-Plane Switching) method, a TN (Twisted Nematic) method, a VA (Vertical Alignment) method, and the like as the liquid crystal driving method. Compared to, it has a feature of excellent viewing angle performance. For this reason, in the case of the IPS system, it is desirable that the phase difference in the resin layer 26 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 26 is 0 to 5 nm and the thickness direction retardation Rt is −10 to 10 nm.

[Details of each layer]
(Thin glass)
As thin film glass which comprises glass with a polarization function, what was shape | molded by various shaping | molding methods can be used. For example, a thin film glass formed by a rollout method, a redraw method, a downdraw method, a float method, or the like can be used.

  The shape of the thin film glass is not particularly limited and may be a chip cut shape, but is preferably a roll shape from the viewpoint of suitability for production on a roll-to-roll basis.

  The average thickness of the thin film glass is preferably 5 to 200 μm, and more preferably 5 to 100 μm. When the thickness is less than 5 μm, handling such as conveyance is difficult, and when the thickness exceeds 200 μm, the value of the thin film is diminished.

  The thin film glass is not particularly limited as long as it is a multicomponent oxide glass. For example, alkali-free glass, borosilicate glass, aluminosilicate glass and the like are particularly suitable as the thin film glass, and among them, alkali-free glass is most preferred.

  The surface of the thin film glass is preferably cleaned appropriately. If organic substances such as sebum and dust are attached, the adhesiveness with the adhesive layer is lowered. The cleaning method follows a known glass cleaning method. For example, alkali cleaning, acid cleaning, detergent cleaning, solvent cleaning, liquid jet cleaning, UV cleaning, excimer cleaning, plasma cleaning, ion cleaning, sputter cleaning, heat cleaning, dry ice jet Cleaning or the like is suitable as a cleaning method, and among them, alkali cleaning, UV cleaning, and excimer cleaning are preferable. Moreover, surface treatment may be performed in advance on the thin film glass. For example, it is preferable that the surface treatment is performed with a silicon alkoxide such as TEOS or TMOS, or a silane coupling agent.

(Polarizing layer)
The polarizing layer is an element (polarizer) that passes only light having a plane of polarization in a certain direction. As a typical element currently used as a polarizing layer, there is a polarizer using a polyvinyl alcohol-based resin, which includes a polyvinyl alcohol-based resin dyed with iodine and a dichroic dye. There is something.

  As a polarizer, a polyvinyl alcohol aqueous solution is formed into a film, and this is uniaxially stretched and dyed as a raw fabric, or 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)
From the viewpoint of improving the strength of the glass, it is preferable that a resin layer is formed on the side opposite to the polarizing layer with respect to the thin film glass via an adhesive layer. The resin layer is not particularly limited as long as it is an optically transparent resin. For example, acrylic resin, polycarbonate resin, cycloolefin resin, polyester resin, polylactic acid resin, polyvinyl alcohol resin, and cellulose resin. Resins can be used.

  Among them, it is preferable to use a cellulose-based resin as the resin layer in consideration of heat resistance when forming the color filter.

  The resin layer preferably has 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 is measured with KOBRA 21ADH (manufactured by Oji Scientific Instruments) when light having a measurement wavelength of 590 nm is incident on the resin layer after humidity adjustment from the normal direction of the resin layer.
3) Retardation value R (θ) when light having a measurement wavelength of 590 nm is incident from the angle θ (incident angle (θ)) with respect to the normal direction of the resin layer by KOBRA 21ADH (manufactured by Oji Scientific Instruments). ). θ can be preferably 30 ° to 50 °.
4) nx, ny, and nz are calculated by KOBRA 21ADH (manufactured by Oji Scientific Instruments) from the measured Ro and R (θ) and the above-described average refractive index and film thickness, and the measurement wavelength is 590 nm. Rt at is calculated. The retardation can be measured after tempering for about 12 hours, for example, at 23 ° C. and 55% RH.

  The resin layer prepared in advance in the form of a film may be adhered to the glass via the adhesive layer, or the adhesive layer is formed on the glass, and the resin layer is directly applied or cast. May be formed.

