CN107533253B - Liquid crystal display device with touch panel and manufacturing method thereof - Google Patents
Liquid crystal display device with touch panel and manufacturing method thereof Download PDFInfo
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- CN107533253B CN107533253B CN201680027241.2A CN201680027241A CN107533253B CN 107533253 B CN107533253 B CN 107533253B CN 201680027241 A CN201680027241 A CN 201680027241A CN 107533253 B CN107533253 B CN 107533253B
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- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
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- G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
- G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
- G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
- G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
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- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
- G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
- G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
- G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
- G06F3/044—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means
- G06F3/0445—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means using two or more layers of sensing electrodes, e.g. using two layers of electrodes separated by a dielectric layer
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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
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- 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
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- 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
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/13363—Birefringent elements, e.g. for optical compensation
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- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F2203/00—Indexing scheme relating to G06F3/00 - G06F3/048
- G06F2203/041—Indexing scheme relating to G06F3/041 - G06F3/045
- G06F2203/04103—Manufacturing, i.e. details related to manufacturing processes specially suited for touch sensitive devices
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Abstract
The invention provides a liquid crystal display device with a touch panel having a VA mode liquid crystal cell with excellent front contrast and a manufacturing method thereof. The liquid crystal display device with a touch panel of the present invention is a liquid crystal display device with a touch panel, which is provided with a polarizing plate-integrated touch panel module having a transparent conductive layer on the identification side of a VA-mode liquid crystal cell, and is characterized in that the polarizing plate-integrated touch panel module having the transparent conductive layer is provided with an optical compensation film having a transparent conductive layer on at least one side, a polarizing plate and a protective film in this order from the VA-mode liquid crystal cell to the identification side, and the glass transition temperature Tg of the optical compensation film is in the range of 155 to 250 ℃.
Description
Technical Field
The invention relates to a liquid crystal display device with a touch panel and a manufacturing method thereof. More particularly, the present invention relates to a touch panel-equipped liquid crystal display device having excellent front contrast and a method for manufacturing the same.
Background
In recent years, liquid crystal display devices equipped with touch panels have been becoming more and more popular, and are expected to continue to increase in the future.
For example, an electrostatic capacitance type touch panel module used in a touch panel forms an X electrode pattern extending in the X direction with a transparent conductive layer (also referred to as a transparent electrode) on a transparent substrate, and forms a Y electrode pattern extending in the Y direction with the other transparent conductive layers. When the surface of the touch panel is touched with a finger, the X electrode pattern and the Y electrode pattern are brought into contact with each other, and the change in electrostatic capacitance at the position is detected by the X and Y electrode patterns.
As a structure in which such a transparent conductive layer having 2 electrodes is combined with a polarizing plate and a liquid crystal cell, for example, a plug-in touch panel module is known.
Fig. 1 is a schematic view showing an example of a conventional touch panel-equipped liquid crystal display device including a plug-in touch panel module.
As will be described later in detail, a polarizing plate in which a polarizer is sandwiched between 2 protective films is disposed adjacent to a liquid crystal cell, and a film sensor (also referred to as a touch panel module) in which a transparent electrode containing ITO (indium tin oxide) or the like and a protective layer for protecting the transparent electrode are formed on a transparent base film via an adhesive layer is provided thereon, and further, the polarizing plate is bonded to a front panel such as glass or acrylic via an adhesive layer.
In the case of such a configuration, the polarizing plate and the film sensor are independent of each other, and thus the touch panel has a certain thickness.
In the future, in the development of thinning of display devices, further thinning of touch panels, which are main components, is also required.
As a touch panel structure for coping with a demand for thin thickness, integration of a film sensor and a polarizing plate has been attempted, and there are touch panel modules called as a so-called Mid-cell type or an in-cell type as opposed to an external type (for example, see patent documents 1 and 2). These polarizing plate-integrated touch panel modules are modules that are designed to reduce the thickness of members by forming the transparent electrodes on optical compensation films and protective films, which are components of polarizing plates.
On the other hand, as 1 of the main components of the liquid crystal display device, a liquid crystal cell is given.
Although there are a plurality of types of liquid crystal cells depending on the liquid crystal molecules used, VA (vertical alignment) mode and IPS (in-plane switching) mode are currently the mainstream. In general, the VA mode is considered to have superior front contrast compared to the IPS mode. This is because the VA mode liquid crystal molecules are aligned vertically when the electric field is off, and thus leakage of backlight light to the viewing side in black display can be further suppressed.
The present inventors combined the above-mentioned so-called Mid-cell or embedded polarizing plate integrated touch panel module with a VA mode liquid crystal display unit, and as a result, failed to obtain an effect of improving the front contrast ratio expected when using an IPS mode liquid crystal display unit.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2011-81810
Patent document 2: japanese patent laid-open publication No. 2013-104847
Disclosure of Invention
The present invention has been made in view of the above problems and situations, and an object of the present invention is to provide a liquid crystal display device with a touch panel including a VA mode liquid crystal cell having excellent front contrast, and a method for manufacturing the same.
In order to solve the above problems, the present inventors have found, in the course of their studies, that: the present invention can solve the problem of the present invention when a liquid crystal display device with a touch panel is provided with a polarizing plate-integrated touch panel module having a transparent conductive layer on the identification side of a VA-mode liquid crystal cell, the polarizing plate-integrated touch panel module having an optical compensation film having a transparent conductive layer on at least one surface, a polarizing plate, and a protective film in this order from the VA-mode liquid crystal cell to the identification side, and the glass transition temperature Tg of the optical compensation film is a specific value or more.
That is, the above problem according to the present invention can be solved by the following method.
1. A liquid crystal display device with a touch panel, comprising a touch panel module integrated with a polarizing plate having a transparent conductive layer on the identification side of a VA mode liquid crystal cell,
the touch panel module integrated with a polarizing plate having the transparent conductive layer comprises an optical compensation film having a transparent conductive layer on at least one surface, a polarizing plate and a protective film in this order from the VA mode liquid crystal cell to the viewing side, and the touch panel module integrated with a polarizing plate has
The glass transition temperature Tg of the optical compensation film is in the range of 155-250 ℃.
2. The touch panel-equipped liquid crystal display device according to claim 1, wherein the optical compensation film contains any one of a cycloolefin resin, a polyimide resin, and a polyarylate resin.
3. The touch panel-equipped liquid crystal display device according to claim 1 or 2, wherein the optical compensation film has a variation of a retardation value Ro in an in-plane direction within a range of ± 3.0% and a variation of a retardation value Rt in a thickness direction within a range of ± 4.0% when subjected to a heat treatment at 150 ℃ for 1 hour.
4. The touch panel-equipped liquid crystal display device according to any one of claims 1 to 3, wherein the optical compensation film has a thickness in a range of 10 to 40 μm.
5. The touch-panel-equipped liquid crystal display device according to any one of claims 1 to 4, wherein the optical compensation film contains a nitrogen-containing heterocyclic compound having a structure represented by the following general formula (3) as a retardation raising agent.
General formula (3)
(wherein A represents a pyrazole ring, Ar1And Ar2Each represents an aromatic hydrocarbon ring or an aromatic heterocyclic ring, and may have a substituent. R1Represents a hydrogen atom, an alkyl group, an acyl group, a sulfonyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group. q represents 1 or 2. n and m are eachRepresents an integer of 1 to 3. )
6. A method for manufacturing a touch-panel-equipped liquid crystal display device, the touch-panel-equipped liquid crystal display device according to any one of items 1 to 5, comprising:
forming the transparent conductive layer on at least one surface of the optical compensation film, and then performing heat treatment at 150 ℃ or higher;
a step of bonding the optical compensation film on which the transparent conductive layer is formed and the protective film so as to sandwich a polarizer, thereby producing a polarizing plate-integrated touch panel module; and
and a step of bonding the optical compensation film side of the polarizing plate-integrated touch panel module to the VA mode liquid crystal cell.
The method of the present invention can provide a touch panel-equipped liquid crystal display device having a VA mode liquid crystal cell with excellent front contrast and a method for manufacturing the same.
The expression mechanism or action mechanism of the effect of the present invention is not clear, but is presumed as follows.
In general, in the case of an IPS mode liquid crystal cell, it is preferable to use a film having no retardation, i.e., a retardation value Ro in the in-plane direction and a retardation value Rt in the thickness direction of about zero, as an optical compensation film. On the other hand, in the case of a VA mode liquid crystal cell, a film having high retardation values Ro and Rt, for example, a retardation film having Ro in the range of 20 to 70nm and Rt in the range of 70 to 200nm is preferably used as the optical compensation film.
Such a film having a high phase difference value is usually subjected to a stretching treatment in the production process, and the polymer molecules constituting the film are highly oriented to obtain the phase difference value.
In order to manufacture the above-mentioned polarization plate integrated touch panel module called Mid-cell type or embedded type, when a transparent conductive layer is provided on the optical compensation film, heat treatment (also called annealing treatment) is required to lower the resistance value of the conductive layer after the transparent conductive layer is formed. For example, it is estimated that, when the heat treatment is performed at 150 ℃ for about 30 minutes, the orientation of the polymer molecules in the optical compensation film is disturbed, and as a result, the required optical compensation performance is insufficient, and the front contrast is lowered.
According to the configuration of the present invention, in order to cope with the above phenomenon, by using the heat-resistant optical compensation film having a glass transition temperature Tg of 155 ℃ or higher, the fluctuation of the retardation value due to the heat treatment is suppressed, and an excellent front contrast which is an inherent characteristic of the VA mode liquid crystal can be achieved.
In addition, as described above, in order to make the touch panel thin, the optical compensation film is sometimes required to be thin with a thickness of 40 μm or less. In this case, since the retardation value and the film thickness have an inverse relationship, it is effective to add an additive (also referred to as a retardation raising agent in the present application) capable of raising the retardation value by addition to the film when the film is made to be a thin film of 40 μm or less. The present inventors have found, in studies on various retardation enhancers, a retardation enhancer having a specific structure which can provide more excellent effects. It is presumed that the addition of the additive causes the retardation raising agent to be disoriented during the heat treatment to cause the retardation of the compound to fluctuate, thereby compensating the fluctuation in the retardation of the polymer molecules constituting the film, and realizing excellent retardation values and heat treatment fluctuation resistance even in the case of a thin film.
Drawings
Fig. 1 is a schematic diagram showing an example of a configuration of a conventional liquid crystal display device with a plug-in touch panel module.
Fig. 2 is a schematic diagram showing an example of the configuration of a touch panel-equipped liquid crystal display device including a polarizing plate integrated touch panel module according to the present invention.
Fig. 3 is a schematic diagram showing another example of the configuration of the touch panel-equipped liquid crystal display device including the polarizing plate integrated touch panel module of the present invention.
Fig. 4 is a schematic diagram showing another example of the configuration of the touch panel-equipped liquid crystal display device including the polarizing plate integrated touch panel module of the present invention.
Fig. 5 is a schematic diagram showing another example of the configuration of the touch panel-equipped liquid crystal display device including the polarizing plate integrated touch panel module of the present invention.
Fig. 6 is a schematic diagram showing another example of the configuration of the touch panel-equipped liquid crystal display device including the polarizing plate integrated touch panel module of the present invention.
