CN106990471B - Polarizing plate and liquid crystal panel - Google Patents

Polarizing plate and liquid crystal panel Download PDF

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Publication number
CN106990471B
CN106990471B CN201611034038.6A CN201611034038A CN106990471B CN 106990471 B CN106990471 B CN 106990471B CN 201611034038 A CN201611034038 A CN 201611034038A CN 106990471 B CN106990471 B CN 106990471B
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film
polarizing
adhesive
polarizing plate
polarizing film
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CN106990471A (en
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松本寿和
伊藤惠启
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
    • G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/02—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving pretreatment of the surfaces to be joined
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133528—Polarisers
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133528—Polarisers
    • G02F1/133531—Polarisers characterised by the arrangement of polariser or analyser axes

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • Nonlinear Science (AREA)
  • Organic Chemistry (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Polarising Elements (AREA)
  • Liquid Crystal (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention provides a polarizing plate, which can inhibit the reduction of polarization degree caused by the deviation of the absorption axis of the polarizing film caused by the dimension change of an optical film in a heat resistance test. A polarizing plate comprising an optical film, a 1 st adhesive layer, a polarizing film and a 2 nd adhesive layer in this order, wherein an angle formed by an absorption axis of the polarizing film and a slow axis of the optical film is about 45 DEG or about 135 DEG, and a dimensional change rate D1 in a direction of 45 DEG with respect to the absorption axis of the polarizing film when the optical film is left standing for 100 hours in an environment of 85 ℃ and a dimensional change rate D2 in a direction of 135 DEG with respect to the absorption axis of the polarizing film when the optical film is left standing for 100 hours in an environment of 85 ℃ satisfy the following formulas (1) and (2). In the case of | D1| > | D2|, in the case of 2 < | D1|/| D2| (1) | D1| < | D2|, 2 < | D2|/| D1| (2).

Description

Polarizing plate and liquid crystal panel
Technical Field
The present invention relates to a polarizing plate and a liquid crystal panel using the same.
Background
In recent years, a lightweight and thin liquid crystal display which consumes low electric power and operates at low voltage has rapidly spread as an information display device such as a mobile phone, a portable information terminal, a monitor for a computer, and a television. With the development of liquid crystal technology, liquid crystal displays of various modes have been proposed, and problems of liquid crystal displays such as response speed, contrast, and narrow viewing angle have been solved. In addition, with the spread of liquid crystal displays for mobile devices, for example, when used outdoors or the like, the screen of the liquid crystal display may be recognized while wearing polarized sunglasses, and in such a case, the liquid crystal display is also required to have excellent visibility even when the screen is viewed through the polarized sunglasses.
Several proposals have been made for means for improving visibility when viewing a screen through a polarized sunglass (patent documents 1 to 9).
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 2009-122454
Patent document 2: japanese patent laid-open publication No. 2011-107198
Patent document 3: japanese patent laid-open publication No. 2011-215646
Patent document 4: japanese laid-open patent publication No. 2012-230390
Patent document 5: japanese laid-open patent publication No. H03-174512
Patent document 6: japanese patent laid-open publication No. 2013-231761
Patent document 7: japanese patent laid-open publication No. 2011-113018
Patent document 8: japanese patent laid-open publication No. 2013-182162
Patent document 9: japanese patent laid-open publication No. 2013-200445
Disclosure of Invention
Problems to be solved by the invention
As a method for improving visibility when viewing a screen through a polarized sunglass, the following method is employed: in order to convert linearly polarized light emitted from a polarizing plate disposed on the viewing side of an image display element such as a liquid crystal cell into elliptically (or circularly) polarized light, a retardation plate (e.g., a λ/4 wavelength plate) is disposed on the viewing side of the polarizing plate (patent documents 1 to 9).
However, such a retardation plate is often subjected to a stretching treatment and is directly laminated on a polarizing film via an adhesive layer. In addition, there are problems as follows: the angle formed by the absorption axis of the polarizing plate and the slow axis of the retardation plate is often set to a predetermined angle (for example, 45 °), and when the retardation plate stretched in the heat resistance test is subjected to a dimensional change in the oblique direction, the absorption axis of the polarizing film is locally changed, and the degree of polarization is lowered.
Means for solving the problems
[1] A polarizing plate comprising an optical film, a 1 st adhesive layer, a polarizing film and a 2 nd adhesive layer in this order,
the angle formed by the absorption axis of the polarizing film and the slow axis of the optical film is about 45 DEG or about 135 DEG,
the optical film satisfies the following expressions (1) and (2) with respect to a dimensional change rate D1 in a direction at 45 DEG with respect to the absorption axis of the polarizing film when left standing at 85 ℃ for 100 hours and a dimensional change rate D2 in a direction at 135 DEG with respect to the absorption axis of the polarizing film when left standing at 85 ℃ for 100 hours.
In the case of | D1| > | D2|, 2 < | D1|/| D2| (1)
In the case of | D1| < | D2|, 2 < | D2|/| D1| (2)
[2] The polarizing plate according to [1], wherein the optical film contains at least one selected from the group consisting of cyclic polyolefin resins, polycarbonate resins, cellulose resins, polyester resins, and (meth) acrylic resins.
[3] The polarizing plate according to [1] or [2], wherein the polarizing film has a thickness of 15 μm or less.
[4] The polarizing plate according to any one of [1] to [3], further comprising a protective film between the polarizing film and the 2 nd adhesive layer.
[5] A liquid crystal panel, wherein the polarizing plate according to any one of [1] to [4] is laminated on at least one surface of a liquid crystal cell with the 2 nd adhesive layer interposed therebetween.
Effects of the invention
According to the present invention, a polarizing plate capable of suppressing a decrease in the degree of polarization caused by a shift (ズレ) in the absorption axis of a polarizing film due to a dimensional change of an optical film in a heat resistance test can be provided.
Drawings
Fig. 1 is an example of a schematic cross-sectional view showing a layer structure of a polarizing plate of the present invention.
Fig. 2 is an example of a plan view showing the relationship in the axial direction in the polarizing plate of the present invention.
Detailed Description
The layer structure of the polarizing plate 10 of the present invention will be explained with reference to fig. 1. The polarizing plate of the present invention is preferably configured by laminating an optical film 11, a 1 st adhesive layer 12, a polarizing film 14, and a 2 nd adhesive layer 16 in this order. The absorption axis of the polarizing film 14 makes an angle of about 45 ° or about 135 ° with the slow axis of the optical film 11. It is also useful to form the surface-treated layer 20 on the surface of the optical film 11 opposite to the surface to be laminated with the polarizing film.
The optical film 11 is preferably a film containing at least one selected from the group consisting of cyclic polyolefin resins, polycarbonate resins, cellulose resins, polyester resins, and (meth) acrylic resins.
The thickness of the polarizing film 14 is preferably 15 μm or less.
In addition, according to the present invention, there is also provided a polarizing plate 10 further having a protective film 15 between the polarizing film 14 and the 2 nd adhesive 16.
In addition, according to the present invention, there is also provided a liquid crystal panel in which the polarizing plate 10 is laminated on at least one side of a liquid crystal cell via the 2 nd adhesive layer 16.
The components constituting the liquid crystal display device of the present invention will be described in detail below.
[ polarizing film 14]
The polarizing film 14 is generally manufactured through the following processes: the method for producing the resin film comprises a step of uniaxially stretching a polyvinyl alcohol resin film, a step of dyeing the polyvinyl alcohol resin film with a dichroic dye to adsorb the dichroic dye, a step of treating the polyvinyl alcohol resin film adsorbed with the dichroic dye with an aqueous boric acid solution to crosslink the film, and a step of crosslinking the film with an aqueous boric acid solution and then washing the film with water.