<Cellulosic resin>
Cellulosic resins used in the resin layer of the present embodiment include cellulose ethers such as methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, cyanoethyl cellulose, triacetyl cellulose (TAC), diacetyl cellulose (DAC), cellulose acetate pro Examples include cellulose esters such as pionate (CAP), cellulose acetate butyrate (CAB), cellulose acetate phthalate, cellulose acetate trimellitate, and cellulose nitrate, and cellulose esters are preferred. Alternatively, aromatic carboxylic acid esters described in paragraph numbers [0010] to [0027] of JP-A No. 2002-179701 are used, and in particular, celluloses of paragraph numbers [0028] to [0036] of JP-A No. 2002-17979. Acylate is preferably used.

  Although there is no limitation in particular as a cellulose of the raw material of the cellulose resin used for the resin layer of this embodiment, Cotton linter, wood pulp, kenaf etc. can be mentioned. Moreover, although the cellulose resin obtained from these can be used individually or in mixture of arbitrary ratios, it is preferable to use 50 mass% or more of cotton linters.

  When the molecular weight of the cellulose ester is large, the elastic modulus is increased. However, when the molecular weight is excessively increased, the viscosity of the cellulose ester solution becomes too high, so that productivity is lowered. The molecular weight of the cellulose ester is preferably 70000-200000 in terms of number average molecular weight, more preferably 100000-200000. The cellulose ester used in the present embodiment preferably has a weight average molecular weight of Mw, a number average molecular weight of Mn, and a Mw / Mn ratio of 1.4 to 3.0, more preferably 1.4 to 2. 3.

  Since the average molecular weight and molecular weight distribution of cellulose ester can be measured using high performance liquid chromatography, the number average molecular weight (Mn) and the weight average molecular weight (Mw) are calculated using this, and the ratio is calculated. be able to. Measurement conditions are as follows.

Solvent: Methylene chloride Column: Shodex K806, K805, K803G (Used by connecting three Showa Denko Co., Ltd.)
Column temperature: 25 ° C
Sample concentration: 0.1% by mass
Detector: RI Model 504 (manufactured by GL Sciences)
Pump: L6000 (manufactured by Hitachi, Ltd.)
Flow rate: 1.0ml / min
Calibration curve: Standard polystyrene STK standard polystyrene (manufactured by Tosoh Corporation) Mw = 1,000,000-500 calibration curves with 13 samples were used. The 13 samples are preferably used at approximately equal intervals.

  The total acyl group substitution degree of the cellulose ester used in the resin layer of this embodiment is preferably 1.0 to 2.9, and more preferably 1.5 to 2.9. The total acyl group substitution degree can be measured according to ASTM-D817-96.

<Additive>
The resin film of the present embodiment includes a plasticizer that imparts processability, flexibility, and moisture resistance to the film, an ultraviolet absorber that imparts an ultraviolet absorbing function, fine particles (matting agent) that impart slipperiness to the film, You may contain the antioxidant which prevents deterioration, the retardation adjusting agent which adjusts the retardation of a film, etc.

《Plasticizer》
There is no particular limitation on the plasticizer used, but it has a functional group capable of interacting with the adhesive layer so as not to cause haze or bleed out or volatilization from the film. preferable.

  Examples of such functional groups include hydroxyl groups, ether groups, carbonyl groups, ester groups, carboxylic acid residues, amino groups, imino groups, amide groups, imide groups, cyano groups, nitro groups, sulfonyl groups, sulfonic acid residues, Examples thereof include a phosphonyl group and a phosphonic acid residue, and a carbonyl group, an ester group and a phosphonyl group are preferred.

  Examples of such plasticizers include phosphate ester plasticizers, phthalate ester plasticizers, trimellitic acid ester plasticizers, pyromellitic acid plasticizers, polyhydric alcohol ester plasticizers, glycolate plasticizers. Agents, citrate plasticizers, fatty acid ester plasticizers, carboxylic acid ester plasticizers, polyester plasticizers, and the like can be preferably used. Particularly preferred are non-phosphate ester plasticizers such as polyhydric alcohol ester plasticizers, glycolate plasticizers, and polycarboxylic acid ester plasticizers.

  The polyhydric alcohol ester is composed of an ester of a dihydric or higher aliphatic polyhydric alcohol and a monocarboxylic acid, and preferably has an aromatic ring or a cycloalkyl ring in the molecule.

<Ultraviolet absorber>
The resin film preferably contains an ultraviolet absorber from the viewpoint of preventing deterioration of the liquid crystal. A layer having an ultraviolet absorbing function may be formed on the resin film.