Detailed Description
The liquid crystal display device with a touch panel of the present invention is a liquid crystal display device with a touch panel, which is provided with a polarizing plate-integrated touch panel module having a transparent conductive layer on the identification side of a VA-mode liquid crystal cell, and is characterized in that the polarizing plate-integrated touch panel module having the transparent conductive layer is provided with an optical compensation film having a transparent conductive layer on at least one side, a polarizing plate and a protective film in this order from the VA-mode liquid crystal cell to the identification side, and the glass transition temperature Tg of the optical compensation film is in the range of 155 to 250 ℃. This feature is a feature common to the inventions recited in the respective claims.
In an embodiment of the present invention, the optical compensation film contains any one of a cycloolefin resin, a polyimide resin, and a polyarylate resin, and is preferably configured to satisfy the glass transition temperature Tg of the optical compensation film, from the viewpoint of exhibiting the effects of the present invention.
Further, the optical compensation film has preferable properties from the viewpoint of sufficiently exhibiting an optical compensation function, suppressing a retardation variation due to heat treatment, and achieving excellent front contrast when a VA mode liquid crystal cell is used, in a range in which a variation in the in-plane direction retardation value Ro is ± 3.0% and a variation in the thickness direction retardation value Rt is ± 4.0% when heat treatment is performed at 150 ℃ for 1 hour.
In addition, the thickness of the optical compensation film is preferably within a range of 10 to 40 μm, which is preferable for thinning of the touch panel, and in this case, the nitrogen-containing heterocyclic compound having the structure represented by the general formula (3) is preferably contained from the viewpoint of providing a desired retardation value and further suppressing variation in retardation with respect to heat treatment.
The method for manufacturing a liquid crystal display device with a touch panel according to the present invention preferably includes: forming the transparent conductive layer on at least one surface of the optical compensation film, and then performing heat treatment at 150 ℃ or higher; a step of manufacturing a polarizing plate-integrated touch panel module by bonding the optical compensation film having the transparent conductive layer formed thereon and the protective film with a polarizer interposed therebetween; and a step of bonding the optical compensation film side of the polarizing plate-integrated touch panel module to the VA mode liquid crystal cell.
The present invention and its constituent elements, and forms and modes for carrying out the present invention will be described in detail below. In the present application, "to" is used to include numerical values described before and after the "to" as the lower limit value and the upper limit value.
Outline of liquid Crystal display device with touch Panel according to the present invention
The liquid crystal display device with a touch panel of the present invention is a liquid crystal display device with a touch panel, which is provided with a polarizing plate-integrated touch panel module having a transparent conductive layer on the identification side of a VA mode liquid crystal cell,
the touch panel module integrated with a polarizing plate having the transparent conductive layer comprises an optical compensation film having a transparent conductive layer on at least one surface, a polarizing plate and a protective film in this order from the VA mode liquid crystal cell to the viewing side, and the touch panel module integrated with a polarizing plate has
The glass transition temperature Tg of the optical compensation film is in the range of 155-250 ℃.
As described above, the touch panel-equipped liquid crystal display device of the present invention is characterized by including the VA mode liquid crystal display unit, and by using the VA mode liquid crystal display unit, the front contrast is improved as compared with the conventional touch panel-equipped liquid crystal display device using the IPS mode liquid crystal display unit.
From the viewpoint of suppressing the phase difference value fluctuation during heat treatment and improving the contrast, the glass transition temperature Tg of the optical compensation film needs to be 155 ℃. When the temperature is less than 155 ℃, a fluctuation in retardation value due to disorder of polymer molecules of the optical compensation film occurs in the heat treatment after the formation of the transparent conductive layer, and the optical compensation function is degraded, so that an excellent front contrast which is an inherent characteristic of the VA mode liquid crystal cannot be obtained.
In addition, various additives are added to the optical compensation film from the viewpoint of improving optical properties and physical functions, but in a state in which they are contained, the above-described range of glass transition temperature needs to be satisfied. For example, when a plasticizer or the like is added, the glass transition temperature may be lowered depending on the kind and the amount of addition, and design attention may be required.
The glass transition temperature Tg can be determined by measurement in accordance with JIS K-7121 using, for example, a differential scanning calorimeter DSC220 manufactured by Seiko Instruments. Specifically, a sample film of about 10mg is fixed to a vessel, the temperature is raised from room temperature to 250 ℃ at 20 ℃/min and the temperature is maintained for 10 minutes under a nitrogen flow rate of 50ml/min (1 st scan), the temperature is lowered at 20 ℃/min to 30 ℃ and the temperature is maintained for 10 minutes (2 nd scan), the temperature is raised at 20 ℃/min to 250 ℃ (3 rd scan), a DSC curve is prepared, and the glass transition temperature Tg is determined from the DSC curve of the 3 rd scan obtained.
Further, as described above, the optical compensation film according to the present invention preferably contains a retardation raising agent having a structure represented by the general formula (3) for the purpose of further suppressing the fluctuation of the retardation value during the heat treatment.
In the course of the present invention, various studies have been made on a general-purpose resin film, and as a result, a cellulose diacetate film has a large dimensional change due to humidity, and when a transparent conductive layer is formed on the film, shrinkage and elongation occur during storage, and breakage of an electrode or the like occurs, which makes it difficult to use the film. Further, the retardation of the PET film is too large to be used as an optical compensation film of a VA mode liquid crystal display device. Similarly, a Polycarbonate (PC) film has a large photoelastic coefficient and is not suitable as an optical compensation film for a VA mode liquid crystal display device. Further, the acrylic resin film has a low glass transition temperature Tg and is not suitable as the optical compensation film of the present invention.
Constitution of liquid crystal display device with touch Panel of the present invention
The liquid crystal display device with a touch panel of the present invention is a liquid crystal display device with a touch panel, which is provided with a polarizing plate-integrated touch panel module having a transparent conductive layer on a viewing side of a VA mode liquid crystal cell, wherein the polarizing plate-integrated touch panel module having the transparent conductive layer is provided with an optical compensation film having a transparent conductive layer on at least one side, a polarizing plate, and a protective film in this order from the VA mode liquid crystal cell to the viewing side, the optical compensation film has a glass transition temperature Tg in the range of 155 to 250 ℃, and the optical compensation film contains any one of a cycloolefin resin, a polyimide resin, and a polyarylate resin, which is preferable from the viewpoint of controlling heat resistance and a phase difference value.
The configuration of the touch panel-equipped liquid crystal display device of the present invention and the configuration of the comparative example will be described together with the drawings.
Fig. 1 is a schematic diagram showing an example of a configuration of a conventional touch panel-equipped liquid crystal display device including a plug-in touch panel module.
The liquid crystal display device 10 with a touch panel as a comparative example includes a polarizing plate P1 in which a polarizer 2 is sandwiched between a protective film T1 and an optical compensation film T2 on one surface of a liquid crystal cell 1, and on the polarizing plate P1, a touch panel module T including a transparent conductive layer 5 and a protective layer 6 on both surfaces of a conductive layer base film 4 is bonded via an adhesive layer 3, and a front panel 7 is further bonded via the adhesive layer 3 to the touch panel module T. The other surface of the liquid crystal cell 1 has a polarizing plate P2 in which the polarizer 2 is sandwiched between an optical compensation film T3 and a protective film T4. The polarizing plate P1 side is the viewing side, and the polarizing plate P2 side is the backlight side. Here, the liquid crystal cell 1 is generally an IPS mode type.
Fig. 2 is a schematic diagram showing an example of the configuration of a touch panel-equipped liquid crystal display device including a polarizing plate integrated touch panel module according to the present invention.
The touch panel-equipped liquid crystal display device 20 of the present invention includes a polarizing plate integrated touch panel module having a so-called Mid-cell or in-cell structure, that is, a polarizing plate P1 in which a polarizer 2 is sandwiched between a protective film T1 and an optical compensation film T2 on one surface of a liquid crystal cell 1, and the optical compensation film T2 has a transparent conductive layer 5 formed on both surfaces thereof. With this configuration, the liquid crystal display device with a touch panel can be made thinner than a plug-in type. The adhesion between the films or layers is preferably performed by appropriately forming the adhesive layer 3.
The other side of the liquid crystal cell 1 similarly has a polarizing plate P2 in which the polarizer 2 is sandwiched between an optical compensation film T3 and a protective film T4. Here, the liquid crystal cell 1 is a VA mode type.
In addition, in the minimum configuration, a functional layer (a hard coat layer, an intermediate layer, an antistatic layer, a smoothing layer, an ultraviolet absorbing layer, a bending prevention layer, or the like) may be provided between the respective members as necessary, and it is preferable to form the hard coat layer as a protective layer of a film or form the antistatic layer.
The thickness of the entire polarizing plate-integrated touch panel module according to the present invention is not particularly limited, and is preferably within a range of 7 to 80 μm, and more preferably within a range of 10 to 60 μm, from the viewpoints of prevention of bending, good resistance value, handleability, and the like.
Fig. 3 is a schematic diagram showing another example of the configuration of the touch panel-equipped liquid crystal display device including the polarizing plate integrated touch panel module of the present invention.
The structure of fig. 3 is a structure in which the transparent conductive layer 5 is formed as an upper layer of the protective film T1 and the optical compensation film T2, respectively.
Fig. 4 is a schematic diagram showing another example of the configuration of the touch panel-equipped liquid crystal display device including the polarizing plate integrated touch panel module of the present invention.
The structure of fig. 4 is a structure in which the transparent conductive layer 5 is formed as an upper layer of the protective film T1 and a lower layer of the optical compensation film T2, respectively.
Fig. 5 is a schematic diagram showing another example of the configuration of the touch panel-equipped liquid crystal display device including the polarizing plate integrated touch panel module of the present invention.
The structure of fig. 5 is a structure in which the transparent conductive layer 5 is formed as one layer and is disposed below the optical compensation film T2. The transparent conductive layer in this case preferably has a configuration in which the X electrode pattern and the Y electrode pattern are provided in layers with an insulating layer interposed therebetween.
Fig. 6 is a schematic diagram showing another example of the configuration of the touch panel-equipped liquid crystal display device including the polarizing plate integrated touch panel module of the present invention.
The structure of fig. 6 is a structure in which the transparent conductive layer 5 is formed as one layer and is disposed on the upper layer of the optical compensation film T2. Similarly, the transparent conductive layer in this case has an X electrode pattern and a Y electrode pattern in layers with an insulating layer interposed therebetween.
Hereinafter, each element constituting the polarizing plate integrated touch panel module of the present invention will be described in detail.
[ 1 ] optical compensation film
The glass transition temperature Tg of the optical compensation film of the present invention is in the range of 155 to 250 ℃, and the lower limit of Tg is required to be 155 ℃ or higher. The optical compensation film generally contains a resin, a plasticizer, various additives, a matting agent, and the like, and the glass transition temperature Tg of the completed film is 155 ℃ or higher in the present invention.
From the viewpoint of suppressing the fluctuation of the phase difference with respect to the heat treatment when forming the transparent conductive layer, the glass transition temperature Tg needs to be 155 ℃ or higher, and the upper limit of the glass transition temperature Tg is 250 ℃ or lower. When Tg is more than 250 ℃, adhesiveness and crack resistance may be reduced with an increase in internal stress. Therefore, in the present invention, an optical compensation film having a glass transition temperature Tg of 250 ℃ is targeted.
The preferred resin used in the optical compensation film according to the present invention preferably contains a single resin having a glass transition temperature Tg of 155 ℃ or higher, and further preferably contains any one of a cellulose ester resin, a cycloolefin resin, a polyimide resin, and a polyarylate resin, more preferably contains any one of a cycloolefin resin, a polyimide resin, and a polyarylate resin, and particularly preferably contains a cycloolefin resin, in consideration of the characteristics of embodying the retardation and the stability.