The polyvinyl alcohol resin can be produced by saponifying a polyvinyl acetate resin. The polyvinyl acetate resin may be a copolymer of vinyl acetate and another monomer copolymerizable therewith, in addition to polyvinyl acetate which is a homopolymer of vinyl acetate. Examples of other monomers copolymerizable with vinyl acetate include: unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, acrylamides having an ammonium group, and the like.
The saponification degree of the polyvinyl alcohol resin is usually about 85 to 100 mol%, and preferably 98 mol% or more. The polyvinyl alcohol resin may be modified, and for example, polyvinyl formal, polyvinyl acetal, or the like modified with aldehydes may be used. The polymerization degree of the polyvinyl alcohol resin is usually about 1000 to 10000, preferably about 1500 to 5000.
The film made of such a polyvinyl alcohol resin can be used as a raw film for a polarizing film. The method for forming the polyvinyl alcohol resin film is not particularly limited, and the film can be formed by a known method. The thickness of the raw film of the polyvinyl alcohol resin is, for example, about 10 to 100 μm, preferably about 10 to 50 μm.
The uniaxial stretching in the machine direction of the polyvinyl alcohol resin film may be performed before, simultaneously with, or after the dyeing with the dichroic dye. In the case where the uniaxial longitudinal stretching is performed after dyeing, the uniaxial longitudinal stretching may be performed before or during the boric acid treatment. Of course, the longitudinal uniaxial stretching may also be performed in multiple stages as shown here. For the longitudinal uniaxial stretching, a method of stretching uniaxially between rolls having different peripheral speeds, a method of stretching uniaxially using a hot roll, or the like can be used. The uniaxial stretching in the machine direction may be performed by dry stretching in which stretching is performed in the air, or may be performed by wet stretching in which stretching is performed in a state where the polyvinyl alcohol resin film is swollen with a solvent such as water. The draw ratio is usually about 3 to 8 times.
The dyeing of the polyvinyl alcohol resin film with the dichroic dye can be performed, for example, by a method of immersing the polyvinyl alcohol resin film in an aqueous solution containing the dichroic dye. As the dichroic dye, specifically, iodine or a dichroic organic dye can be used. The polyvinyl alcohol resin film is preferably subjected to a treatment of immersing in water to swell the film before the dyeing treatment.
When iodine is used as the dichroic dye, a method of dyeing a polyvinyl alcohol resin film by immersing the film in an aqueous solution containing iodine and potassium iodide is generally used.
The aqueous solution generally contains about 0.01 to 1 part by weight of iodine per 100 parts by weight of water, and about 0.5 to 20 parts by weight of potassium iodide per 100 parts by weight of water. The temperature of the aqueous solution used for dyeing is usually about 20 to 40 ℃. The immersion time (dyeing time) in the aqueous solution is usually about 20 to 1800 seconds.
On the other hand, when a dichroic organic dye is used as the dichroic dye, it is generally adopted to impregnate a polyvinyl alcohol resin film with a solution containing a polyvinyl alcoholA method for dyeing in an aqueous solution containing a water-soluble dichroic organic dye. The content of the dichroic organic dye in the aqueous solution is usually 1X 10 per 100 parts by weight of water-4About 10 parts by weight, preferably 1X 10-3About 1 part by weight. The aqueous dye solution may contain an inorganic salt such as sodium sulfate as a dyeing assistant. The temperature of the dichroic organic dye aqueous solution used for dyeing is usually about 20 to 80 ℃. The immersion time (dyeing time) in the aqueous solution is usually about 10 to 1800 seconds.
The boric acid treatment after dyeing with the dichroic dye can be performed by a method of immersing the dyed polyvinyl alcohol resin film in an aqueous solution containing boric acid. The boric acid content of the aqueous solution containing boric acid is usually about 2 to 15 parts by weight, preferably 5 to 12 parts by weight, per 100 parts by weight of water. When iodine is used as the dichroic dye, the aqueous solution containing boric acid preferably contains potassium iodide. The content of potassium iodide in the aqueous solution containing boric acid is usually about 0.1 to 15 parts by weight, preferably 5 to 12 parts by weight, per 100 parts by weight of water. The immersion time in the aqueous solution containing boric acid is usually about 60 to 1200 seconds, preferably 150 to 600 seconds, and more preferably 200 to 400 seconds. The temperature of the aqueous solution containing boric acid is usually 50 ℃ or higher, preferably 50 to 85 ℃, and more preferably 60 to 80 ℃.
The polyvinyl alcohol resin film after the boric acid treatment is usually subjected to a water washing treatment. The water washing treatment can be performed, for example, by a method of immersing the boric acid-treated polyvinyl alcohol resin film in water. The temperature of water in the water washing treatment is usually about 5 to 40 ℃. The dipping time is usually about 1 to 120 seconds.
After washing, the film was dried to obtain a polarizing film. The drying treatment may be performed using a hot air dryer or a far infrared heater. The temperature of the drying treatment is usually about 30 to 100 ℃, preferably 50 to 80 ℃. The drying time is usually about 60 to 600 seconds, preferably 120 to 600 seconds. The moisture content in the polarizing film is reduced to a practical level by the drying treatment. The water content is usually about 5 to 20% by weight, preferably 8 to 15% by weight. When the moisture content is less than 5% by weight, the flexibility of the polarizing film is lost, and damage or breakage may occur after drying. When the water content exceeds 20% by weight, the thermal stability tends to be insufficient.
In this way, the polarizing film 14 in which the dichroic dye is adsorbed and oriented on the polyvinyl alcohol resin film can be produced.
From the viewpoint of suppressing the decrease in the degree of polarization in the heat resistance test, it is also preferable to decrease the shrinkage force of the polarizing film itself. In order to suppress the shrinkage force of the polarizing film 14, the thickness of the polarizing film 14 is preferably set to 12 μm or less. The thickness of the polarizing film is usually 3 μm or more from the viewpoint of imparting good optical characteristics.
[ optical film 11]
In the polarizing plate used in the present invention, the optical film 11 is preferably made of a material having excellent transparency, mechanical strength, thermal stability, moisture barrier property, and the like. Examples thereof include: polyolefin resins such as chain polyolefin resins (polypropylene resins and the like) and cyclic polyolefin resins (norbornene resins and the like); cellulose resins such as cellulose ester resins including cellulose triacetate and cellulose diacetate; a polyester resin; a polycarbonate-based resin; (meth) acrylic resins; a polystyrene-based resin; or mixtures, copolymers, etc. thereof.
The optical film 11 preferably satisfies the following formula.
(5)100nm≤Re(590)≤180nm、
(6)0.5＜Rth(590)/Re(590)≤0.8、
(7)0.85≤Re(450)/Re(550) < 1.00, and
(8)1.00＜Re(630)/Re(550)≤1.1
in the formula, Re(590)、Re(450)、Re(550)、Re(630) Respectively represents the in-plane phase difference values at measurement wavelengths of 590nm, 450nm, 550nm and 630nm, Rth(590) The thickness direction phase difference value at a measurement wavelength of 590nm is shown. These in-plane phase difference values and thickness direction phase difference values are at temperatureThe measurement was carried out at 23 ℃ under an atmosphere of 55% relative humidity.
The refractive index in the in-plane slow axis direction is nxAnd n represents a refractive index in an in-plane fast axis direction (a direction orthogonal to an in-plane slow axis direction)yN represents a refractive index in a thickness directionzAnd d is the thickness of the optical film 11, the in-plane retardation value R of the optical film 11eA phase difference value R in the thickness directionthIs defined by the following formula.
Re＝(nx-ny)×d
Rth＝[{(nx+ny)/2}-nz]×d
In a liquid crystal display in which the optical film 11 exhibiting the retardation characteristics and the wavelength dispersion characteristics of the above-described formulas (5) to (8) is disposed on the viewing side, it is possible to effectively suppress a change in color when a screen is observed from each direction (orientation angle and polar angle) through the polarizing sunglasses, and to improve the visibility of the liquid crystal display. On the other hand, when any one or more of the above equations (5) to (8) is not satisfied, the suppression of the color tone change may be insufficient.