  As the ultraviolet absorber having an ultraviolet absorbing function, those having an excellent ability to absorb ultraviolet rays having a wavelength of 370 nm or less and little absorption of visible light having a wavelength of 400 nm or more are preferably used. Specific examples of preferably used ultraviolet absorbers include triazine compounds, oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, nickel complex compounds, and the like. However, it is not limited to these. Moreover, the polymeric ultraviolet absorber described in JP-A-6-148430 is also preferably used.

《Matting agent》
To the resin film of this embodiment, fine particles such as a matting agent can be added in order to impart slipperiness. Examples of the fine particles include fine particles of an inorganic compound or fine particles of an organic compound.

  Examples of the inorganic compound include fine particles such as silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, and tin oxide. In this, it is preferable that it is a compound containing a silicon atom, and especially a silicon dioxide fine particle is preferable. Examples of the silicon dioxide fine particles include AEROSIL 200, 200V, 300, R972, R972V, R974, R202, R812, R805, OX50, and TT600 manufactured by Aerosil Co., Ltd.

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

"Antioxidant"
Antioxidants are also referred to as deterioration inhibitors. When the liquid crystal display device is placed in a high humidity and high temperature state, the optical film may be deteriorated. Antioxidants have the role of delaying or preventing the optical film from being decomposed by, for example, the residual solvent amount of halogen in the optical film or phosphoric acid of the phosphoric acid plasticizer, so it is contained in the optical film. It is preferable to do so.

  As such an antioxidant, a hindered phenol compound is preferably used, and in particular, 2,6-di-t-butyl-p-cresol, pentaerythrityl-tetrakis [3- (3,5-di- -T-butyl-4-hydroxyphenyl) propionate] and triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] are preferred. Further, for example, hydrazine-based metal deactivators such as N, N′-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine and tris (2,4-di- A phosphorus processing stabilizer such as t-butylphenyl) phosphite may be used in combination.

(Adhesive layer)
As the adhesive layer, a condensate of an inorganic reactive metal compound and an organic hydroxyl group-containing polymer compound is used. 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 is highly compatible and compatible with the organic components in the polarizing layer and the resin layer. The polarizing layer, the thin film glass, and the resin 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-exchanged water is preferable for hydrolyzing the reactive metal compound, and ion-exchanged 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 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 acryl 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.

  Polysaccharides include starch, hydroxymethyl starch, hydroxyethyl starch, hydroxypropyl starch, glycogen, inulin, lichenin, cellulose, hemicellulose, amylopectin, heparin, heparitin sulfate, chondroitin sulfate, hyaluronic acid, keratosulfate, chitin, chitosan, agar , Carrageenan, alginic acid, fur celerane, locust bean gum, galactomannan, guar gum, syrup gum, tamarind gum, gum arabic, tragacanth gum, caraya gum, pectin, arabinogalactan, xanthan gum, gellan gum, pullulan, dextran, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxy Propylmethylcellulose, carboxymethylcellulose, methylcellulose Scan, ethylcellulose, and the like of these cationic products can be mentioned.

  As the hydroxyl group-containing polymer compound used in the present embodiment, cellulose derivatives are preferably used. Among them, diacetyl cellulose (DAC), cellulose acetate propionate (CAP), cellulose acetate butyrate (CAB), cellulose acetate phthalate, cellulose Cellulose esters such as acetate trimellitate and cellulose nitrate are preferred. More preferably, the acyl group substitution degree is 0.5 to 2.9, and more preferably, the acyl group substitution degree is 1.0 to 2.6.

(Liquid crystal display device)
The glass with polarization function of this embodiment is TN, IPS, FLC (Ferroelectric Liquid Crystal), AFLC (Anti-ferroelectric Liquid Crystal), OCB (Optically Compensatory Bend), STN (Supper Twisted Nematic), VA, HAN (Hybrid Aligned). Nematic) can be used as a cell substrate for liquid crystal display devices of various display modes, and among them, it is preferably used as an IPS cell substrate.

  When the glass with a polarizing function of this embodiment is used as a cell substrate, it is possible to form a color filter on the side opposite to the polarizing layer in the glass with a polarizing function.

〔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>
(Preparation of inline additive solution)
10 parts by weight of Aerosil 972V (manufactured by Nippon Aerosil Co., Ltd., average particle diameter of 16 nm, apparent specific gravity of 90 g / liter) and 90 parts by weight of methanol were stirred and mixed with a dissolver for 30 minutes, and then dispersed with Manton Gorin. A fine particle dispersion was obtained.