[ 1.1 ] cellulose ester resin
When contained in the optical compensation film, the cellulose ester resin having a glass transition temperature Tg of 155 ℃ or higher (hereinafter also referred to as cellulose ester) is preferably a lower fatty acid ester of cellulose. Among them, mixed fatty acid esters such as cellulose acetate propionate and cellulose acetate butyrate are preferably used from the viewpoint of easy occurrence of retardation and dimensional stability with respect to humidity.
Among the above, a lower fatty acid ester of cellulose particularly preferably used is cellulose acetate propionate (also referred to as CAP in the present application).
Cellulose acetate propionate and cellulose acetate butyrate have acyl groups having 2 to 4 carbon atoms as substituents, and preferably satisfy both the following formulae (I) and (II) when the substitution degree of acetyl is X and the substitution degree of propionyl or butyryl is Y.
Preferably:
x + Y is more than or equal to 2.0 and less than or equal to 3.0 in the formula (I),
x is more than or equal to 1.0 and less than or equal to 2.0 and Y is more than or equal to 0.1 and less than or equal to 1.0 in the formula (II).
The degree of substitution of the acyl group can be measured in accordance with ASTM-D817-96.
As the molecular weight of cellulose acetate propionate and cellulose acetate butyrate, preferred are: the number average molecular weight (Mn) is 100000 or more and less than 180000, Mw is 200000 or more and less than 360000, and Mw/Mn is in the range of 1.8 to 2.0.
The number average molecular weight (Mn) and molecular weight distribution (Mw) of cellulose esters can be measured by high performance liquid chromatography. The measurement conditions were as follows.
Solvent: methylene dichloride
Column: shodex K806, K805, K803G
(3 columns manufactured by Showa Denko K.K. K. K.K. used in connection with)
Column temperature: 25 deg.C
Sample concentration: 0.1% by mass
A detector: RI Model 504 (manufactured by GLScience corporation)
A pump: l6000 (manufactured by Hitachi Kagaku K.K.)
Flow rate: 1.0ml/min
And (3) correcting a curve: calibration curves obtained from 13 samples of standard polystyrene STKstandard polystyrene (manufactured by Tosoh corporation) until Mw becomes 500 to 1000000 were used. The 13 samples are preferably used at almost equal intervals.
[ 1.2 ] cycloolefin resin
As the cycloolefin resin, polymers of various cycloolefin monomers can be used, and preferably, a polymer obtained by homopolymerizing or copolymerizing a cycloolefin monomer having a norbornene skeleton is used.
The cycloolefin monomer used in the present invention is explained below.
The cycloolefin resin according to the present invention is preferably a polymer obtained by homopolymerizing or copolymerizing cycloolefin monomers represented by the following general formulae (A-1) and (A-2).
The cycloolefin monomer having the structure represented by the general formula (A-1) will be described.
General formula (A-1)
(in the general formula (A-1), R1～R4Each independently represents a hydrogen atom or a halogen atom. Or a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms which may have a linking group containing an oxygen atom, a nitrogen atom, a sulfur atom or a silicon atom, or a polar group. p represents a natural number of 0 to 2. )
The polar group is a functional group that generates polarization by using an atom having high electronegativity, such as oxygen, sulfur, nitrogen, or halogen. Examples of the polar group include a carboxyl group, a hydroxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an amino group, an amido group, a cyano group, a halogen atom, and the like, and these polar groups may be bonded to each other through a linking group such as a methylene group. Further, a substituted or unsubstituted hydrocarbon group of 1 to 30 carbon atoms which may have a linking group containing an oxygen atom, a nitrogen atom, a sulfur atom or a silicon atom, for example, a hydrocarbon group of 1 to 30 carbon atoms to which a polar 2-valent organic group such as a carbonyl group, an ether group, a silyl ether group, a thioether group or an imino group is bonded as a linking group, and the like can be cited as the polar group. Among these, a carboxyl group, a hydroxyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group is preferable, and an alkoxycarbonyl group or an aryloxycarbonyl group is particularly preferable, and is preferable from the viewpoint of ensuring solubility in solution film formation.
Next, the cycloolefin monomer represented by the general formula (A-2) will be described.
General formula (A-2)
(in the general formula (A-2), R5Independently represents a hydrogen atom, a hydrocarbon group having 1 to 5 carbon atoms, or an alkylsilyl group having an alkyl group having 1 to 5 carbon atoms. R6Represents a carboxyl group, a hydroxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an amino group, an amido group, a cyano group, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. p represents an integer of 0 to 2. )
In the present invention, the substituent R represented by the general formula (A-2) is used5And R6The cycloolefin monomer substituted for one-sided carbon is preferable from the viewpoint of the presence of an additive because the symmetry of the molecule is lost, or the diffusion movement of the additive to the film surface to be formed is promoted by the diffusion movement of the resin and the additive to each other at the time of the volatilization of the solvent.
R5Preferably a hydrocarbon group having 1 to 3 carbon atoms, R6A carboxyl group, a hydroxyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group is preferable, and an alkoxycarbonyl group or an aryloxycarbonyl group is particularly preferable, and is also preferable from the viewpoint of ensuring solubility in solution film formation.
The structures of the general formulae (A-1) and (A-2) in the present application will be specifically shown below, but the structures are not limited to the specific examples below.
The cycloolefin resin is a polymer obtained by homopolymerizing or copolymerizing cycloolefin monomers having structures represented by the general formulae (A-1) and (A-2) having a norbornene skeleton, and examples thereof include the following polymers.
(1) Ring-opened polymer of cycloolefin monomer
(2) Ring-opened copolymer of cycloolefin monomer and copolymerizable monomer
(3) Hydrogenated (co) polymers of the Ring-opened (co) polymers (1) or (2) above
(4) (Co) Polymer obtained by cyclizing the ring-opened (co) polymer of the above (1) or (2) by a Friedel-crafts reaction and then hydrogenating the cyclized (co) polymer
(5) Saturated polymer of cycloolefin monomer and unsaturated double bond-containing compound
(6) Addition type (co) polymer of cycloolefin monomer and hydrogenated (co) polymer thereof
(7) Alternating copolymers of cycloolefin monomers with methacrylates or with acrylates
The polymers (1) to (7) can be obtained by any known method, for example, the methods described in Japanese patent application laid-open Nos. 2008-107534 and 2005-227606. For example, the catalyst or solvent used in the ring-opening copolymerization of the above (2) can be, for example, the catalyst or solvent described in paragraphs 0019 to 0024 of Japanese patent application laid-open No. 2008-107534. The catalysts used for the hydrogenation in (3) and (6) can be, for example, the catalysts described in paragraphs 0025 to 0028 of Japanese patent application laid-open No. 2008-107534. The acidic compound used in the Friedel-crafts reaction of (4) above can be, for example, the acidic compound described in paragraph 0029 of Japanese patent application laid-open No. 2008-107534. The catalysts used in the addition polymerizations of the above (5) to (7) can be, for example, the catalysts described in paragraphs 0058 to 0063 of Japanese patent laid-open No. 2005-227606. The alternating copolymerization reaction (7) can be carried out, for example, by the method described in paragraphs 0071 and 0072 of Japanese patent laid-open publication No. 2005-227606.
Among them, the polymers (1) to (3) and (5) are preferable, and the polymers (3) and (5) are more preferable.
As the preferred cycloolefin polymer according to the present invention, there can be mentioned a polymer having a structural unit represented by the following general formula (B-1) and general formula (B-2). Such a cycloolefin-based resin may be a copolymer containing only a structural unit represented by the general formula (B-1), containing only a structural unit represented by the general formula (B-2), and containing each of the structural units represented by the general formulae (B-1) and (B-2).
Preferred is a resin containing only the structure of the general formula (B-2) or a copolymer containing both the structural units of the general formulae (B-1) and (B-2). The cycloolefin resin obtained is preferably a resin having a high glass transition temperature and a high transmittance.
General formula (B-1)
(in the general formula (B-1), X is a group represented by-CH ═ CH-or a group represented by the formula: -CH2CH2-a group represented by (a). R1～R4Each independently represents a hydrogen atom; a halogen atom; a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms which may have a linking group containing oxygen, nitrogen, sulfur or silicon; or a polar group. p represents a natural number of 0 to 2. )
General formula (B-2)
(in the general formula (B-2), X is a group represented by-CH ═ CH-or a group represented by the formula: -CH2CH2-a group represented by (a). R5Each independently represents a hydrogen atom, a hydrocarbon group having 1 to 5 carbon atoms, or an alkylsilyl group having an alkyl group having 1 to 5 carbon atoms. R6Represents a carboxyl groupA hydroxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an amino group, an amido group, a cyano group, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. p represents an integer of 0 to 2. )
In the present specification, the description of jp 2008-107534 a and the like is incorporated for the method for producing the cycloolefin resin according to the present application, and the description thereof is omitted.
The cycloolefin resin may be used alone in 1 kind or in combination with 2 or more kinds.
The cycloolefin resin according to the present invention preferably has a molecular weight in the range of 8000 to 100000, more preferably 10000 to 80000, particularly 12000 to 50000, and a weight average molecular weight (Mw) of 20000 to 300000, more preferably 30000 to 250000, and particularly 40000 to 200000 in terms of polystyrene as measured by Gel Permeation Chromatography (GPC).
The glass transition temperature (Tg) of the cycloolefin resin according to the present invention is usually 110 ℃ or higher, preferably 110 to 350 ℃, more preferably 120 to 250 ℃, and particularly preferably 120 to 220 ℃. When the Tg is 110 ℃ or higher, deformation due to use under high temperature conditions or secondary processing such as coating or printing is less likely to occur, and therefore, this is preferable.
On the other hand, by setting Tg to 350 ℃ or lower, it is possible to avoid the difficulty of molding processing and suppress the possibility of resin degradation due to heat during molding processing.
The cycloolefin resin may contain a specific hydrocarbon resin as described in, for example, japanese patent laid-open nos. 9-221577 and 10-287732, a known thermoplastic resin, a thermoplastic elastomer, a rubbery polymer, organic fine particles, inorganic fine particles, or the like, or may contain an additive such as a specific wavelength dispersing agent, a plasticizer, an antioxidant, a peeling accelerator, rubber particles, or an ultraviolet absorber, as long as the effects of the present invention are not impaired.
Further, as the cycloolefin resin, commercially available products can be preferably used, and examples of the commercially available products are sold under trade names such as ARTON (ARTON: registered trademark) G, ARTON F, ARTONR and ARTON RX by JSR corporation, and they can be used.
[ 1.3 ] polyimide-based resin
The polyimide resin according to the present invention is preferably a polyimide resin represented by the following formula (P1) obtained by chemically imidizing a polyimide precursor.
Formula (P1)
[ polymerization of polyimide precursor ]
An example of a method for producing a polyimide precursor having a structure represented by formula (P1) used in the present invention is shown below.
First, 2 '-bis (trifluoromethyl) -4, 4' -diaminobiphenyl (TFMB), which is a diamine, is dissolved in a polymerization solvent in a polymerization vessel. The diamine solution is gradually added with 2, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropionic dianhydride (6FDA) powder, and stirred with a mechanical stirrer at-20 to 100 ℃, preferably 20 to 60 ℃ for 1 to 72 hours. By using TFMB and 6FDA, the transmittance and solubility of visible light are improved. The number of moles of the diamine and the number of moles of the tetracarboxylic dianhydride are added substantially in equimolar amounts. The total monomer concentration during polymerization is 5 to 40 mass%, preferably 10 to 30 mass%. By performing the polymerization in this monomer concentration range, a polyimide precursor solution having a uniform and high polymerization degree can be obtained. When the polymerization is carried out at a concentration lower than the above monomer concentration range, the polymerization degree of the polyimide precursor may not be sufficiently increased, and the finally obtained polyimide resin film may become brittle, which is not preferable.