From the viewpoint of more effectively suppressing the change in hue, R in the formula (5)e(590) Preferably 105 to 170nm, R in the formula (6)th(590)/Re(590) Preferably 0.6 to 0.75, R in the formula (7)e(450)/Re(550) Preferably 0.86 to 0.98, R in the formula (8)e(630)/Re(550) Preferably 1.01 to 1.06.
The optical film 11 is a phase difference film having a function of converting linearly polarized light emitted from the polarizing film 14 to elliptically polarized light (including the case of circularly polarized light) and emitting the elliptically polarized light, and is laminated so that an angle formed by an absorption axis of the polarizing film and a slow axis of the optical film is about 45 ° or about 135 ° in order to exhibit the function. When the angle is outside the above range, a function of converting linearly polarized light into elliptically polarized light and emitting the elliptically polarized light cannot be obtained, and as a result, the suppression of the color tone change may be insufficient. In the present invention, about 45 ° or about 135 ° means 25 to 65 ° or 115 to 155 °, preferably 35 to 55 ° or 125 to 145 °, and more preferably 40 to 50 ° or 130 to 140 °.
The stretched optical film preferably contains a cyclic polyolefin resin, a polycarbonate resin, a cellulose resin, a polyester resin, or a (meth) acrylic resin, or two or more thereof, and more preferably the resin component is composed of one or two or more selected from the above, because the retardation properties and the wavelength dispersion properties of the above formulae (5) to (8) are easily imparted, the moisture permeability is relatively low, and the moisture resistance and the moist heat resistance of the optical laminate can be improved.
Examples of the chain polyolefin resin include homopolymers of chain olefins such as polyethylene resins and polypropylene resins, and copolymers of two or more kinds of chain olefins.
The cyclic polyolefin resin is a general term for resins obtained by polymerizing cyclic olefins as polymerization units. Specific examples of the cyclic polyolefin resin include ring-opened (co) polymers of cyclic olefins, addition polymers of cyclic olefins, copolymers of cyclic olefins with linear olefins such as ethylene and propylene (typically random copolymers), graft polymers obtained by modifying these with unsaturated carboxylic acids or derivatives thereof, and hydrogenated products of these. Among them, norbornene-based resins using norbornene-based monomers such as norbornene and polycyclic norbornene-based monomers as cyclic olefins are preferably used.
The cellulose ester resin is an ester of cellulose and a fatty acid. Specific examples of the cellulose ester-based resin include: cellulose triacetate, cellulose diacetate, cellulose tripropionate, cellulose dipropionate. Further, copolymers thereof and modified products in which a part of the hydroxyl groups is modified with another substituent may also be used. Among these, cellulose triacetate (triacetyl cellulose: TAC) is particularly preferable.
The polyester resin is a resin having an ester bond, and generally contains a polycondensate of a polycarboxylic acid or a derivative thereof and a polyol. As the polycarboxylic acid or a derivative thereof, a divalent dicarboxylic acid or a derivative thereof can be used, and examples thereof include: terephthalic acid, isophthalic acid, dimethyl terephthalate, dimethyl naphthalate, and the like. As the polyol, a divalent diol can be used, and examples thereof include: ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, cyclohexanedimethanol, and the like.
Specific examples of the polyester-based resin include: polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polypropylene terephthalate, polypropylene naphthalate, polycyclohexanedimethylene terephthalate, polycyclohexanedimethylene naphthalate.
The polycarbonate-based resin includes a polymer in which monomer units are bonded via a carbonate group. The polycarbonate-based resin may be a resin called modified polycarbonate in which the main chain is modified, a copolymerized polycarbonate, or the like.
The (meth) acrylic resin is a resin containing a compound having a (meth) acryloyl group as a main constituent monomer. Specific examples of the (meth) acrylic resin include, for example: poly (meth) acrylates such as polymethyl methacrylate; methyl methacrylate- (meth) acrylic acid copolymer; methyl methacrylate- (meth) acrylate copolymers; methyl methacrylate-acrylate- (meth) acrylic acid copolymer; methyl (meth) acrylate-styrene copolymers (MS resins and the like); a copolymer of methyl methacrylate and a compound having an alicyclic hydrocarbon group (for example, a methyl methacrylate-cyclohexyl methacrylate copolymer, a methyl methacrylate-norbornyl (meth) acrylate copolymer, etc.). Preferably used is a poly (meth) acrylic acid C such as poly (methyl (meth) acrylate)1-6The polymer containing an alkyl ester as a main component is preferably a methyl methacrylate resin containing methyl methacrylate as a main component (50 to 100% by weight, preferably 70 to 100% by weight).
The optical film 11 can be produced by stretching a film containing the thermoplastic resin. Examples of the stretching treatment include: uniaxial stretching, biaxial stretching, and the like. Examples of the stretching direction include: the machine flow direction (MD) of the unstretched film, The Direction (TD) orthogonal to the machine flow direction, the direction oblique to the machine flow direction (MD), and the like. The biaxial stretching may be simultaneous biaxial stretching in which stretching is performed simultaneously in two stretching directions, or sequential biaxial stretching in which stretching is performed in a predetermined direction and then stretching is performed in the other direction. The stretching treatment may be performed, for example, by stretching in the longitudinal direction (machine flow direction: MD) using two or more pairs of nip rollers having an increased peripheral speed on the exit side, or by spreading in The Direction (TD) orthogonal to the machine flow direction by nipping both side ends of the unstretched film with a jig. In this case, the retardation value can be controlled within the ranges of the above-described equations (5) to (6) by adjusting the thickness of the film or adjusting the stretch ratio. Further, by adding a wavelength dispersion adjusting agent to the resin, the wavelength dispersion value can be controlled within the ranges of the above-mentioned formulas (7) to (8).
The thickness of the optical film 11 is not particularly limited as long as the above-described formulas (5) to (8) are satisfied, but is preferably 90 μm or less, more preferably 60 μm or less, from the viewpoint of making the polarizing plate thinner, and is preferably 5 μm or more, more preferably 10 μm or more, from the viewpoint of handling.
The optical film 11 may contain one or more additives such as a lubricant, a plasticizer, a dispersant, a heat stabilizer, an ultraviolet absorber, an infrared absorber, an antistatic agent, and an antioxidant.
In addition, in order to impart desired surface optical characteristics or other features, a coating layer (surface treatment layer 20) may be provided on the outer face of the optical film 11. Specific examples of the coating layer include a hard coat layer, an antiglare layer, an antireflection layer, an antistatic layer, and an antifouling layer. The method for forming the coating layer is not particularly limited, and a known method can be used.
In the present invention, as the optical film 11, in order to impart desired retardation characteristics, an optical film satisfying the following expression is used, in which the dimensional change rate D1 in the direction of 45 ° from the absorption axis of the polarizing film and the dimensional change rate D2 in the direction of 135 ° from the absorption axis of the polarizing film when left standing still for 100 hours in an environment of 85 ℃. When the polarizing film 14 is viewed from the stretched optical film 11, the counterclockwise rotation angle is positive.
In the case of | D1| > | D2|, 2 < | D1|/| D2| (1)
In the case of | D1| < | D2|, 2 < | D2|/| D1| (2)
D1 and D2 in the above formulas (1) to (2) can be measured in the following manner with reference to fig. 2. Fig. 2(a) is an example of a plan view showing an absorption axis of a polarizing plate of the present invention, and a direction of 45 ° with respect to the absorption axis and a direction of 135 ° with respect to the absorption axis. As discussed above, the slow axis of the optical film preferably approximately coincides with either direction 31 or direction 32.