  88 parts by mass of dichloromethane was added to the obtained fine particle dispersion while stirring, and the mixture was stirred and mixed with a dissolver for 30 minutes to dilute. The obtained solution was filtered with a polypropylene wind cartridge filter TCW-PPS-1N manufactured by Advantech Toyo Co., Ltd. to obtain a fine particle dispersion dilution.

  15 parts by mass of Tinuvin 928 (manufactured by BASF Japan Ltd.) and 100 parts by mass of dichloromethane were put into a sealed container, heated and stirred to completely dissolve, and then filtered. To the obtained solution, 36 parts by mass of the fine particle dispersion diluent was added with stirring, and further stirred for 30 minutes, and then 6 parts by mass of cellulose ester 1 (acetyl group substitution degree 2.9, Mn = 90000, Mw = 152000, Mw / Mn = 1.7) was added with stirring, and the mixture was further stirred for 60 minutes. The obtained solution was filtered with Finemet NF manufactured by Nippon Seisen Co., Ltd. to obtain an in-line additive solution. The filter medium having a nominal filtration accuracy of 20 μm was used.

(Preparation of main dope solution)
The following components were put into a sealed container and completely dissolved with heating and stirring. The obtained solution was prepared as Azumi Filter Paper No. 24. The main dope liquid was obtained by filtration.

<Composition of main dope solution>
Cellulose acetate (acetyl group substitution degree 2.9, Mn = 90000, Mw = 152000, Mw / Mn = 1.7)
90 parts by mass Ester compound A 10 parts by mass

  100 parts by mass of the main dope solution and 2.5 parts by mass of the in-line additive solution were sufficiently mixed with an in-line mixer (Toray static in-tube mixer Hi-Mixer, SWJ) to obtain a dope solution A.

<Ester compound A>
251 g of 1,2-propylene glycol, 278 g of phthalic anhydride, 91 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 a thermometer, stirrer, and slow cooling tube The flask is charged and gradually heated with stirring until it reaches 230 ° C. in a nitrogen stream. The ester compound A having an acid value of 0.10 and a number average molecular weight of 450 was obtained by dehydrating and condensing for 15 hours, and distilling off unreacted 1,2-propylene glycol at 200 ° C. after completion of the reaction.

(Film A film formation)
The obtained dope solution A was uniformly cast on a stainless steel band support using a belt casting apparatus under conditions of a dope solution temperature of 35 ° C. and a width of 1.8 m. On the stainless steel band support, the solvent in the obtained dope film was evaporated until the residual solvent amount reached 100% to obtain a web, and then the web was peeled from the stainless steel band support. The obtained web was further dried at 35 ° C. and then slit to have a width of 1.65 m. Thereafter, the web was dried at a drying temperature of 160 ° C. while being stretched 1.5 times in the TD direction (the width direction of the film) with a tenter. The residual solvent amount of the web at the start of stretching was 20%. Moreover, the draw ratio of MD direction computed from the rotational speed of a stainless steel band support body and the driving speed of a tenter was 1.0.

  After that, the film obtained was dried at 125 ° C. for 15 minutes while being conveyed by a number of rolls in the drying apparatus, then slit to 2.2 m width, and the height of the convex portion was 8 μm at both ends in the width direction. A film A having a thickness of 20 μm and a knurling width of 15 mm was obtained. When measured at a wavelength of 590 nm under the conditions of 23 ° C. and 55% RH, the film A has an in-plane retardation Ro of 3 nm, a thickness direction retardation Rt of 15 nm, and a slow axis in the width direction. It was.

<Manufacture of film B>
A dope solution B was prepared in the same manner as for the film A except that the composition of the main dope solution was changed to the following.
Cellulose acetate (acetyl group substitution degree 2.9, Mn = 90000, Mw = 152000, Mw / Mn = 1.7)
100 parts by mass Methylene chloride 380 parts by mass Ethanol 70 parts by mass (Meth) acrylic polymer A 5.5 parts by mass

  The (meth) acrylic polymer A was obtained by the following method. First, bulk polymerization was performed by the polymerization method described in JP-A No. 2000-128911. In other words, methyl acrylate as a monomer was introduced into a flask equipped with a stirrer, nitrogen gas inlet tube, thermometer, inlet, and reflux condenser, and nitrogen gas was introduced and the flask was replaced with nitrogen gas. Added under.