The polymerization solvent is not particularly limited, and N, N-dimethylacetamide, N-diethylacetamide, N-dimethylformamide, N-methyl-2-pyrrolidone, hexamethylphosphoramide, dimethyl sulfoxide, γ -butyrolactone, 1, 3-dimethyl-2-imidazolidinone, 1, 2-dimethoxyethane-bis (2-methoxyethyl) ether, tetrahydrofuran, and 1, 4-bis (2-methoxyethyl) ether can be used
Aprotic solvents such as alkane, picoline, pyridine, acetone, chloroform, toluene and xylene, and protic solvents such as phenol, o-cresol, m-cresol, p-cresol, o-chlorophenol, m-chlorophenol and p-chlorophenol. These solvents may be used alone or in combination of 2 or more.
[ method for producing polyimide resin ]
The polyimide-based resin represented by formula (P1) can be produced by a dehydration ring-closure reaction (imidization reaction) of the polyimide precursor obtained by the above-described method. The imidization reaction uses chemical imidization in which the obtained polyimide-based resin exhibits more excellent dimensional stability. The chemical imidization can be carried out using a cyclodehydration agent (chemical imidization agent) comprising an acid anhydride of an organic acid and an organic tertiary amine. For example, the imidization can be easily performed by directly using the polyimide precursor varnish or by appropriately diluting the polyimide precursor varnish with a solvent, adding a dehydrating cyclization agent thereto, and stirring the mixture at 0 to 100 ℃, preferably 20 to 60 ℃ for 0.5 to 48 hours.
The acid anhydride of the organic acid used in this case is not particularly limited, and acetic anhydride, propionic anhydride, maleic anhydride, phthalic anhydride, or the like can be used, and acetic anhydride is preferably used from the viewpoint of cost and easiness of post-treatment. The organic tertiary amine is not particularly limited, and pyridine, 1, 5-lutidine, β -picoline, γ -picoline, lutidine, isoquinoline, triethylamine, N-dimethylaniline, and the like can be used.
In the chemical imidization reaction, the amount of the acid anhydride used in the cyclodehydration reagent is preferably in the range of 1 to 10 times by mole the theoretical dehydration amount of the polyimide precursor, and the amount of the basic catalyst used in the cyclodehydration reagent is preferably in the range of 0.1 to 2 times by mole with respect to the acid anhydride. If the chemical imidization is carried out outside these ranges, the imidization reaction may be incomplete, or a polyimide-based resin whose imidization is incomplete may be precipitated in the reaction solution and the imidization may still be insufficient.
After completion of the imidization, the reaction solution may be used as it is for coating, or the reaction solution may be dropped into a large amount of a poor solvent or a poor solvent may be added to the reaction solution to precipitate and wash the polyimide-based resin to remove the reaction solvent or to remove an excessive amount of a chemical imidizing agent at the time of chemical imidization, followed by drying under reduced pressure to obtain a powder of the polyimide-based resin. The poor solvent to be used is not particularly limited as long as it does not dissolve the polyimide-based resin, and water, methanol, ethanol, n-propanol, isopropanol, and the like are preferably used from the viewpoint of affinity with the reaction solvent and the chemical imidizing agent and ease of removal by drying.
The weight average molecular weight of the polyimide resin is not particularly limited, but is preferably 5000 to 2000000, more preferably 10000 to 1000000, and still more preferably 50000 to 500000. When the weight average molecular weight is 5000 or more, sufficient strength can be obtained in the case of producing a film, and since dimensional stability tends to be improved, sufficient dimensional stability can be obtained. On the other hand, if the viscosity is 2000000 or less, the solution viscosity is not too high, and handling is easy. The weight average molecular weight is a value converted into polyethylene glycol by Size Exclusion Chromatography (SEC).
[ 1.3 ] polyarylate-based resin
The polyarylate resin according to the present invention is preferably a polyarylate resin containing a bisphenol residue and an aromatic dicarboxylic acid residue.
The bisphenol residue has a structure represented by the general formula (P2).
General formula (P2)
In the general formula (P2), X is desirably a divalent group containing a fluorine atom. By setting X in the general formula (P2) to a divalent group containing a fluorine atom, a polyarylate resin can be obtained which is excellent in heat resistance and light transmittance in a visible light region and a wavelength region (ultraviolet region) shorter than the visible light region, has excellent flame retardancy as compared with the conventional one, and is suppressed in yellowing due to ultraviolet rays. When X is a divalent group containing no fluorine atom, flame retardancy is lowered, yellowing occurs by ultraviolet irradiation, and light transmittance is lowered.
The divalent group containing a fluorine atom is represented by, for example, the general formula (P2 a).
General formula (P2a)
In the general formula (P2a), R1aAnd R2aIndependently trifluoromethyl (CF)3Yl), difluoromethyl (CF)2H radical), monofluoromethyl radical (CH)2F radicals), or fluorine atoms. Among these, R1aAnd R2aPreferably trifluoromethyl.
R1And R2Represents a substituent bonded to the benzene ring in the general formula (P2).
Starting from bisphenols which are readily available industrially or are readily synthesized to give a structure represented by the general formula (P2), in the general formula (P2), R1And R2Independently a hydrocarbon group having 1 to 6 carbon atoms, a haloalkyl group or a halogen atom. Among these, a chlorine atom, a bromine atom, a methyl group, an ethyl group, a phenyl group, and a cyclohexyl group are preferable, and a bromine atom and a methyl group are more preferable.
p and q each represent a substituent R bonded to a benzene ring1And R2The number of (b) is independently an integer of 0 to 4. For example, when P and q are 0, it means that all hydrogen atoms bonded to the benzene ring in the general formula (P2) are not substituted by R1And R2And (4) substitution. When p is 2-4, a plurality of R1The substituents may be the same as each other or different from each other. When q is 2 to 4, a plurality of R2The substituents may be the same as each other or different from each other. P and q are preferably 0, from the viewpoint of industrial availability or ease of synthesis of bisphenols giving a structure represented by the general formula (P2).
Examples of the bisphenol having a structure represented by the general formula (P2) include 2, 2-bis (4-hydroxyphenyl) hexafluoropropane [ BisAF ] and 2, 2-bis (3)5-dimethyl-4-hydroxyphenyl) hexafluoropropane and 2, 2-bis (tetramethyl-4-hydroxyphenyl) hexafluoropropane. Among these, BisAF is preferable because it is industrially easily available. When BisAF is used, in the general formula (P2), P is 0, q is 0, and X is — C (CF)3)2－。
In the present invention, the bisphenol residue may contain a residue of a bisphenol other than the bisphenol having the structure given by the general formula (P2) within a range not impairing the effects of the present invention. Examples of the bisphenol to which such a residue is to be imparted include 2, 2-bis (4-hydroxyphenyl) propane [ BisA ], 2-bis (3-methyl-4-hydroxyphenyl) propane [ BisC ], 9-bis (3-methyl-4-hydroxyphenyl) fluorene [ BCF ], 2-bis (3, 5-dimethyl-4-hydroxyphenyl) propane, 1-bis (4-hydroxyphenyl) -1-phenylethane, 1-bis (4-hydroxyphenyl) cyclohexane, 1-bis (4-hydroxyphenyl) ethane, 1-bis (3, 5-dimethyl-4-hydroxyphenyl) ethane, 1-bis (3-methyl-4-hydroxyphenyl) ethane, bis (4-hydroxyphenyl) methane, bis (3, 5-dimethyl-4-hydroxyphenyl) methane, bis (3-methyl-4-hydroxyphenyl) methane, 1, 1-bis (4-hydroxyphenyl) hexane, 1-bis (3, 5-dimethyl-4-hydroxyphenyl) hexane.
In order to impart high flame retardancy to the polyarylate resin and further suppress yellowing due to ultraviolet rays, the proportion of the bisphenol residue represented by the general formula (P2) in the total bisphenol residues present in the polyarylate resin is preferably 50 to 100 mol%, more preferably 80 to 100 mol%, and still more preferably 100 mol%.
The aromatic dicarboxylic acid residue preferably has a structure represented by the general formula (P3). By having the structure represented by the general formula (P2) and the structure represented by the general formula (P3), excellent heat resistance, flame retardancy, and suppression of light transmittance in the visible ray region and a wavelength region (ultraviolet ray region) shorter than the visible ray region and yellowing due to ultraviolet rays can be achieved at the same time. When the aromatic dicarboxylic acid residue does not have the structure of the general formula (P2), the light transmittance in the short wavelength region (ultraviolet region) is reduced, or yellowing due to ultraviolet light is likely to occur. For example, when only terephthalic acid having a structure not shown in the general formula (P3) is used as the aromatic dicarboxylic acid, the light transmittance in the short wavelength region (ultraviolet region) of the polyarylate resin is lowered, and yellowing due to ultraviolet light is likely to occur.
General formula (P3)
In the general formula (P3), R3And R4Represents a substituent bonded to the benzene ring in the general formula (P3).
R is derived from an aromatic dicarboxylic acid which is industrially easily available or easily synthesized to give a structure represented by the general formula (P3)3And R4Independently a hydrocarbon group having 1 to 6 carbon atoms, a haloalkyl group or a halogen atom. Among these, chlorine, bromine, methyl, ethyl, phenyl, and cyclohexyl are preferable, and bromine and methyl are more preferable.
r and s represent the number of substituents bonded to the benzene ring, and are independently integers of 0 to 4. For example, when R and s are 0, it means that all hydrogen atoms bonded to the benzene ring in the general formula (P2) are not substituted by R3And R4And (4) substitution. When R is 2 to 4, a plurality of R3The substituents may be the same as each other or different from each other. When s is 2 to 4, a plurality of R4The substituents may be the same as each other or different from each other.
Examples of the aromatic dicarboxylic acid having a structure represented by the general formula (P3) include diphenyl ether-2, 2 '-dicarboxylic acid, diphenyl ether-2, 3' -dicarboxylic acid, diphenyl ether-2, 4 '-dicarboxylic acid, diphenyl ether-3, 3' -dicarboxylic acid, diphenyl ether-3, 4 '-dicarboxylic acid, and diphenyl ether-4, 4' -dicarboxylic acid. Among these, diphenyl ether-4, 4' -dicarboxylic acid is preferable because it is industrially easily available. When diphenyl ether-4, 4' -dicarboxylic acid is used, r is 0 and s is 0 in the general formula (P3).
In the present invention, the aromatic dicarboxylic acid residue may contain a residue of an aromatic dicarboxylic acid other than the aromatic dicarboxylic acid having a structure according to general formula (P3) within a range not impairing the effects of the present invention. Examples of the aromatic dicarboxylic acid to which such a residue is imparted include terephthalic acid, isophthalic acid, and phthalic acid, and among them, isophthalic acid is preferable. By using isophthalic acid in combination, yellowing due to ultraviolet rays can be suppressed.
In order to further suppress yellowing by ultraviolet rays, the proportion of the aromatic dicarboxylic acid residue having a structure represented by the general formula (P3) (the total of the aromatic dicarboxylic acid residue having a structure represented by the general formula (P3) and the isophthalic acid residue when an isophthalic acid residue is contained) in the entire aromatic dicarboxylic acid residues present in the polyarylate resin is preferably 35 to 100 mol%, more preferably 50 to 100 mol%, even more preferably 80 to 100 mol%, and most preferably 100 mol%.