First, as shown in fig. 2(b), the optical film was cut so that the dimension was 100mm in the direction of 45 ° and 100mm in the direction of 135 ° with respect to the absorption axis of the polarizing film. The cut optical film 40 was left to stand at a temperature of 23 ℃ and a humidity of 55% for one day, and the dimension (L0(45)) in the direction (direction 31) at 45 ° with respect to the absorption axis of the polarizing film and the dimension (L0(135)) in the direction (direction 32) at 135 ° with respect to the absorption axis of the polarizing film were measured. Then, the dimension in the direction 31 (L1(45)) and the dimension in the direction 32 (L1(135)) were measured after the sheet was left to stand at 85 ℃ for 100 hours. The dimensional change rates D1 (%) and D2 (%) can be determined from the expressions (3) and (4) based on the results.
Dimensional change rate D1 ═ L0(45) -L1(45))/L0(45) ] × 100 (3)
Dimension change rate D2 ═ L0(135) -L1(135))/L0(135) ] × 100 (4)
The optical film 11 satisfying the above formulas (1) to (2) can be produced by, for example, biaxially stretching a film containing the above thermoplastic resin. Among the thermoplastic resins, cellulose resins such as cellulose ester resins such as cellulose triacetate and cellulose diacetate are preferably contained in view of easy availability of films satisfying the above formulae (1) to (2).
The stretching method may be simultaneous biaxial stretching or sequential biaxial stretching, but a film produced by simultaneous biaxial stretching is preferable because a film satisfying the above formulas (1) to (2) can be easily obtained. The method of simultaneous biaxial stretching is not particularly limited, and both ends of the unstretched film may be sandwiched by clamps, and the feed rates of the clamps at both ends may be varied to further expand the unstretched film in The Direction (TD) orthogonal to the machine flow direction. In the simultaneous biaxial stretching, stretching in one direction and contraction by relaxing the tension in the other direction are also included.
In general, since a long polarizing film has an absorption axis in the longitudinal direction, the optical film is preferably a film produced by biaxial stretching and oblique stretching in view of being able to bond a long optical film to a long polarizing film in a roll-to-roll manner.
[ protective film 15]
The protective film 15 is preferably made of a material having excellent transparency, mechanical strength, thermal stability, moisture barrier property, and the like. The protective film 15 preferably contains a cellulose-based resin, a polyolefin-based resin, or an acrylic resin, because the retardation value can be easily controlled and obtained. The polyolefin-based resin referred to herein includes a chain polyolefin-based resin and a cyclic polyolefin-based resin.
As the cellulose-based resin, the cycloolefin-based resin, or the acrylic resin, the same ones as exemplified for the optical film 11 can be used.
The method of forming a film from the resin as described above may be appropriately selected depending on the respective resins, and for example, a solvent casting method, a melt extrusion method, or the like may be used. Among these, the polyolefin-based resin and the acrylic resin are preferably melt-extruded from the viewpoint of productivity. On the other hand, cellulose-based resins are generally formed into films by a solvent casting method.
In the case where the liquid crystal cell is In-Plane switching (IPS) mode, the protective film preferably has a retardation value Rth In the thickness direction In the range of-10 to 10nm so as not to impair the wide viewing angle characteristics inherent In the IPS mode liquid crystal cell.
As a method for controlling the retardation value Rth in the thickness direction of the protective film within the range of-10 to 10nm, the following methods can be mentioned: when a film is produced, the deviation remaining in the plane and in the thickness direction is reduced as much as possible. For example, in the solvent casting method, a method of relaxing residual shrinkage strain in the in-plane and thickness directions generated when the casting resin solution is dried by heat treatment or the like can be used. On the other hand, in the melt extrusion method, in order to prevent the resin film from being stretched until the resin film is extruded from the die and cooled, a method of controlling the extrusion amount and the rotation speed of the cooling drum so that the film is not stretched while shortening the distance from the die to the cooling drum as much as possible may be employed. In addition, as in the solvent casting method, a method of relaxing strain remaining in the obtained film by heat treatment may be employed.
The thickness of the protective film is preferably 90 μm or less, more preferably 60 μm or less, from the viewpoint of thinning of the polarizing plate, and is preferably 5 μm or more, more preferably 10 μm or more, from the viewpoint of handling.
[ adhesive layer ]
The polarizing film and the protective film may be attached by an adhesive or a bonding agent.
The thickness of the adhesive layer for bonding the polarizing film and the protective film may be about 0.01 to 30 μm, preferably 0.01 to 10 μm, and more preferably 0.05 to 5 μm. When the thickness of the adhesive layer is within the above range, the laminated protective film and the polarizing film are not floated or peeled off, and an adhesive force having no practical problem can be obtained. The thickness of the adhesive layer for bonding the polarizing film and the protective film may be about 5 to 50 μm, preferably 5 to 30 μm, and more preferably 10 to 25 μm.
In the case of bonding the polarizing film and the protective film, it is also useful to preliminarily perform saponification treatment, corona treatment, plasma treatment, or the like on the polarizing film and the protective film.
In the formation of the adhesive layer, a suitable adhesive can be suitably used depending on the kind and purpose of the adherend, and a primer can be used as needed. Examples of the adhesive include: solvent-based adhesives, emulsion-based adhesives, pressure-sensitive adhesives, remoistenable adhesives, condensation-type adhesives, solventless adhesives, film-like adhesives, hot-melt adhesives, and the like.
As one of the preferable adhesives, an aqueous adhesive, that is, an adhesive in which an adhesive component is dissolved or dispersed in water can be cited. There is a polyvinyl alcohol resin as an example of the binder component that can be dissolved in water. Further, there is a polyurethane resin having a hydrophilic group as an example of the adhesive component which can be dispersed in water. The aqueous adhesive can be prepared by mixing such an adhesive component with an additional additive added as needed in water. Examples of commercially available polyvinyl alcohol resins that can form a water-based adhesive include carboxyl-modified polyvinyl alcohol "KL-318" sold by KURARAAY K.K.
The aqueous adhesive may contain a crosslinking agent as needed. Examples of the crosslinking agent include amine compounds, aldehyde compounds, methylol compounds, water-soluble epoxy resins, isocyanate compounds, polyvalent metal salts, and the like. When a polyvinyl alcohol resin is used as the adhesive component, an aldehyde compound typified by glyoxal, a methylol compound typified by methylolmelamine, a water-soluble epoxy resin, or the like is preferably used as the crosslinking agent.
The water-soluble epoxy resin may be, for example, a polyamide epoxy resin obtained by reacting epichlorohydrin with a polyamide polyamine which is a reaction product of a polyalkylene polyamine such as diethylenetriamine or triethylenetetramine and a dicarboxylic acid such as adipic acid. Examples of commercially available products of water-soluble epoxy resins include "スミレ - ズレ ジ ン (registered trademark) 650 (30)", which is sold by Tianga chemical industries, Ltd.
A polarizing plate is obtained by applying a water-based adhesive to the adhesive surface of a polarizing film and/or a protective film laminated thereto, laminating them, and then drying the laminate. It is also effective to subject the protective film to an easy-adhesion treatment such as saponification treatment, corona discharge treatment, plasma treatment or undercoating treatment to improve the wettability in advance before the adhesion. The drying temperature may be set to about 50 to 100 ℃, for example. In order to further improve the adhesion, it is preferable that the curing is performed at a temperature slightly higher than room temperature (for example, at a temperature of about 30 to 50 ℃) for about 1 to 10 days after the drying treatment.
Another preferable adhesive is a curable adhesive composition containing an epoxy compound that is cured by irradiation with active energy rays or heating. Here, the curable epoxy compound is a compound having at least 2 epoxy groups in a molecule. In this case, the polarizing film and the protective film may be bonded by a method of curing a curable epoxy compound contained in the adhesive by irradiating the coating layer of the adhesive composition with active energy rays or applying heat. Curing of the epoxy compound is generally carried out by cationic polymerization of the epoxy compound. In addition, from the viewpoint of productivity, the curing is preferably performed by irradiation with an active energy ray.