  After the addition of thioglycerol, polymerization was carried out for 4 hours, the contents were returned to room temperature, and 20 parts by mass of a 5% by mass benzoquinone tetrahydrofuran solution was added thereto to stop the polymerization. The contents were transferred to an evaporator, and tetrahydrofuran, residual monomer and residual thioglycerol were removed under reduced pressure at 80 ° C. to obtain a (meth) acrylic polymer A having a molecular weight of 1000.

  The obtained dope solution B was uniformly cast on a stainless steel band support using a belt casting apparatus under conditions of a dope solution temperature of 35 ° C. and a width of 1.8 m. On the stainless steel band support, the solvent in the obtained dope film was evaporated until the residual solvent amount reached 100% to obtain a web, and then the web was peeled from the stainless steel band support. The obtained web was further dried at 35 ° C. and then slit to have a width of 1.65 m. Thereafter, the web was dried at a drying temperature of 160 ° C. while being stretched 1.5 times in the TD direction (the width direction of the film) with a tenter. The residual solvent amount of the web at the start of stretching was 20%. In addition, the draw ratio in the MD direction calculated from the rotational speed of the stainless steel band support and the operating speed of the tenter was 1.4 times.

  After that, the film obtained was dried at 125 ° C. for 15 minutes while being conveyed by a number of rolls in the drying apparatus, then slit to 2.2 m width, and the height of the convex portion was 8 μm at both ends in the width direction. A film B having a thickness of 20 μm and a knurling width of 15 mm was obtained. When measured at a wavelength of 590 nm under the conditions of 23 ° C. and 55% RH, the film B has an in-plane retardation Ro of 1 nm, a thickness direction retardation Rt of 3 nm, and a slow axis in the width direction. It was.

<Example 1>
(Manufacture of glass with polarization function)
(Preparation of adhesive A)
The materials were mixed at the following ratios and stirred at room temperature for 2 hours, and then the solid catalyst was separated by filtration to prepare an adhesive A.
Acetone 100 parts by mass Tetramethoxysilane (TMOS) 10 parts by mass Amberlyst 15 (solid catalyst) 2 parts by mass Cellulose ester (DAC, acetyl group substitution degree 2.45)
10 parts by mass

(Manufacture of laminates)
<Polarizing layer>
A PVA aqueous solution having a concentration of 4 to 5% in which polyvinyl alcohol (hereinafter referred to as PVA) powder having a polymerization degree of 1000 or more and a saponification degree of 99% or more was dissolved in water was prepared. By applying and 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 substrate 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 A in which an amorphous PET base material and a 5 μm polarizing layer were laminated was obtained.

  And after apply | coating the following adhesive agent M to the surface of the PVA layer of the laminated body A, the film A was bonded together with the laminator, and it hardened | cured and adhered by ultraviolet irradiation. The thickness of the cured layer was 0.05 μm. A laminate B was obtained by peeling the amorphous PET substrate from this laminate.

<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.

  A 30 μm thick thin glass made by Nippon Electric Glass Co., Ltd. is prepared and bonded with a laminator in such a way that adhesive A is sandwiched between one side of the glass and the polarizing layer side of the laminate B. After that, it was heat-pressed in an oven to obtain a glass with a polarizing function. The glass with polarizing function of Example 1 is referred to as glass 1 with polarizing function.

<Example 2>
A 30 μm-thick thin film glass manufactured by Nippon Electric Glass Co., Ltd. is heated while being bonded with a laminator through an adhesive A in between so as to be sandwiched between the laminate B (polarizing layer side) and the film A from both sides. Thus, a glass with a polarizing function was obtained. The glass with polarization function of Example 2 is referred to as glass 2 with polarization function.

<Example 3>
As the base material layer, an acrylic resin film (lactonized polymethyl methacrylate film (Ro = 2 nm, Rt = 0 nm)) having a thickness of 80 μm was used. The acrylic resin film is a (meth) acrylic resin having a lactone ring structure [weight ratio of copolymerization monomer: methyl methacrylate / 2- (hydroxymethyl) methyl acrylate = 8/2; lactone cyclization rate of about 100 %] A mixture of 90 parts by weight and 10 parts by weight of acrylonitrile-styrene (AS) resin {Toyo AS AS20, manufactured by Toyo Styrene Co., Ltd.} (manufactured by Nippon Shokubai Co., Ltd.) was melt-extruded, and the length 2.0 It was obtained by stretching twice.

  Using the acrylic resin film as a base material, a PVA aqueous solution was applied in the same manner as in Example 1, and then dried at 120 ° C. for 10 minutes to obtain a laminate in which a PVA coating film having a thickness of 5 μm was formed. Further, in the same manner as in Example 1, stretching treatment and dyeing treatment were performed to obtain a laminate C in which an acrylic film and a polarizing layer having a thickness of 2 μm were laminated.