From the viewpoint of tensile elongation at break of the polyarylate resin, the proportion of the aromatic dicarboxylic acid residue having a structure represented by the general formula (P3) in the whole aromatic dicarboxylic acid residues present in the polyarylate resin is preferably 35 to 100 mol%, and more preferably 100 mol%.
The polyarylate resin according to the present invention preferably has a terminal group for terminating the terminal of the molecule. When the molecular end is capped, the acid value of the polyarylate resin decreases, and the polyarylate resin is hardly decomposed by light. The terminal group is preferably a monohydric phenol residue, a monohydric acid chloride residue, a monohydric alcohol residue and/or a monocarboxylic acid residue, and more preferably a monohydric phenol residue and a monohydric alcohol residue, from the viewpoint that the acid value can be reduced.
In the present invention, the polyarylate resin may contain a residue of an aliphatic diol, a residue of an alicyclic diol, a residue of an aliphatic dicarboxylic acid, or a residue of an alicyclic dicarboxylic acid, as long as the effects of the present invention are not impaired. Examples of the aliphatic diol include ethylene glycol and propylene glycol. Examples of the alicyclic diol include 1, 4-cyclohexanediol, 1, 3-cyclohexanediol, and 1, 2-cyclohexanediol. Examples of the aliphatic dicarboxylic acid include adipic acid and sebacic acid. Examples of the alicyclic dicarboxylic acid include 1, 4-cyclohexanedicarboxylic acid, 1, 3-cyclohexanedicarboxylic acid, and 1, 2-cyclohexanedicarboxylic acid.
The method for producing the polyarylate resin according to the present invention includes a method of reacting in an organic solvent such as an interfacial polymerization method or a solution polymerization method, and a method of reacting in a molten state such as a melt polymerization method. From the viewpoint of polymerizability and appearance of the obtained resin, an interfacial polymerization method in which the reaction is carried out in an organic solvent, particularly at a low temperature, is preferably used.
The weight average molecular weight of the polyarylate resin is preferably 12000 or more, more preferably 50000 or more, from the viewpoint of obtaining a high tensile elongation at break.
[2 ] phase difference increasing agent
The phase difference raising agent as used herein refers to a compound having the following functions: the retardation value Rt (measured at 23 ℃ C. 55% RH and a wavelength of 590 nm) in the thickness direction of the optical compensation film containing 3 parts by mass of the compound per 100 parts by mass of the resin used in the optical compensation film is 1.1 times or more larger than that of the optical compensation film to which the compound is not added.
The retardation raising agent according to the present invention is not particularly limited, and for example, a disk-shaped compound having an aromatic ring (1,3, 5-triazine-based compound or the like) described in the conventionally known Japanese patent application laid-open Nos. 2006-113239 [ 0143 ] to [ 0179 ], a rod-shaped compound described in the Japanese patent application laid-open Nos. 2006-113239 [ 0106 ] to [ 0112 ], a pyrimidine-based compound described in the Japanese patent application laid-open Nos. 2012-214682 [ 0118 ] to [ 0133 ], an epoxy ester compound or the like described in the Japanese patent application laid-open Nos. 2011-140637 [ 0022 ] to [ 0028 ], and a polyester compound or the like described in the International patent application laid-open Nos. 2012/014571 [ 0044 ] to [ 0058 ] can be used.
The properties required for the retardation raising agent according to the present invention include excellent compatibility with a resin, excellent retardation expression when a film is formed into a thin film, excellent precipitation resistance, and excellent resistance to phase difference value fluctuation accompanying the entrance and exit of moisture under high humidity, and the addition of the retardation raising agent is preferable because the retardation raising agent itself is disturbed in orientation during the heat treatment, and causes phase difference fluctuation from the compound, thereby making it possible to cancel out phase difference fluctuation from polymer molecules constituting the film.
From this viewpoint, the following nitrogen-containing heterocyclic compound is preferably used as the phase difference increasing agent.
[ Nitrogen-containing heterocyclic Compound ]
The phase difference increasing agent according to the present invention is preferably a nitrogen-containing heterocyclic compound having a structure represented by the following general formula (1).
The nitrogen-containing heterocyclic compound according to the present invention is preferably a nitrogen-containing heterocyclic compound having a pyrrole ring, a pyrazole ring, a triazole ring or an imidazole ring, from the viewpoint of bringing about a preferable interaction with a phase difference increasing function and orientation of resin molecules at the time of heat treatment, particularly a nitrogen-containing heterocyclic compound having a structure represented by the following general formula (1).
A compound having a structure represented by the general formula (1)
General formula (1)
In the above general formula (1), A1、A2And B each independently represents an alkyl group (e.g., methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-octyl, 2-ethylhexyl), a cycloalkyl group (e.g., cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl), an aromatic hydrocarbon ring or an aromatic heterocyclic ring. Among them, an aromatic hydrocarbon ring or an aromatic heterocyclic ring is preferable, and an aromatic hydrocarbon ring or an aromatic heterocyclic ring having 5 or 6 members is particularly preferable.
Examples of the structure of the aromatic hydrocarbon ring or aromatic heterocyclic ring not limited to 5-or 6-membered, include benzene ring, pyrrole ring, pyrazole ring, imidazole ring, 1,2, 3-triazole ring, 1,2, 4-triazole ring, tetrazole ring, furan ring, and the like,
Azolyl ring, iso
An azolyl ring,
Diazole ring, isoxazole
A dioxane ring, a thiophene ring, a thiazole ring, an isothiazole ring, a thiadiazole ring, an isothiazole ring, etc.
From A1、A2The 5-or 6-membered aromatic hydrocarbon ring or aromatic heterocycle represented by B may have a substituent, and examples of the substituent include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), an alkyl group (methyl group, ethyl group, n-propyl group, isopropyl group, tert-butyl group, n-octyl group, 2-ethylhexyl group, etc.), a cycloalkyl group (cyclohexyl group, cyclopentyl group, 4-n-dodecylcyclohexyl group, etc.), an alkenyl group (vinyl group, propenyl group, etc.), a cycloalkenyl group (2-cyclopenten-1-yl group, 2-cyclohexen-1-yl group, etc.), an alkynyl group (ethynyl group, propargyl group, etc.), an aromatic hydrocarbon ring group (phenyl group, p-tolyl group, naphthyl group, etc.), an aromatic heterocyclic group (2-pyrrolyl group, 2-furyl group, 2-thienyl group, pyrrolyl group, imidazolyl group, etc.),
Azolyl, thiazolyl, benzimidazolyl, benzo
Azolyl, 2-benzothiazolyl, pyrazolonyl, pyridyl, pyridonyl, 2-pyrimidinyl, triazinyl, pyrazolyl, 1,2, 3-triazolyl, 1,2, 4-triazolyl,
Azolyl radical, iso
Azolyl, 1,2, 4-
Oxadiazolyl, 1,3, 4-
Oxadiazolyl, thiazolyl, isothiazolyl, 1,2, 4-thiadiazolyl, 1,3, 4-thiadiazolyl, etc.), cyano, hydroxy, nitro, carboxy, alkoxy (methoxy, ethoxy, isopropoxy, tert-butoxy, N-octyloxy, 2-methoxyethoxy, etc.), aryloxy (phenoxy, 2-methylphenoxy, 4-tert-butylphenoxy, 3-nitrophenoxy, 2-tetradecylaminophenoxy, etc.), acyloxy (formyloxy, acetoxy, pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy, etc.), amino (amino, methylamino, dimethylamino, anilino, N-methylanilino, diphenylamino, etc.), acylamino (formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, etc.), amino, etc.), Alkyl and arylsulfonylamino (methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3, 5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino and the like), mercapto, alkylthio (methylthio, ethylthio, N-hexadecylthio and the like), arylthio (phenylthio, p-chlorophenylthio, m-methoxyphenylthio and the like), sulfamoyl (N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N-dimethylsulfamoyl, N-acetylsulfamoyl, N-benzoylsulfamoyl, N- (N' -phenylcarbamoyl) sulfamoyl and the like), sulfo, acyl (acetyl, pivaloylbenzoyl and the like), carbamoyl (carbamoyl, N-methylcarbamoyl, N-dimethylcarbamoyl, N-trichlorosulfonylamino and the like), sulfonyl, N-ethylsulfamoyl and the like, N, N-di-N-octylcarbamoyl group, N- (methylsulfonyl) carbamoyl group, etc.).
In the above general formula (1), A1、A2And B represents a benzene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, a1, 2, 3-triazole ring or a1, 2, 4-triazole ring, it is preferable because an optical compensation film having an excellent effect of changing optical characteristics and excellent durability can be obtained.
In the above general formula (1), T1And T2Each independently represents a pyrrole ring, a pyrazole ring, an imidazole ring, a1, 2, 3-triazole ring or a1, 2, 4-triazole ring. Among these, a pyrazole ring, a triazole ring orThe imidazole ring is particularly preferable because a resin composition having an especially excellent effect of suppressing the fluctuation of the phase difference during heat treatment and excellent durability can be obtained, and a pyrazole ring is particularly preferable. From T1And T2The pyrazole ring, the 1,2, 3-triazole ring, the 1,2, 4-triazole ring and the imidazole ring shown in the specification may be tautomers. Specific structures of the pyrrole ring, the pyrazole ring, the imidazole ring, the 1,2, 3-triazole ring, or the 1,2, 4-triazole ring are shown below.
Wherein L in the formula (1) is as shown in the specification1、L2、L3Or L4The location of the bond. R5Represents a hydrogen atom or a non-aromatic substituent. As a group consisting of R5The non-aromatic substituent represented by the formula (1) includes A1The same group as the non-aromatic substituent may be used as the substituent. From R5When the substituent represented is a substituent having an aromatic group, A1And T1Or B and T1Become easily distorted A1B and T1Since the resin cannot interact with the resin, it is difficult to suppress the variation in optical characteristics. In order to improve the effect of suppressing the fluctuation of the optical characteristics, R5Preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 5 carbon atoms, and particularly preferably a hydrogen atom.
In the above general formula (1), T1And T2May have a substituent, and examples of the substituent include those represented by A in the general formula (1)1And A2The same group as the substituent may be present.
In the above general formula (1), L1、L2、L3And L4Each independently represents a single bond or a 2-valent linking group, and is connected to a 5-or 6-membered aromatic hydrocarbon ring or aromatic heterocyclic ring through 2 or less atoms. The number of atoms intervening by 2 or less means the minimum number of atoms present between the substituents bonded among the atoms constituting the linking group. As a linking group having 2 valences and having 2 or less linking atomsThe substituent is particularly limited to a 2-valent linking group selected from alkylene, alkenylene, alkynylene, O, (C ═ O), NR, S, (O ═ S ═ O), or a linking group obtained by combining 2 of these groups. R represents a hydrogen atom or a substituent. Examples of the substituent represented by R include an alkyl group (e.g., methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-octyl, 2-ethylhexyl), a cycloalkyl group (e.g., cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl), an aromatic hydrocarbon ring group (e.g., phenyl, p-tolyl, naphthyl), an aromatic heterocyclic group (e.g., 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl, 2-pyridyl), a cyano group, and the like. From L1、L2、L3And L4The 2-valent linking group may have a substituent, and the substituent is not particularly limited, and examples thereof include those represented by A in the general formula (1)1And A2The same group as the substituent may be present.