The epoxy compound contained in the curable adhesive composition is preferably an epoxy compound containing no aromatic ring in the molecule from the viewpoints of weather resistance, refractive index, cationic polymerization, and the like. Examples of the epoxy compound containing no aromatic ring in the molecule include: hydrogenated epoxy compounds, alicyclic epoxy compounds, aliphatic epoxy compounds, and the like. The epoxy compound preferably used in such a curable adhesive composition is described in detail in, for example, Japanese patent application laid-open No. 2004-24925, and the general contents thereof will be described here.
The hydrogenated epoxy compound may be a compound as described below: a compound obtained by subjecting an aromatic polyhydroxy compound as a raw material of an aromatic epoxy compound to a nuclear hydrogenation reaction selectively in the presence of a catalyst under pressure, and subjecting the thus-obtained nuclear hydrogenated polyhydroxy compound to glycidyl etherification. Examples of the aromatic polyhydroxy compound to be a raw material of the aromatic epoxy compound include: bisphenols such as bisphenol a, bisphenol F and bisphenol S; novolak resins such as phenol novolak resins, cresol novolak resins and hydroxybenzaldehyde phenol novolak resins; and polyfunctional compounds such as tetrahydroxydiphenylmethane, tetrahydroxybenzophenone, and polyvinyl phenol. Glycidyl etherification can be performed by subjecting such an aromatic polyol to a nuclear hydrogenation reaction and reacting epichlorohydrin with the nuclear hydrogenated polyol obtained above. As a preferred hydrogenated epoxy compound, a hydrogenated glycidyl ether of bisphenol A can be cited.
The alicyclic epoxy compound is a compound having at least one epoxy group bonded to an alicyclic ring in a molecule. The "epoxy group bonded to an alicyclic ring" refers to a bridged oxygen atom-O-in the structure represented by the following formula, wherein m is an integer of 2 to 5.
Figure BDA0001153041120000131
Will be (CH) in the formula2)mCompounds in which one or more of the hydrogen atoms are removed and bonded to other chemical structures may form alicyclic epoxy compounds. In addition, forming an alicyclic ring (CH)2)mOne or more hydrogen atoms in (b) may be appropriately substituted with a linear alkyl group such as a methyl group or an ethyl group. Among the alicyclic epoxy compounds, an epoxy compound having an oxabicyclohexane ring (a structure in which m is 3 in the above formula) or an oxabicycloheptane ring (a structure in which m is 4 in the above formula) is preferably used in order to exhibit excellent adhesiveness. Specific examples of the alicyclic epoxy compound are shown below. Here, the compound names are listed first, and then the chemical formulae corresponding thereto are shown, respectively, and the compound names and the chemical formulae corresponding thereto are denoted by the same symbols.
A: 3, 4-epoxycyclohexanecarboxylic acid 3, 4-epoxycyclohexylmethyl ester,
B: 3, 4-epoxy-6-methylcyclohexanecarboxylic acid 3, 4-epoxy-6-methylcyclohexylmethyl ester,
C: ethylidene bis (3, 4-epoxycyclohexane formate),
D: bis (3, 4-epoxycyclohexylmethyl) adipate,
E: adipic acid di (3, 4-epoxy-6-methylcyclohexylmethyl) ester,
F: diethylene glycol di (3, 4-epoxycyclohexylmethyl ether),
G: ethylene glycol di (3, 4-epoxy cyclohexyl methyl ether),
H: 2, 3, 14, 15-diepoxy-7, 11, 18, 21-tetraoxatrispiro [5.2.2.5.2.2] heneicosane,
I: 3- (3, 4-epoxycyclohexyl) -8, 9-epoxy-15-dioxaspiro [5.5] undecane,
J: 4-vinylcyclohexene dioxide,
K: a limonene dioxide,
L: di (2, 3-epoxycyclopentyl) ether,
M: dicyclopentadiene dioxide, and the like.
Figure BDA0001153041120000151
The aliphatic epoxy compound may be a polyglycidyl ether of an aliphatic polyhydric alcohol or an alkylene oxide adduct thereof. More specifically, there may be mentioned: a diglycidyl ether of propylene glycol; a diglycidyl ether of 1, 4-butanediol; a diglycidyl ether of 1, 6-hexanediol; triglycidyl ethers of glycerol; triglycidyl ether of trimethylolpropane; polyglycidyl ethers of polyether polyols (for example, diglycidyl ethers of polyethylene glycol) obtained by adding alkylene oxides (ethylene oxide and propylene oxide) to aliphatic polyols such as ethylene glycol, propylene glycol, and glycerin.
In the curable adhesive composition, only one epoxy compound may be used alone, or two or more epoxy compounds may be used in combination. Among them, the epoxy compound preferably contains an alicyclic epoxy compound having at least one epoxy group bonded to an alicyclic ring in the molecule.
The epoxy compound used in the curable adhesive composition has an epoxy equivalent generally in the range of 30 to 3000 g/equivalent, and the epoxy equivalent is preferably in the range of 50 to 1500 g/equivalent. When an epoxy compound having an epoxy equivalent of less than 30 g/equivalent is used, the flexibility of the cured polarizing plate may be reduced or the adhesive strength may be reduced. On the other hand, in the case of a compound having an epoxy equivalent of more than 3000 g/equivalent, compatibility with other components contained in the adhesive composition may be lowered.
From the viewpoint of reactivity, cationic polymerization is preferably used as the curing reaction of the epoxy compound. For this reason, it is preferable to add a cationic polymerization initiator to the curable adhesive composition containing an epoxy compound. The cationic polymerization initiator generates a cationic species or lewis acid by irradiation or heating of active energy rays such as visible light, ultraviolet rays, X-rays, and electron rays, thereby initiating a polymerization reaction of an epoxy group. From the viewpoint of handling properties, it is preferable to impart latency to the cationic polymerization initiator. Hereinafter, a cationic polymerization initiator that generates a cationic species or a lewis acid by irradiation with an active energy ray to initiate a polymerization reaction of an epoxy group is referred to as a "photo cationic polymerization initiator", and a cationic polymerization initiator that generates a cationic species or a lewis acid by heat to initiate a polymerization reaction of an epoxy group is referred to as a "thermal cationic polymerization initiator".
The method of curing the adhesive composition by irradiation with an active energy ray using a photo cation polymerization initiator is advantageous in that the curing can be performed at normal temperature and normal humidity, and the protective film and the polarizing film can be favorably adhered in consideration of the reduction in the necessity of heat resistance of the polarizing film or deformation due to expansion. Further, the photo cation polymerization initiator exhibits a catalytic action by light, and therefore, even when mixed in an epoxy compound, is excellent in storage stability and handling properties.
Examples of the photo cation polymerization initiator include: an aromatic diazonium salt; and onium salts such as aromatic iodonium salts and aromatic sulfonium salts, iron-arene complexes, and the like. The amount of the photo cation polymerization initiator is usually 0.5 to 20 parts by weight, preferably 1 part by weight or more, and more preferably 15 parts by weight or less based on 100 parts by weight of the epoxy compound.
When the compounding amount of the photo cation polymerization initiator is less than 0.5 parts by weight with respect to 100 parts by weight of the epoxy compound, there is a tendency that: the curing becomes insufficient, and the mechanical strength and adhesive strength of the cured product decrease.
On the other hand, when the amount of the photo cation polymerization initiator is more than 20 parts by weight based on 100 parts by weight of the epoxy compound, the increase of ionic substances in the cured product may increase the hygroscopicity of the cured product, thereby deteriorating the durability.
When a photo cationic polymerization initiator is used, the curable adhesive composition may further contain a photosensitizer as necessary. By using the photosensitizer, the reactivity of cationic polymerization can be improved, and the mechanical strength and adhesive strength of a cured product can be improved. As the photosensitizer, for example: carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, azo compounds, diazo compounds, halogen compounds, photoreducible pigments, and the like. When the photosensitizer is added, the amount thereof is preferably set in the range of 0.1 to 20 parts by weight with respect to 100 parts by weight of the curable adhesive composition. In addition, a sensitizing additive such as a naphthoquinone derivative can be used in order to increase the curing speed.