  Then, in the same manner as in Example 2, an adhesive A was interposed between the laminate C (polarizing layer side) and the film A so that a thin film glass having a thickness of 30 μm manufactured by Nippon Electric Glass Co., Ltd. was sandwiched from both sides. The glass with polarization function was obtained by heating while laminating through a laminator. The glass with polarization function of Example 3 is referred to as glass 3 with polarization function.

<Example 4>
A 30 μm-thick thin film glass manufactured by Nippon Electric Glass Co., Ltd. was heated while being bonded via an adhesive A between them with a laminator so as to be sandwiched between the laminate A (polarizing layer side) and the film A from both sides. Thereafter, the amorphous PET was peeled off. Further, the following hard coat layer coating solution was applied to the exposed polarizing layer by an extrusion coater, dried, and then cured with ultraviolet rays to obtain a glass with a polarizing function. The glass with polarizing function of Example 4 is referred to as glass 4 with polarizing function.

(Hard coat layer coating solution)
The following hard coat layer composition was filtered through a polypropylene filter having a pore size of 0.4 μm to prepare a hard coat layer coating solution.
Dipentaerythritol hexaacrylate (NK ester A-DPH, manufactured by Shin-Nakamura Chemical Co., Ltd.)
180 parts by mass Irgacure 184 (manufactured by Ciba Japan) 6 parts by mass Irgacure 907 (manufactured by Ciba Japan) 8 parts by mass Polyether-modified silicone compound (trade name; KF-355A, Shin-Etsu Chemical Co., Ltd.) Company-made)
9 parts by mass Propylene glycol monomethyl ether 10 parts by mass Ethyl acetate 80 parts by mass Methyl ethyl ketone 100 parts by mass

<Example 5>
A glass with a polarizing function was obtained in the same manner as in Example 2 except that the 30 μm-thick thin film glass manufactured by Nippon Electric Glass Co., Ltd. was changed to 50 μm. The glass with a polarizing function of Example 5 is referred to as a glass 5 with a polarizing function.

<Example 6>
100 parts by mass of PVA having a saponification degree of 99.95 mol% and a polymerization degree of 2400 were melt-kneaded with 10 parts by mass of glycerin and 170 parts by mass of water. The film was formed. Then, it dried and heat-processed and obtained the PVA film. The obtained PVA film had an average thickness of 25 μm, a moisture content of 4.4%, and a film width of 3 m.

  Next, the obtained PVA film was continuously processed in the order of preliminary swelling, dyeing, uniaxial stretching by a wet method, fixing treatment, drying, and heat treatment to prepare a polarizing layer.

  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 had an average thickness of 13 μm, a polarizing performance of a transmittance of 43.0%, a degree of polarization of 99.5%, and a dichroic ratio of 40.1.

  And the laminated body D was obtained by bonding the film A to the single side | surface of the polarizing layer through the adhesive agent M, and carrying out ultraviolet curing. Thereafter, in the same manner as in Example 2, a thin film glass having a thickness of 30 μm manufactured by Nippon Electric Glass Co., Ltd. was sandwiched between the laminate D (polarizing layer side) and the film A from both sides, and the adhesive A was interposed therebetween. A glass with a polarizing function was obtained by heating while laminating with a laminator. Let the glass with a polarization function of Example 6 be the glass 6 with a polarization function.

<Example 7>
A glass with a polarizing function was obtained in the same manner as in Example 2 except that the adhesive A was changed to the following adhesive B. The glass with polarization function of Example 7 is referred to as glass 7 with polarization function.

(Adhesive B)
Acetone 100 parts by mass Tetraethoxysilane (TEOS) 10 parts by mass Amberlyst 15 (solid catalyst) 2 parts by mass Cellulose ester (DAC, acetyl group substitution degree 2.45)
10 parts by mass

<Example 8>
A glass with a polarizing function was obtained in the same manner as in Example 2 except that the film A on the side opposite to the polarizing layer with respect to the glass was changed to the film B. The glass with polarization function of Example 8 is referred to as glass 8 with polarization function.

<Comparative Example 1>
A glass with a polarizing function was obtained in the same manner as in Example 2 except that an acrylic pressure-sensitive adhesive (PSA; Pressure Sensitive Adhesive, pressure-sensitive adhesive) was used instead of the adhesive A. The glass with polarizing function of Comparative Example 1 is referred to as glass 9 with polarizing function.