Since the compound having the structure represented by the above general formula (1) has high planarity, interaction with a resin is strong, and fluctuation in optical properties is suppressed, L in the above general formula (1)1、L2、L3And L4Preferably a single bond or O, (C ═ O) -O, O- (C ═ O), (C ═ O) -NR or NR- (C ═ O), more preferably a single bond.
In the general formula (1), n represents an integer of 0 to 5. When n represents an integer of 2 or more, a plurality of A in the above general formula (1)2、T2、L3、L4May be the same or different. The larger n is, the stronger the interaction between the compound having the structure represented by the above general formula (1) and the resin is, and therefore, the excellent effect of suppressing the fluctuation of the optical characteristics is obtained, and the smaller n is, the more excellent the compatibility with the resin is. Therefore, n is preferably an integer of 1 to 3, more preferably an integer of 1 or 2.
A compound having a structure represented by the general formula (2)
The compound having a structure represented by the general formula (1) is preferably a compound having a structure represented by the general formula (2).
General formula (2)
(in the formula, A)1、A2、T1、T2、L1、L2、L3And L4Each of which is identical with A in the above general formula (1)1、A2、T1、T2、L1、L2、L3And L4Synonymously. A. the3And T3Each represents A in the general formula (1)1And T1The same groups. L is5And L6Is represented by the general formula (1) as described above1The same groups. m represents an integer of 0 to 4. )
The smaller m is, the more excellent the compatibility with the resin is, and therefore m is preferably an integer of 0 to 2, more preferably an integer of 0 to 1.
A compound having a structure represented by the general formula (1.1)
The compound having a structure represented by the general formula (1) is preferably a triazole compound having a structure represented by the following general formula (1.1).
General formula (1.1)
(in the formula, A)1、B、L1And L2Represents A in the above general formula (1)1、B、L1And L2The same groups. k represents an integer of 1 to 4. T is1Represents a1, 2, 4-triazole ring. )
Further, the triazole compound having the structure represented by the above general formula (1.1) is preferably a triazole compound having a structure represented by the following general formula (1.2).
General formula (1.2)
(wherein Z represents a structure represented by the following general formula (1.2 a.) q represents an integer of 2 to 3. at least two of Z's are bonded to the ortho-position or meta-position relative to at least one of Z's substituted on the benzene ring.)
General formula (1.2a)
(in the formula, R10Represents a hydrogen atom, an alkyl group or an alkoxy group. p represents an integer of 1 to 5. Represents a position bonded to a benzene ring. T is1Represents a1, 2, 4-triazole ring. )
The compound having the structure represented by the above general formula (1), (2), (1.1) or (1.2) may also form a hydrate, a solvate or a salt. In the present invention, the hydrate may contain an organic solvent, and the solvate may contain water. That is, "hydrate" and "solvate" include mixed solvates containing both water and an organic solvent. The salt includes an acid addition salt formed with an inorganic or organic acid. Examples of the inorganic acid include hydrohalic acid (hydrochloric acid, hydrobromic acid, and the like), sulfuric acid, phosphoric acid, and the like, and are not limited thereto. Examples of the organic acid include, but are not limited to, acetic acid, trifluoroacetic acid, propionic acid, butyric acid, oxalic acid, citric acid, benzoic acid, alkylsulfonic acid (methanesulfonic acid, etc.), allylsulfonic acid (benzenesulfonic acid, 4-toluenesulfonic acid, 1, 5-naphthalenedisulfonic acid, etc.), and the like. Among these, hydrochloride, acetate, propionate and butyrate are preferable.
Examples of the salt include salts formed when an acidic moiety present in the parent compound is substituted with a metal ion (for example, an alkali metal salt such as a sodium or potassium salt, an alkaline earth metal salt such as a calcium or magnesium salt, an ammonium salt, an alkali metal ion, an alkaline earth metal ion, or an aluminum ion), or when the acid moiety is adjusted to an organic base (for example, ethanolamine, diethanolamine, triethanolamine, morpholine, piperidine, etc.), and the salts are not limited thereto. Among these, sodium salt and potassium salt are preferable.
Examples of the solvent contained in the solvate include any of general organic solvents. Specific examples thereof include alcohols (e.g., methanol, ethanol, 2-propanol, 1-butanol, 1-methoxy-2-propanol, and t-butanol), esters (e.g., ethyl acetate), hydrocarbons (e.g., toluene, hexane, and heptane), ethers (e.g., tetrahydrofuran), nitriles (e.g., acetonitrile), and ketones (acetone). Solvates of alcohols (e.g., methanol, ethanol, 2-propanol, 1-butanol, 1-methoxy-2-propanol, tert-butanol) are preferred. These solvents may be reaction solvents used in the synthesis of the above-mentioned compounds, solvents used in purification by crystallization after the synthesis, or mixtures thereof.
In addition, 2 or more solvents may be contained at the same time, or a form including water and a solvent (for example, water and alcohol (for example, methanol, ethanol, tert-butanol, and the like)) may be used.
The compound having the structure represented by the general formula (1), (2), (1.1) or (1.2) may be added in the form of water, a solvent or a salt, or a hydrate, a solvate or a salt may be formed in the optical compensation film of the present invention.
The molecular weight of the compound having a structure represented by the general formula (1), (2), (1.1) or (1.2) is not particularly limited, and the smaller the molecular weight, the more excellent the compatibility with the resin, and the larger the effect of suppressing the fluctuation of the optical value with respect to the change in the ambient humidity, and therefore, the range of 150 to 2000 is preferable, the range of 200 to 1500 is more preferable, and the range of 300 to 1000 is more preferable.
Further, the nitrogen-containing heterocyclic compound according to the present invention is particularly preferably a compound having a structure represented by the following general formula (3).
General formula (3)
(wherein A represents a pyrazole ring, Ar1And Ar2Each represents an aromatic hydrocarbon ring or an aromatic heterocyclic ring, and may have a substituent. R1Represents a hydrogen atom, an alkyl group, an acyl group, a sulfonyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group. q represents 1 or 2. n and m each represent an integer of 1 to 3. )
From Ar1And Ar2An aromatic hydrocarbon ring represented byThe aromatic heterocycle is preferably a 5-or 6-membered aromatic hydrocarbon ring or aromatic heterocycle, respectively, as exemplified in the general formula (1). In addition, as Ar1And Ar2Examples of the substituent(s) include the same substituents as those shown in the compound having a structure represented by the above general formula (1).
As R1Specific examples thereof include a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkyl group (e.g., a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a tert-butyl group, an n-octyl group, a 2-ethylhexyl group, etc.), an acyl group (e.g., an acetyl group, a pivaloylbenzoyl group, etc.), a sulfonyl group (e.g., a methylsulfonyl group, an ethylsulfonyl group, etc.), an alkoxycarbonyl group (e.g., a methoxycarbonyl group), an aryloxycarbonyl.
q represents 1 or 2, and n and m represent an integer of 1 to 3.
The compound having an aromatic hydrocarbon ring or an aromatic heterocyclic ring having 5 or 6 members used in the present invention is preferably a compound having a structure represented by the above general formula (1), (2), (1.1) or (1.2), and more preferably a compound further having a structure represented by the general formula (3). The compounds having the above-mentioned 5-or 6-membered aromatic hydrocarbon ring or aromatic heterocyclic ring which can be used in the present invention include, as specific examples, compounds described in paragraphs [0140] to [0214] of International publication No. 2014/109350. The present invention is not limited to the specific examples. In addition, specific examples may be tautomers, and hydrates, solvates, or salts may also be formed.
The synthetic methods of the compounds mentioned in the above specific examples can be similarly referred to paragraphs [0215] to [0239] of International publication No. 2014/109350.
Method for using compounds having structures represented by general formulae (1) to (3)
The compounds having the structures represented by the general formulae (1) to (3) according to the present invention may be contained in the optical compensation film in an appropriate amount, and the amount of the compound to be added is preferably 0.1 to 10% by mass, particularly preferably 1 to 5% by mass, and particularly preferably 2 to 5% by mass in the optical compensation film. The amount of addition varies depending on the type of resin and the type of the compound, but an optimum value may be determined depending on the amount of addition in which the optical compensation film of the present invention exhibits a desired retardation value. Within this range, the mechanical strength of the optical compensation film of the present invention is not impaired, and the variation in phase difference can be reduced even during heat treatment.
In addition, as a method of adding the compound having the structure represented by the above general formulae (1) to (3), the compound may be added as a powder to the resin for forming the optical compensation film, or may be added to the resin for forming the optical compensation film after being dissolved in a solvent.
[3 ] other additives
The optical compensation film according to the present invention may contain, in addition to the above additives, a plasticizer, an antioxidant, a matting agent, a light stabilizer, an optical anisotropy controlling agent, an antistatic agent, a releasing agent, and the like. The details of the main additives are described below.
[ plasticizer ]
In general, a plasticizer refers to an additive having the following effects: in general, brittleness is improved, melt viscosity is decreased, or flexibility is imparted by adding a polymer, but the glass transition temperature Tg of the optical compensation film may be decreased by adding the polymer, and therefore, it is preferable to use the polymer in a range where the glass transition temperature Tg of the optical compensation film is controlled within the range of the present invention.
In the present invention, as the plasticizer, known plasticizers such as phthalate ester, fatty acid ester, trimellitate ester, phosphate ester, polyester ester, sugar ester, and acrylic polymer can be used.
The amount of the plasticizer added is preferably in the range of 0.1 to 10% by mass, and more preferably in the range of 0.5 to 5% by mass, based on the resin.
[ ultraviolet absorbers ]
The optical compensation film according to the present invention may contain an ultraviolet absorber.
Examples of the ultraviolet absorber include hydroxybenzophenone-based compounds, benzotriazole-based compounds, salicylate-based compounds, benzophenone-based compounds, cyanoacrylate-based compounds, and nickel complex salt-based compounds, and benzotriazole-based compounds with little coloration are preferred. Further, the ultraviolet absorbers described in Japanese patent application laid-open Nos. H10-182621 and H8-337574, and the polymeric ultraviolet absorbers described in Japanese patent application laid-open No. H6-148430 are also preferably used.
The ultraviolet absorber used in the present invention preferably has a property of absorbing less visible light having a wavelength of 400nm or more from the viewpoint of preventing deterioration of the polarizing plate and the liquid crystal display cell, because the ultraviolet absorber has excellent absorption ability of ultraviolet light having a wavelength of 370nm or less and the liquid crystal display cell has good display properties.
The amount of the ultraviolet absorber added is preferably in the range of 0.1 to 5% by mass, more preferably 0.5 to 5% by mass, based on the resin.
Examples of the benzotriazole-based ultraviolet absorber useful in the present invention include 2- (2 ' -hydroxy-5 ' -methylphenyl) benzotriazole, 2- (2 ' -hydroxy-3 ', 5 ' -di-tert-butylphenyl) benzotriazole, 2- (2 ' -hydroxy-3 ' -tert-butyl-5 ' -methylphenyl) benzotriazole, 2- (2 ' -hydroxy-3 ', 5 ' -di-tert-butylphenyl) -5-chlorobenzotriazole, 2- [2 ' -hydroxy-3 ' - (3 ', 4 ', 5 ', 6 ' -tetrahydrophthalimidomethyl) -5 ' -methylphenyl ] benzotriazole, 2-methylenebis [ 4- (1,1,3, 3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol ], 2- (2 ' -hydroxy-3 ' -tert-butyl-5 ' -methylphenyl) -5-chlorobenzotriazole, 2- (2H-benzotriazol-2-yl) -6- (linear and side chain dodecyl) -4-methylphenol, a mixture of octyl 3- [ 3-tert-butyl-4-hydroxy-5- (chloro-2H-benzotriazol-2-yl) phenyl ] propionate and 2-ethylhexyl 3- [ 3-tert-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl ] propionate, and the like, but is not limited thereto.