On the other hand, as the thermal cationic polymerization initiator, there can be mentioned: benzylsulfonium salts, thiophenium salts, thialanium (thiolanium) salts, benzylammonium, pyridinium salts, hydrazinium salts, carboxylic acid esters, sulfonic acid esters, and aminimides.
The curable adhesive composition containing an epoxy compound is preferably cured by the photo cationic polymerization as described above, and may be cured by the thermal cationic polymerization in the presence of the thermal cationic polymerization initiator, or may be used in combination of the photo cationic polymerization and the thermal cationic polymerization. When both the photo cation polymerization and the thermal cation polymerization are used, it is preferable that both the photo cation polymerization initiator and the thermal cation polymerization initiator are contained in the curable adhesive composition.
The curable adhesive composition may further contain a compound that promotes cationic polymerization, such as an oxetane compound or a polyol compound. Oxetane compounds are compounds having a quaternary cyclic ether in the molecule. When the oxetane compound is blended, the amount thereof in the curable adhesive composition is usually 5 to 95% by weight, preferably 5 to 50% by weight. The polyol compound may be an alkylene glycol or its oligomer including ethylene glycol, 1, 6-hexanediol, polyethylene glycol, etc., a polyester polyol, a polycaprolactone polyol, a polycarbonate polyol, etc. When the polyol compound is blended, the amount thereof in the curable adhesive composition is usually 50% by weight or less, preferably 30% by weight or less.
The curable adhesive composition may contain other additives such as an ion trapping agent, an antioxidant, a chain transfer agent, a sensitizer, a thickener, a thermoplastic resin, a filler, a flow control agent, a plasticizer, and an antifoaming agent, as long as the adhesiveness is not impaired. Examples of the ion-capturing agent include powdery inorganic compounds such as bismuth-based, antimony-based, magnesium-based, aluminum-based, calcium-based, titanium-based, and mixtures thereof, and examples of the antioxidant include hindered phenol-based antioxidants.
After a curable adhesive composition containing an epoxy compound is applied to the adhesive surface of a polarizing film or a protective film or both of them, the surfaces coated with the adhesive are bonded to each other, and the uncured adhesive layer is cured by irradiation with an active energy ray or heating, whereby the polarizing film and the protective film can be bonded to each other. As a method for applying the adhesive, various application methods such as a doctor blade, a wire bar, a die coater, a comma coater (comma coater), and a gravure roll coater can be used.
The curable adhesive composition can be used as a solvent-free adhesive substantially free of a solvent, and has an optimum viscosity range for each application method, and therefore, a solvent may be contained for adjusting the viscosity. The solvent is preferably an organic solvent which can dissolve each component represented by an epoxy compound well without lowering the optical performance of the polarizing film, and for example, hydrocarbons represented by toluene, esters represented by ethyl acetate, and the like can be used.
When the adhesive composition is cured by irradiation with an active energy ray, various active energy rays as described above can be used as the active energy ray, but ultraviolet rays are preferably used because handling is easy and control of the amount of irradiation light and the like is easy. The irradiation intensity and the irradiation amount of the active energy ray, for example, ultraviolet ray are appropriately determined within a range not affecting various optical properties represented by the degree of polarization of the polarizing film and various optical properties represented by the transparency and the phase difference characteristics of the protective film so as to maintain appropriate productivity.
When the adhesive composition is cured by heat, heating may be performed by a generally known method. The thermal cationic polymerization initiator to be added to the curable adhesive composition is generally heated at a temperature not lower than the temperature at which the cationic species and the Lewis acid are generated, and the heating temperature is, for example, about 50 to 200 ℃.
[ lamination of polarizing film 14 and optical film 11]
The polarizing film 14 and the optical film 11 are preferably directly laminated via the 1 st adhesive layer 12. By laminating the polarizing film 14 and the optical film 11 with the adhesive layer interposed therebetween, stress applied to the polarizing film due to anisotropic dimensional change of the optical film 11 can be relaxed at the time of the heat resistance test.
[1 st adhesive layer 12]
The 1 st pressure-sensitive adhesive layer 12 used for laminating the polarizing film 14 and the optical film 11 may be a pressure-sensitive adhesive having excellent optical transparency and excellent adhesive properties including appropriate wettability, cohesiveness, adhesiveness, and the like, and more preferably a pressure-sensitive adhesive having excellent durability and the like. Specifically, the adhesive forming the 1 st adhesive layer 12 is preferably an adhesive containing an acrylic resin (acrylic adhesive).
The acrylic resin contained in the acrylic adhesive is a resin containing, as a main monomer, an alkyl acrylate such as butyl acrylate, ethyl acrylate, isooctyl acrylate, and 2-ethylhexyl acrylate. The acrylic resin is usually copolymerized with a polar monomer. The polar monomer is a compound having a polymerizable unsaturated bond and a polar functional group, wherein the polymerizable unsaturated bond is generally derived from a (meth) acryloyl group, and the polar functional group may be a carboxyl group, a hydroxyl group, an amide group, an amino group, an epoxy group, or the like. Specific examples of the polar monomer include (meth) acrylic acid, 2-hydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) acrylamide, 2-N, N-dimethylaminoethyl (meth) acrylate, and glycidyl (meth) acrylate.
In addition, a crosslinking agent is generally blended with the acrylic resin in the acrylic adhesive. Typical examples of the crosslinking agent include isocyanate compounds having at least 2 isocyanate groups (-NCO) in the molecule.
Various additives may be further blended in the binder. Preferable additives include silane coupling agents and antistatic agents. The silane coupling agent is effective in improving adhesion to glass. The antistatic agent is effective in reducing or preventing the generation of static electricity.
The 1 st pressure-sensitive adhesive layer 12 can be formed by a method of preparing a pressure-sensitive adhesive composition in which the above-mentioned pressure-sensitive adhesive component is dissolved in an organic solvent, directly applying the composition to any one of bonding surfaces (a polarizing film or an optical film) to be bonded, and then drying and removing the solvent, or a method of applying the above-mentioned pressure-sensitive adhesive composition to a release-treated surface of a base film made of a release-treated resin film, then drying and removing the solvent to prepare a pressure-sensitive adhesive layer, bonding the pressure-sensitive adhesive layer to any one of the bonding surfaces (the polarizing film or the optical film), and transferring the pressure-sensitive adhesive. In the case of forming the 1 st pressure-sensitive adhesive layer 12 by the former direct coating method, a general example is to temporarily protect the surface of the pressure-sensitive adhesive layer until use by bonding a resin film (also referred to as a separator) subjected to a release treatment to the surface thereof. The latter transfer method is often used from the viewpoint of workability of the adhesive composition as an organic solvent solution, and in this case, the base film subjected to the releasing treatment for forming the 1 st adhesive layer is preferably used because the interlayer can be formed directly after the base film is bonded to the polarizing plate.
In the heat resistance test, the storage elastic modulus of the adhesive at 80 ℃ is preferably 5MPa or less, and preferably 1MPa or less, in order to ensure sufficient adhesion and dimensional stability and suppress a decrease in the degree of polarization during the heat resistance test.
It is also useful to subject the polarizing film surface to be bonded and the optical film surface or adhesive surface to corona treatment, plasma treatment, or the like in advance before lamination with an adhesive or an adhesive.
[2 nd adhesive layer 16]
Adhesive layer 16 may be used to bond polarizer plate 10 to the adhesive layer of the liquid crystal cell.