<Comparative example 2>
A glass with a polarizing function was obtained in the same manner as in Example 2 except that a thermosetting epoxy adhesive (Epotech 310 manufactured by Daizonichi Mori Co., Ltd.) was used instead of the adhesive A. The glass with polarization function of Comparative Example 2 is referred to as glass 10 with polarization function.

<Evaluation of glass with polarization function>
About the glasses 1-10 with a polarizing function produced above, polarization degree nonuniformity and bending tolerance were evaluated. Table 1 has shown the evaluation result about the polarization degree nonuniformity and bending rigidity of the glasses 1-10 with a polarizing function.

  The evaluation methods and evaluation criteria for the degree of polarization unevenness and the bending rigidity are as follows.

(Uneven polarization)
Two prepared glasses with a polarizing function of 40 cm × 50 cm size were prepared, subjected to wet heat treatment at 50 ° C. and 90% RH for 24 hours, and then conditioned at 23 ° C. and 55% RH for 24 hours. Thereafter, two pieces of polarizing glass were placed in crossed Nicols on the Schaukasten, observed from the front, and unevenness was evaluated visually. In addition, about polarization degree nonuniformity, if evaluation is more than (circle), there is no problem.
A: 0 out of 5 people can confirm unevenness.
○: One out of five people can confirm unevenness.
Δ: 2 out of 5 people can confirm unevenness.
X: 3 or more out of 5 people can confirm unevenness.

(Bending resistance)
According to JIS K 5600-5-1, the bending resistance of the polarizing glass produced above was measured. That is, the size (diameter) of a cylindrical mandrel for a bending test was selected, and cracks and cracks of each glass were confirmed when bent on the peripheral surface of the selected mandrel. Then, the diameter of the mandrel was changed to a small one until cracks and cracks occurred, and the minimum diameter (mm) of the mandrels that began to crack and cracks was determined. In addition, about bending rigidity, if evaluation is (circle) or more, there is no problem.
A: The minimum diameter of the mandrel is less than 20 mm.
○: The minimum diameter of the mandrel is 20 mm or more and less than 30 mm.
X: The minimum diameter of the mandrel is 30 mm or more.

  From Table 1, about the glasses 1-8 with a polarizing function of Examples 1-8, both evaluation of polarization degree unevenness and bending rigidity are (circle) or more. This is because the organic-inorganic hybrid glue (HB glue) is used as the adhesive layer between the glass and the polarizing layer, so that the adhesive layer has good adhesion to both the glass and the polarizing layer (resin) of different materials. This is considered to be because the adhesion between the glass and the polarizing layer was improved.

  On the other hand, in the glasses with polarization function 9 to 10 of Comparative Examples 1 and 2, both the polarization degree unevenness and the bending rigidity are evaluated as x. This is because when the adhesive layer is PSA or epoxy resin, the adhesiveness between the adhesive layer and the thin film glass and the adhesive property between the adhesive layer and the polarizing layer cannot be improved at the same time. This is thought to be because it cannot be improved.

<Visibility of liquid crystal display>
Next, liquid crystal display devices (LCD) I and II were produced by the following procedures using the polarizing functions glass 2 and 8 of Examples 2 and 8, and the visibility at that time was evaluated.

(Production of liquid crystal display device)
A color filter was formed on the surfaces of the films A of the polarizing function glass 2 and 8 by an ink jet method, and glass substrates I and II with a color filter were formed, respectively.

  On the other hand, ITO (Indium Tin Oxide) was sputtered on a separately prepared 0.3 μm glass substrate through a mask having a predetermined pattern, and a pixel electrode was formed by etching with a resist pattern. Further, a polyimide solution for a photo-alignment film was applied on the pixel electrode, and baked and rubbed at 180 ° C. to form a photo-alignment film. This obtained the glass substrate with TFT.

  An adhesive containing spherical resin balls as spacers was applied and formed in a frame shape on each of the glass substrates with color filters I and II. An opening for injecting the liquid crystal layer composition was provided in the frame made of the adhesive. Next, both substrates were bonded via a frame-shaped adhesive so that the color filter side of the glass substrates with color filter I and II faced the alignment film side of the glass substrate with TFT.

  The particle size of the plastic beads, which are spacers contained in the adhesive, was 4.5 μm, and the gap of the liquid crystal cell was 5 μm.