Further, as commercially available products, "TINUVIN 928", "TINUVIN 171", "TINUVIN 326" and "TINUVIN 328" (trade name, manufactured by BASF Japan) can be preferably used.
[ antioxidant ]
The antioxidant preferably contains a film because it has a function of retarding or preventing decomposition of the optical compensation film by halogen of a residual solvent in the optical compensation film, phosphoric acid of a phosphoric acid plasticizer, or the like.
As such an antioxidant, a hindered phenol-based compound is preferably used, and examples thereof include 2, 6-di-tert-butyl-p-cresol, pentaerythrityl-tetrakis [ 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], triethylene glycol-bis [ 3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate ], 1, 6-hexanediol-bis [ 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], 2, 4-bis- (N-octylthio) -6- (4-hydroxy-3, 5-di-tert-butylanilino) -1, 3, 5-triazine, 2-thiodiethylene bis [ 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], octadecyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, N' -hexamethylene bis (3, 5-di-tert-butyl-4-hydroxy-hydrocinnamamide), 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, tris- (3, 5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate, and the like.
Particularly preferred are 2, 6-di-tert-butyl-p-cresol, pentaerythrityl-tetrakis [ 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], triethylene glycol-bis [ 3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate ]. Further, for example, a hydrazine-based metal deactivator such as N, N' -bis [ 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hydrazine, or a phosphorus-based processing stabilizer such as tris (2, 4-di-tert-butylphenyl) phosphite may be used in combination.
The amount of the antioxidant added is preferably in the range of 0.1 to 5% by mass, and more preferably in the range of 0.5 to 3% by mass, based on the resin.
[ matting agent ]
In order to prevent the produced film from being scratched or deteriorated in transportability during handling, it is also preferable to add fine particles as a matting agent to the optical compensation film of the present invention.
Examples of the fine particles include fine particles of an inorganic compound and fine particles of a resin. Examples of the fine particles of the inorganic compound include silica, titania, alumina, zirconia, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate, and calcium phosphate. The fine particles contain silicon, and silica is particularly preferable because the turbidity is reduced.
The average particle diameter of the primary particles of the fine particles is preferably in the range of 5 to 400nm, more preferably in the range of 10 to 300 nm. They may be contained mainly as 2-stage aggregates having a particle diameter of 0.05 to 0.3 μm, but are preferably contained as primary particles without aggregation as long as they are particles having an average particle diameter of 80 to 400 nm.
The content of these fine particles in the film is preferably in the range of 0.01 to 1 mass%, and particularly preferably in the range of 0.05 to 0.5 mass%.
For example, fine particles of silica are commercially available under the trade name of AEROSIL R972, R972V, R974, R812, 200V, 300, R202, OX50, and TT600 (manufactured by AEROSIL Co., Ltd., Japan).
The fine particles of zirconia can be used commercially under the trade names of AEROSIL R976 and R811 (manufactured by AEROSIL CORPORATION, Japan).
Examples of the fine particles of the resin include silicone resin, fluororesin, and acrylic resin. Silicone resins are preferred, and fine particles having a three-dimensional network structure are particularly preferred, and can be commercially available and used, for example, under the trade names tospearll 103, tospearll 105, tospearll 108, tospearll 120, tospearll 145, tospearll 3120, and tospearll 240 (manufactured by toshiba silicone co., ltd.).
Of these, AEROSIL 812 and AEROSIL R972V are particularly preferably used because they have a large effect of reducing the friction coefficient while keeping the haze of the film low.
The optical compensation film according to the present invention preferably has a dynamic friction coefficient of at least one surface within a range of 0.2 to 1.0.
[ 4] method for producing optical compensation film
The method for producing the optical compensation film according to the present invention will be described by taking an example in which a cycloolefin resin is used.
[ 4.1 ] method for casting solution into film
The method for producing the optical compensation film of the present invention is preferably performed by a solution casting film forming method (hereinafter, also referred to as a solution casting method), and a known method can be appropriately used.
Examples of the solvent used in the solution casting method include chlorine-based solvents such as chloroform and methylene chloride; aromatic solvents such as toluene, xylene, benzene, and mixed solvents thereof; alcohol solvents such as methanol, ethanol, isopropanol, n-butanol, and 2-butanol; methyl cellosolve, ethyl cellosolve, butyl cellosolve, dimethylformamide, dimethyl sulfoxide, and di (methyl ethyl methyl ethyl methyl ethyl methyl ethyl
Alkanes, cyclohexanone, tetrahydrofuran, acetone, Methyl Ethyl Ketone (MEK), ethyl acetate, diethyl ether, and the like. These solvents may be used alone in 1 kind, or 2 or more kinds may be used in combination.
The solvent used in the present invention is preferably a mixed solvent of a good solvent and a poor solvent, and the good solvent includes, for example, a chlorine-based organic solvent such as methylene chloride, and a non-chlorine-based organic solvent such as methyl acetate, ethyl acetate, amyl acetate, acetone, methyl ethyl ketone, tetrahydrofuran, 1, 3-dioxolane, 1, 4-dioxolane
Alkane, cyclohexanone, ethyl formate, 2,2, 2-trifluoroethanol, 2,2,3, 3-hexafluoro-1-propanol, 1, 3-difluoro-2-propanol, 1,1,1,3,3, 3-hexafluoro-2-methyl-2-propanol, 1,1,1,3,3, 3-hexafluoro-2-propanol, 2,2,3,3, 3-pentafluoro-1-propanol, nitroethane, methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, etc., and among them, dichloromethane is preferable.
The poor solvent is preferably an alcohol-based solvent selected from methanol, ethanol and butanol, which is preferable from the viewpoint of improving the releasability and enabling high-speed casting.
In the present invention, if the solvent is a mixed solvent, the good solvent is preferably used in an amount of 55 mass% or more, more preferably 70 mass% or more, and still more preferably 80 mass% or more, based on the whole amount of the solvent.
When an optical compensation film is produced by a solution casting method, for example, a dope containing a compound having the cycloolefin resin and the structure represented by the general formula (3) and a solvent is prepared, and the dope is cast onto a support.
That is, it is preferable to have the following steps: a step of dissolving at least a cycloolefin resin and a compound having a structure represented by general formula (3) to prepare a cement; casting the dope on a metal support in a belt or drum shape; a step of drying the cast dope in the form of a web (ウェブ); a step of peeling the metal support; a step of stretching or holding the width; a step of further drying; and a step of winding the completed film.
In the solution casting method, it is preferable that the concentration of the cycloolefin resin in the dope is higher because the drying load after casting on the metal support can be reduced, but if the concentration of the cycloolefin resin is too high, the load at the time of filtration increases, and the filtration accuracy deteriorates. The concentration having both of these effects is preferably 10 to 35% by mass, and more preferably 15 to 25% by mass. The metal support in the casting (casting) step is preferably mirror-finished on the surface, and a stainless steel belt or a drum whose surface is cast and polished is preferably used as the metal support.
The casting width can be set to be 1-4 m. The surface temperature of the metal support in the casting step is appropriately determined to be 0 to 100 ℃, and more preferably 5 to 30 ℃, and is set to be not higher than the temperature at which the solvent does not boil and foams. The higher the temperature is, the more the drying speed of the web can be accelerated, and therefore, this is preferable, but if the remaining temperature is too high, the web may be foamed or the planarity may be deteriorated.
Further, it is also a preferable method to gel the web by cooling and to peel it from the drum in a state containing a large amount of residual solvent. The method of controlling the temperature of the metal support is not particularly limited, and there are a method of blowing warm air or cold air, and a method of bringing warm water into contact with the back side of the metal support. Since heat transfer can be efficiently performed using warm water, the time for the temperature of the metal support to reach a constant value is preferably short.
When warm air is used, warm air having a temperature higher than the target temperature may be used in consideration of a decrease in the temperature of the web due to latent heat of evaporation of the solvent, and air having a temperature higher than the target temperature may be used while preventing foaming.
In particular, it is preferable to change the temperature of the support and the temperature of the drying air during the period from the casting to the peeling to efficiently perform the drying.
In order to provide an optical compensation film with good planarity, the amount of the residual solvent in the process of peeling the web from the metal support is preferably 10 to 150 mass%, more preferably 20 to 40 mass% or 60 to 130 mass%, and particularly preferably 20 to 30 mass% or 70 to 120 mass%.
The residual solvent amount is defined by the following formula.
Residual solvent amount (% by mass) { (M-N)/N } × 100
M is the mass of a sample obtained by extracting a web or film at any time during or after production, and N is the mass of M after heating at 115 ℃ for 1 hour.
In the step of drying the optical film, the web is preferably peeled off from the metal support and further dried so that the residual solvent amount is 1 mass% or less, more preferably 0.1 mass% or less, and particularly preferably 0 to 0.01 mass% or less.
In the film drying step, a roll drying method (a method of drying a web by passing it alternately through a plurality of rolls arranged above and below) and a method of drying a web while conveying it by a tenter method are generally used.
The optical compensation film according to the present invention is preferably stretched from the viewpoint of smoothness of the film and adjustment of retardation.
In the method for producing an optical film according to the present invention, stretching is preferably performed in the longitudinal direction and/or the width direction, or in an oblique direction.
The stretching operation may be performed in multiple stages. In the case of biaxial stretching, simultaneous biaxial stretching may be performed, or the biaxial stretching may be performed in stages. In this case, the stepwise stretching means that, for example, stretching in different stretching directions may be performed sequentially, or stretching in the same direction may be divided into a plurality of stages, and stretching in different directions may be applied at any one stage.
That is, for example, the following stretching step may be performed:
stretching in the longitudinal direction → stretching in the width direction → stretching in the longitudinal direction
Stretching in the widthwise direction → stretching in the longitudinal direction
The simultaneous biaxial stretching also includes stretching in one direction and contracting by relaxing the tension in the other direction.
The amount of the residual solvent at the start of stretching is preferably in the range of 2 to 50 mass%.
When the amount of the residual solvent is 2% by mass or more, the variation in film thickness is small, and is preferable from the viewpoint of planarity, and when the amount is 50% by mass or less, the unevenness on the surface is reduced, and planarity is improved, which is preferable.
In the method for producing an optical compensation film according to the present invention, stretching may be performed in the longitudinal direction and/or the width direction, preferably the width direction, so that the film thickness after stretching falls within a desired range. Although the stretching temperature varies depending on the type of resin, it is preferable to stretch the film at a temperature in the range of (TgL-200 ℃) to (TgH +50 ℃) where TgL is the lowest Tg and TgH is the highest Tg among the glass transition temperatures Tg of the film. When the stretching is performed in the above temperature range, the stretching stress can be reduced, and thus the haze is reduced. Further, an optical compensation film containing a cycloolefin resin can be obtained which suppresses the occurrence of cracks and is excellent in planarity and coloring property of the film itself. The stretching temperature is more preferably in the range of (TgL-150 ℃) to (TgH +40 ℃).