The 2 nd pressure-sensitive adhesive layer 16 formed on the surface of the protective film 15 opposite to the surface to be bonded to the polarizing film 14 may be a pressure-sensitive adhesive layer having excellent optical transparency and excellent adhesive properties including appropriate wettability, cohesiveness, adhesiveness, and the like, and more preferably a pressure-sensitive adhesive layer having excellent durability and the like. Specifically, as the adhesive for forming the 2 nd adhesive layer 16, an adhesive containing an acrylic resin (acrylic adhesive) is preferably used. Specifically, the same adhesive as the 1 st adhesive 12 described above can be used.
The 2 nd adhesive layer 16 may contain various additives as in the 1 st adhesive layer 12. Among them, the 2 nd adhesive layer 16 preferably contains an antistatic agent. In general, when a polarizing plate is bonded to a liquid crystal cell with an adhesive layer interposed therebetween, a surface protective film (interlayer) that has been once protected by the adhesive layer is peeled off and then bonded to the liquid crystal cell. As a method for reducing or preventing such static electricity generation, it is effective to add an antistatic agent to the adhesive.
In the case of bonding the protective film 15 and the 2 nd pressure-sensitive adhesive layer 16, it is also useful to subject the surfaces where the protective film 15 and the 2 nd pressure-sensitive adhesive layer 16 are bonded to each other to corona treatment, plasma treatment, or the like.
[ method for producing polarizing plate ]
The method for producing the polarizing plate of the present invention is not particularly limited, and for example, the polarizing plate 10 is obtained by laminating a polarizing plate in which a polarizing film 14 and a protective film 15 are laminated and an optical film with an adhesive in which an optical film 11 and a 1 st adhesive layer 12 are laminated, in a roll-to-roll manner, with the 1 st adhesive layer 12 interposed therebetween. Further, the 2 nd adhesive layer 16 was formed on the protective film 15, thereby obtaining an adhesive-attached polarizing plate. The polarizing plate with an adhesive may be bonded to the liquid crystal cell via the 2 nd adhesive layer 16.
[ liquid Crystal cell ]
The liquid crystal cell has 2 unit substrates and a liquid crystal layer sandwiched between the 2 unit substrates. The unit substrate is generally made of glass in many cases, but may be a plastic substrate. In addition, the liquid crystal cell itself used in the liquid crystal panel of the present invention may be composed of various substances employed in the art.
[ liquid Crystal Panel ]
The liquid crystal panel can be manufactured by bonding the polarizing plate 10 to the liquid crystal cell via the 2 nd adhesive layer 16. In general, polarizing plates are attached to both sides of the liquid crystal cell, but the polarizing plate of the present invention is preferably used on the viewing side of the liquid crystal display device.
Examples
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In the examples, unless otherwise specified, parts and% indicating contents or amounts used are on a weight basis. The measurement of each physical property in the following examples was performed by the following method.
(1) Measurement of thickness:
the measurement was carried out using a digital micrometer "MH-15M" manufactured by Nikon K.K.
(2) Measurement of in-plane phase difference value and phase difference value in thickness direction:
an in-plane retardation value and a retardation value in the thickness direction at a predetermined wavelength were measured at a temperature of 23 ℃ using a retardation meter "KOBRA-21 ADH" manufactured by prince instruments co.
(3) Measurement of degree of polarization and monomer transmittance of polarizing plate:
using a spectrophotometer with an integrating sphere ("V7100" manufactured by japan spectrographic corporation, 2 degree field of view; c illuminant ] was measured.
(4) Method for measuring dimensional change rate of film
The dimensional change rate D1 in the direction of 45 ° with respect to the absorption axis of the polarizing film and the dimensional change rate D2 in the direction of 135 ° with respect to the absorption axis of the polarizing film when the film was left standing at 85 ℃ for 100 hours were measured by a two-dimensional measuring instrument "NEXIVVMR-12072" manufactured by nikon corporation as follows. First, the optical film was cut so as to have a dimension of 100mm in the direction of 45 ° with respect to the absorption axis of the polarizing film and a dimension of 100mm in the direction of 135 °. The cut optical film was allowed to stand still for one day in an environment of 23 ℃ and 55% humidity, and the dimension in the direction of 45 ° with respect to the absorption axis of the polarizing film (L0(45)) and the dimension in the direction of 135 ° with respect to the absorption axis of the polarizing film (L0(135)) were measured. Next, the polarizing film was left to stand at 85 ℃ for 100 hours, and the dimension in the direction of 45 ° with respect to the absorption axis of the polarizing film (L1(45)) and the dimension in the direction of 135 ° with respect to the absorption axis of the polarizing film (L1(135)) after the standing at a high temperature were measured. Based on the above results, the dimensional change rates D1 (%) and D2 (%) were determined from the expressions (3) and (4).
Dimensional change rate D1 ═ L0(45) -L1(45))/L0(45) ] × 100 (3)
Dimension change rate D2 ═ L0(135) -L1(135))/L0(135) ] × 100 (4)
(method of measuring storage modulus of elasticity)
The storage modulus of elasticity (G') of the adhesive was determined as follows: a cylindrical test piece having a diameter of 8mm × a thickness of 1mm and composed of a binder to be measured was prepared, and the measurement was performed by a Dynamic viscoelasticity measuring apparatus (Dynamic Analyzer RDA II: manufactured by REMOMETRIC corporation) under a condition that an initial strain was set to 1N and a temperature was 80 ℃ by a torsional shear method at a frequency of 1 Hz.
Production example 1 production of polarizing film
A polyvinyl alcohol film (average degree of polymerization: 2400, degree of saponification: 99.9 mol% or more) having a thickness of 20 μm was uniaxially stretched by dry stretching at about 4 times, immersed in pure water at 40 ℃ for 40 seconds while being kept under tension, and then immersed in an aqueous solution having a weight ratio of iodine/potassium iodide/water of 0.052/5.7/100 at 28 ℃ for 30 seconds to perform dyeing treatment. Then, the plate was immersed in an aqueous solution having a weight ratio of potassium iodide/boric acid/water of 11.0/6.2/100 at 70 ℃ for 120 seconds. Subsequently, the polarizing film was washed with pure water at 8 ℃ for 15 seconds, dried at 60 ℃ for 50 seconds and then at 75 ℃ for 20 seconds while being held under a tension of 300N, thereby obtaining a polarizing film having a thickness of 7 μm in which iodine was adsorbed and oriented on the polyvinyl alcohol film.
Production example 2 preparation of aqueous adhesive
An aqueous adhesive was prepared by dissolving 3 parts by weight of carboxyl-modified polyvinyl alcohol [ trade name "KL-318" from KURARAY corporation ] in 100 parts by weight of water, and adding 1.5 parts by weight of a polyamide epoxy additive [ trade name "スミレ - ズレ ジ ン (registered trademark) 650 (30)" from tianggang chemical industries, inc., and an aqueous solution having a solid content concentration of 30% by weight ] as a water-soluble epoxy resin to the aqueous solution.
[ Binders ]
The following adhesives a to E were prepared.
Adhesive A: sheet-like adhesive having a thickness of 25 μm ("P-3132" manufactured by LINTEC corporation)
And (3) adhesive B: sheet adhesive having a thickness of 15 μm ("P-0082" manufactured by LINTEC corporation, having a storage modulus of elasticity of 0.04MPa at 80 ℃)
And (3) adhesive C: sheet-like adhesive having a thickness of 5 μm ("NCF # L2" manufactured by LINTEC corporation; storage modulus of elasticity at 80 ℃ of 0.2 MPa.)
Adhesive D: sheet-like adhesive having a thickness of 25 μm ("NCF # E4" manufactured by LINTEC corporation; storage modulus of elasticity at 80 ℃ of 0.8 MPa)
And (3) a binder E: a sheet-like adhesive having a thickness of 25 μm [ obtained by processing "# E5" manufactured by LINTEC K.K. ] into a sheet-like adhesive, and having a storage modulus of elasticity of 1.3MPa at 80 ]
[ protective film ]
The following protective film was prepared.