  A liquid crystal material for display (Δn = 0.08, Δε = 4) having a positive dielectric anisotropy was injected into the obtained liquid crystal cell by a vacuum injection method. After injecting the liquid crystal material for display, the injection port was sealed with an ultraviolet curable resin to obtain a liquid crystal cell. The obtained liquid crystal cell was an IPS system in which liquid crystal molecules were driven in parallel with the substrate.

  And the peeling protective film of the following polarizing plate F was peeled off and bonded to the glass substrate with TFT of a liquid crystal cell, and the liquid crystal display devices I and II which respectively have the glass substrates I and II with a color filter were produced.

(Preparation of polarizing plate F)
According to the following processes 1-4, the polarizing plate F was produced by bonding the film A and the film B to the polarizing layer.

  Process 1: The above-mentioned polarizing layer was immersed in the storage tank of the polyvinyl alcohol adhesive agent solution of 2 mass% of solid content for 1-2 seconds.

  Step 2: Excess adhesive adhered to the polarizing layer immersed in the polyvinyl alcohol adhesive solution in Step 1 was gently removed, and this polarizing layer was sandwiched between film A and film B and laminated.

Step 3: The laminate was bonded at a speed of about 2 m / min at a pressure of ^{20 to} 30 N / cm ² with two rotating rollers. At this time, it was carried out with care to prevent bubbles from entering.

  Step 4: The sample prepared in Step 3 was dried in a dryer at a temperature of 80 ° C. for 5 minutes to prepare a polarizing plate.

  Step 5: Apply a commercially available acrylic adhesive to the polarizing plate film B prepared in Step 4 so that the thickness after drying is 10 μm, and dry in an oven at 110 ° C. for 5 minutes to form an adhesive layer. A peelable protective film was attached to the adhesive layer to obtain a polarizing plate F.

(Evaluation of liquid crystal display devices I and II)
About the liquid crystal display devices I and II produced above, the visibility from an oblique direction was confirmed by visual observation in a black display state. Table 2 shows the evaluation results for the visibility of the liquid crystal display devices I and II.

In addition, the reference | standard of evaluation of visibility is as follows.
A: Black tightening is the best and visibility is the best.
○: Black tightening is good and visibility is good.
X: Black tightening is not good, and there is a problem in practical use.

  From Table 2, the liquid crystal display device II had better black tightening and better visibility than the liquid crystal display device I. The liquid crystal display device I also has a level of visibility that is not problematic in practical use. As described above, in the IPS liquid crystal display device, in order to improve visibility, the film A (resin layer) bonded to the thin film glass on the color filter side has a retardation in the in-plane direction and the thickness direction. It can be said that it is desirable that is close to zero.

  The glass with a polarizing function of the present invention can be used for a liquid crystal display device.

1 Liquid crystal display device 11 Substrate (glass with polarization function)
12 Substrate 13 Liquid crystal layer 21 Thin film glass 22 Adhesive layer (first adhesive layer)
23 Polarizing layer 25 Adhesive layer (second adhesive layer)
26 Resin layer

Claims (8)

A thin glass and a polarizing layer are laminated via an adhesive layer,
The glass with polarizing function, wherein the adhesive layer contains a condensate of a reactive metal compound and a hydroxyl group-containing polymer compound.   The said polarizing layer contains polyvinyl alcohol, Glass with a polarizing function of Claim 1 characterized by the above-mentioned.   The glass with a polarizing function according to claim 1, wherein the polarizing layer has a thickness of 10 μm or less.   The glass with a polarizing function according to any one of claims 1 to 3, wherein the hydroxyl group-containing polymer compound is a cellulose ester having a total acyl group substitution degree of 1.0 to 2.6. When the adhesive layer is a first adhesive layer,
The glass with a polarizing function according to any one of claims 1 to 4, wherein a resin layer is laminated on a side opposite to the polarizing layer with respect to the thin film glass via a second adhesive layer. .   The glass with a polarizing function according to claim 5, wherein the resin layer is made of a cellulose-based resin.   The in-plane retardation Ro of the resin layer is 0 to 5 nm, and the thickness direction retardation Rt is -10 to 10 nm. The glass with a polarizing function according to claim 5 or 6. A liquid crystal display device having a liquid crystal layer sandwiched between two substrates,
One substrate is comprised with the glass with a polarization function in any one of Claim 1 to 7, The liquid crystal display device characterized by the above-mentioned.

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