Protecting the film: a cyclic polyolefin resin film manufactured by Zeon corporation; ZF14-013 (thickness 13 μm, in-plane retardation at wavelength 590nm of 0.5nm, thickness direction retardation at wavelength 590nm of 3.3nm)
[ optical film ]
The following optical films were prepared.
An optical film: a triacetyl cellulose film manufactured by konica minolta corporation; KC4UGR-HC (thickness 44 μm, in-plane phase difference at wavelength 590nm of 106nm, thickness direction phase difference at wavelength 590nm of 75nm, Rth (590)/Re (590) of 0.71, Re (450)/Re (550) of 0.96, Re (630)/Re (550) of 1.02, dimensional change D1 of 0.08%, dimensional change D2 of 0.26%, | D2|/| D1| of 3.25)
[ example 1]
One surface of the protective film is subjected to corona treatment, and the optical film is subjected to saponification treatment. The corona-treated surface of the protective film and the polarizing film were bonded with an aqueous adhesive to obtain a polarizing plate with a single-sided protective film. Next, adhesive B was laminated on one side of the optical film, to obtain an optical film with an adhesive. The polarizing film side of the obtained polarizing plate with the single-sided protective film and the adhesive surface of the optical film with an adhesive were bonded so that the absorption axis of the polarizing plate and the slow axis of the optical film were at 45 °, to obtain a polarizing plate. Further, an adhesive a was laminated on the protective film side of the obtained polarizing plate, to obtain a polarizing plate with an adhesive. The degree of polarization of the polarizing plate was 99.993%.
The polarizing plate thus produced was cut into a 40mm square, and bonded to EAGLE XG manufactured by corning corporation to produce a sample for heat resistance evaluation. The sample for heat resistance evaluation was put into an oven at 105 ℃ for 30 minutes. The degree of polarization after the heat resistance test was 99.975%.
[ example 2]
One surface of the protective film is subjected to corona treatment, and the optical film is subjected to saponification treatment. The corona-treated surface of the protective film and the polarizing film were bonded with an aqueous adhesive to obtain a polarizing plate with a single-sided protective film. Next, adhesive C was laminated on one side of the optical film, to obtain an adhesive-attached optical film. The polarizing film side of the obtained polarizing plate with the single-sided protective film and the adhesive surface of the optical film with an adhesive were bonded so that the absorption axis of the polarizing plate and the slow axis of the optical film were at 45 °, to obtain a polarizing plate. Further, an adhesive a was laminated on the protective film side of the obtained polarizing plate, to obtain a polarizing plate with an adhesive. The degree of polarization of the polarizing plate was 99.997%.
The polarizing plate thus produced was cut into a 40mm square, and bonded to EAGLE XG manufactured by corning corporation to produce a sample for heat resistance evaluation. The sample for heat resistance evaluation was put into an oven at 105 ℃ for 30 minutes. The degree of polarization after the heat resistance test was 99.974%.
[ example 3]
One surface of the protective film is subjected to corona treatment, and the optical film is subjected to saponification treatment. The corona-treated surface of the protective film and the polarizing film were bonded with an aqueous adhesive to obtain a polarizing plate with a single-sided protective film. Next, an adhesive D was laminated on one surface of the optical film, to obtain an optical film with an adhesive. The polarizing film side of the obtained polarizing plate with the single-sided protective film and the adhesive surface of the optical film with an adhesive were bonded so that the absorption axis of the polarizing plate and the slow axis of the optical film were at 45 °, to obtain a polarizing plate. Further, an adhesive a was laminated on the protective film side of the obtained polarizing plate, to obtain a polarizing plate with an adhesive. The degree of polarization of the polarizing plate was 99.996%.
The polarizing plate thus produced was cut into a 40mm square, and bonded to EAGLE XG manufactured by corning corporation to produce a sample for heat resistance evaluation. The sample for heat resistance evaluation was put into an oven at 105 ℃ for 30 minutes. The degree of polarization after the heat resistance test was 99.975%.
[ example 4]
One surface of the protective film is subjected to corona treatment, and the optical film is subjected to saponification treatment. The corona-treated surface of the protective film and the polarizing film were bonded with an aqueous adhesive to obtain a polarizing plate with a single-sided protective film. Next, an adhesive E was laminated on one surface of the optical film, to obtain an optical film with an adhesive. The polarizing film side of the obtained polarizing plate with the single-sided protective film and the adhesive surface of the optical film with an adhesive were bonded so that the absorption axis of the polarizing plate and the slow axis of the optical film were at 45 °, to obtain a polarizing plate. Further, an adhesive a was laminated on the protective film side of the obtained polarizing plate, to obtain a polarizing plate with an adhesive. The degree of polarization of the polarizing plate was 99.994%.
The polarizing plate thus produced was cut into a 40mm square, and bonded to EAGLE XG manufactured by corning corporation to produce a sample for heat resistance evaluation. The sample for heat resistance evaluation was put into an oven at 105 ℃ for 30 minutes. The degree of polarization after the heat resistance test was 99.973%.
Comparative example 1
One surface of the protective film is subjected to corona treatment, and the optical film is subjected to saponification treatment. The corona-treated surface of the protective film, the polarizing film, and the optical film were bonded in this order with a water-based adhesive to obtain a polarizing plate. The absorption axis of the resulting polarizing plate and the slow axis of the optical film were set to 45 °. Further, an adhesive a was laminated on the protective film B side of the obtained polarizing plate, to obtain a polarizing plate with an adhesive. The degree of polarization of the polarizing plate was 99.995%.
The polarizing plate thus produced was cut into a 40mm square, and bonded to EAGLE XG manufactured by corning corporation to produce a sample for heat resistance evaluation. The sample for heat resistance evaluation was put into an oven at 105 ℃ for 30 minutes. The degree of polarization after the heat resistance test was 99.962%.
The results are summarized in Table 1.
[ Table 1]
Figure BDA0001153041120000251
Industrial applicability
According to the present invention, it is possible to provide a polarizing plate capable of suppressing a decrease in the degree of polarization caused by a shift in the absorption axis of a polarizing film due to a dimensional change of an optical film during a heat resistance test.
Description of the symbols
10 polarizing plate
11 optical film
12 st adhesive layer
14 polarizing film
15 protective film
16 nd 2 adhesive layer
20 surface treatment layer
30 absorption axis of polarizing film
31 is oriented at 45 ° with respect to the absorption axis of the polarizing film
32 is oriented at 135 deg. relative to the absorption axis of the polarizing film
33 45°
34 135°
40 cut optical film 11

Claims (5)

1. A polarizing plate comprising a phase difference film, a 1 st adhesive layer, a polarizing film, and a 2 nd adhesive layer for attachment to a liquid crystal cell in this order,
the angle formed by the absorption axis of the polarizing film and the slow axis of the phase difference film is about 45 DEG or about 135 DEG,
a dimensional change rate D1 in a direction of 45 DEG with respect to the absorption axis of the polarizing film when the retardation film is left standing for 100 hours in an environment of 85 ℃ and a dimensional change rate D2 in a direction of 135 DEG with respect to the absorption axis of the polarizing film when the retardation film is left standing for 100 hours in an environment of 85 ℃ satisfy the following formulas (1) and (2),
in the case of | D1| > | D2|, 2 < | D1|/| D2| (1)
In the case of | D1| < | D2|, 2 < | D2|/| D1| (2).
2. The polarizing plate according to claim 1, wherein the phase difference film comprises at least one selected from the group consisting of cyclic polyolefin-based resins, polycarbonate-based resins, cellulose-based resins, polyester-based resins, and (meth) acrylic resins.
3. The polarizing plate according to claim 1 or 2, wherein the polarizing film has a thickness of 15 μm or less.
4. The polarizing plate of claim 1 or 2, further comprising a protective film between the polarizing film and the 2 nd adhesive layer.
5. A liquid crystal panel, wherein the polarizing plate according to any one of claims 1 to 4 is laminated on at least one surface of a liquid crystal cell via the 2 nd adhesive layer.
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