In the method for producing an optical compensation film according to the present invention, the film having self-supporting properties and being peeled from the support can be stretched in the longitudinal direction by limiting the running speed with a stretching roll. The stretching ratio in the longitudinal direction is preferably 1.03 to 2.00 times, more preferably 1.10 to 1.80 times, and even more preferably 1.20 to 1.60 times at a temperature of 30 to 250 ℃.
In the case of stretching in the widthwise direction, for example, a method (referred to as a tenter system) of drying the film while maintaining the width of both widthwise ends of the film by clips or needle plates in the widthwise direction by all or a part of the drying process as described in japanese patent laid-open No. 62-46625 is preferably used, and among them, a tenter system using clips is preferably used.
The film stretched in the longitudinal direction or the unstretched film is preferably introduced into a tenter while both widthwise ends are held by clips, and stretched in the widthwise direction while traveling together with the clips of the tenter. The stretching ratio in the width direction is not particularly limited, but is preferably 1.03 to 2.00 times, more preferably 1.10 to 1.80 times, and still more preferably 1.20 to 1.60 times at a temperature of 30 to 300 ℃.
When stretching in the widthwise direction, it is preferable to stretch the film at a stretching speed of 50 to 1000%/min in the widthwise direction of the film from the viewpoint of improving the flatness of the film.
When the stretching rate is 50%/min or more, the planarity is improved, and the film can be processed at a high speed, and therefore, the stretching rate is preferably from the viewpoint of production suitability, and when the stretching rate is 1000%/min or less, the film can be processed without breaking, which is preferable.
More preferably, the stretching speed is in the range of 100 to 500%/min. The drawing speed is defined by the following formula.
Stretching speed (%/min) [ (d)1/d2)－1]×100(％)/t
(in the above formula, d1Is the width dimension in the stretching direction of the stretched resin film, d2The width dimension of the resin film before stretching in the stretching direction is t, and the time (min) required for stretching is t. )
In the stretching step, holding and relaxation are usually performed after stretching. That is, in this step, it is preferable to sequentially perform a stretching step of stretching the film, a holding step of holding the film in a stretched state, and a relaxation step of relaxing the film in the stretching direction. In the holding step, the stretching at the stretching ratio achieved in the stretching step is held at the stretching temperature in the stretching step. In the relaxation stage, after the stretching in the stretching stage is held in the holding stage, the tension for stretching is released, thereby relaxing the stretching. The relaxation step may be performed at a temperature not higher than the stretching temperature in the stretching step.
In addition, in the case of oblique stretching, reference is made to japanese patent laid-open nos. 2005-321543 and 2013-120208.
Next, the stretched film is heated and dried. When the film is heated by hot air or the like, it is also preferable to use a method of preventing the used hot air from being mixed by providing a nozzle capable of discharging the used hot air (air containing a solvent or air mixed with moisture). The temperature of the hot air is more preferably in the range of 40-350 ℃. The drying time is preferably about 5 seconds to 30 minutes, and more preferably 10 seconds to 15 minutes.
Further, the heating and drying method is not limited to hot air, and for example, infrared rays, heating rollers, microwaves, or the like can be used. From the viewpoint of simplicity, it is preferable to dry the film with hot air or the like while conveying the film with rollers arranged in a staggered manner. The drying temperature is more preferably in the range of 40 to 350 ℃ in consideration of the amount of the residual solvent, the expansion and contraction rate during transportation, and the like.
In the drying step, the film is preferably dried until the residual solvent amount is 0.5% by mass or less.
The winding step is a step of winding the obtained film and cooling the film to room temperature. The coiler may be any one that is generally used, and for example, coiling may be performed by a coiling method such as a constant tension method, a constant torque method, a taper tension method, or a programmed tension control method in which an internal stress is constant.
The thickness of the optical compensation film according to the present invention is usually in the range of 5 to 500 μm, preferably 10 to 150 μm, depending on the purpose of use, and is preferably 10 to 80 μm when used in a liquid crystal display device, and is particularly preferably 10 to 40 μm in view of recent thinning.
When the optical compensation film is formed into a film of 40 μm or less, it is generally necessary to increase the content of an additive such as a retardation raising agent in order to maintain the performance of the retardation film, and although bleeding of the additive becomes a problem, the compound having the structure represented by the general formula (3) according to the present invention is excellent in bleeding resistance and can be made into a film.
The film thickness may be prepared by adjusting the concentration of the solid content in the dope, the slit gap of the nozzle of the die, the extrusion pressure from the die, the metal support speed, and the like so as to have a desired thickness. The width of the transparent resin film obtained in the above manner is preferably in the range of 0.5 to 4m, more preferably in the range of 0.6 to 3m, and further preferably in the range of 0.8 to 2.5 m. The length is preferably in the range of 100 to 10000m, more preferably 500 to 9000m, and further preferably 1000 to 8000m, per roll.
The optical compensation film according to the present invention can realize desired optical characteristics by appropriately adjusting the polymer structure used, the type and amount of additives used, the stretch ratio, and the process conditions such as residual volatile components during peeling.
The optical compensation film according to the present invention has a desired retardation value by being subjected to a stretching treatment or preferably by being subjected to a stretching treatment with a retardation raising agent. The in-plane retardation value Ro and the retardation value Rt in the thickness direction can be measured three-dimensionally using an automatic birefringence meter Axo Scan (Axo Scan Mueller Matrix Polarimeter, manufactured by Axo Metrix) at a wavelength of 590nm in an atmosphere of 23 ℃ and 55% RH, and the obtained refractive index nx、ny、nzAnd (6) calculating.
When the optical compensation film according to the present invention is included in a VA-mode liquid crystal display device, it is preferable that the retardation value Ro in the in-plane direction of the optical compensation film represented by the following formulae (i) and (ii) is in the range of 40 to 60nm and the retardation value Rt in the film thickness direction is in the range of 110 to 140nm, from the viewpoint of improving visibility such as a viewing angle and contrast. The optical compensation film can be adjusted to be within the range of the retardation value by stretching the optical compensation film while adjusting the stretching ratio at least in the width direction.
Formula (i): ro ═ nx－ny)×d(nm)
Formula (ii): rt { (n)x+ny)/2－nz}×d(nm)
[ in formulae (i) and (ii), nxThe refractive index in the direction x in which the refractive index is the largest in the in-plane direction of the film is shown. n isyThe refractive index in the in-plane direction of the film in the direction y orthogonal to the direction x is shown. n iszWhich represents the refractive index in the thickness direction z of the film. d represents the thickness (nm) of the film. Angle (c)
In addition, the optical compensation film according to the present invention preferably has a variation of the retardation value Ro in the in-plane direction within a range of ± 3.0% and a variation of the retardation value Rt in the thickness direction within a range of ± 4.0% when heat-treated at 150 ℃ for 1 hour.
The heat treatment can determine the variation of the phase difference before and after the film sample is left at 150 ℃ for 1 hour in a thermostatic bath such as an oven according to the following equation.
Variation in retardation value Ro or Rt { (Ro value or Rt value after heat treatment-Ro value or Rt value before heat treatment)/(Ro value or Rt value before heat treatment) } × 100 (%)
In order to control the variation in Ro value and the variation in Rt value of the optical compensation film due to the heat treatment within the above ranges, it is effective to combine the selection of the resin according to the present invention and the addition (type and amount of addition) of the retardation raising agent, and it can be achieved by appropriately combining and adjusting the selection.
[ 4.2 ] melt casting film-forming method
The method for producing the optical compensation film of the present invention may be carried out by a melt casting film formation method (hereinafter also referred to as a melt casting method).
The case of producing the optical compensation film according to the present invention by the melt casting method will be described.
[ Process for producing molten particles ]
The resin-containing composition used for melt extrusion is usually preferably kneaded and pelletized in advance.
The pelletization may be carried out by a known method, for example, by supplying the dried resin and additive to an extruder from a supply machine, kneading the mixture by using a single-screw or twin-screw extruder, extruding the kneaded mixture from a die into a linear shape, and cooling the linear shape with water or air to cut the linear shape.
As for the raw materials, preliminary drying before extrusion is important in preventing decomposition of the raw materials. Particularly, the resin is likely to absorb moisture, and therefore, it is preferable to dry the resin in advance at 70 to 140 ℃ for 3 hours or more by a hot air drier or a vacuum drier so that the moisture content is 200ppm or less, and further 100ppm or less.
The additives may be supplied to the extruder in combination with the extruder, or may be supplied from different feeders. A small amount of additives such as an antioxidant is preferably mixed in advance in order to uniformly mix the additives.
The antioxidant may be mixed as a solid material, or may be mixed by dissolving the antioxidant in a solvent in advance and impregnating the thermoplastic resin with the antioxidant, or may be mixed by spraying, as necessary.
Vacuum nauta mixer or the like is preferable because drying and mixing can be performed simultaneously. In addition, when contacting with air from the feeder section, the outlet of the die, or the like, it is preferable to use dehumidified air or dehumidified N2Gas, etc.
The extruder is preferably capable of processing at as low a temperature as possible while suppressing shearing force and without causing deterioration of the resin (such as lowering of molecular weight, coloration, gel formation, etc.). For example, in the case of a twin-screw extruder, it is preferable to use a deep groove screw and rotate in the same direction. The intermeshing type is preferred from the viewpoint of kneading uniformity.
Film production was performed using the particles obtained in the above manner. The raw material powder may be directly supplied to the extruder by a feeder without granulation, and film production may be directly performed.
[ procedure for extruding the molten mixture from the die onto the chill roll ]
First, the melt temperature Tm when the produced pellets are extruded using a uniaxial or biaxial extruder is set to about 200 to 300 ℃, and after foreign matter is removed by filtration using a leaf-disk filter or the like, the pellets are extruded from a T-die into a film shape, solidified on a chill roll, and cast while being pressed against an elastic contact roll.
When the raw material is introduced into the extruder from the hopper, it is preferable to prevent oxidative decomposition or the like under vacuum or reduced pressure or in an inert gas atmosphere. Note that Tm is the temperature of the die outlet portion of the extruder.
If foreign matter such as scratches and coagulated plasticizer adheres to the die, a streak-like defect may occur. Such a defect is also referred to as a die mark, and in order to reduce a surface defect such as a die mark, it is preferable to have a structure in which a staying portion of the resin is reduced as much as possible in a pipe from the extruder to the die. It is preferable to use a structure in which the lip portion is as free from scratches and the like as possible inside the die.
The inner surface of the extruder, die, or the like, which is in contact with the molten resin, is preferably subjected to surface processing in which the molten resin is less likely to adhere thereto, for example, by using a material having a low surface energy or the like, while reducing the surface roughness. Specifically, the surface subjected to hard chrome plating or ceramic thermal spraying is polished to have a surface roughness of 0.2S or less.
The cooling roll is not particularly limited, and is a metal roll having high rigidity and a structure in which a heat medium or a cooling medium having a controllable temperature flows inside, and the size is not limited as long as the size is sufficient to cool the melt-extruded film, and the diameter of the cooling roll is usually about 100mm to 1 m.
The surface material of the cooling roll includes carbon steel, stainless steel, aluminum, titanium, and the like. In order to further increase the hardness of the surface or improve the peelability from the resin, it is preferable to perform surface treatment such as hard chromium plating, nickel plating, amorphous chromium plating, or ceramic thermal spraying.
The surface roughness of the surface of the cooling roll is preferably 0.1 μm or less in Ra, and more preferably 0.05 μm or less. This is because the smoother the roll surface, the smoother the surface of the resulting film can also be. It is of course preferable that the surface-finished surface is further ground to make the above-mentioned surface roughness.
As the elastic contact roller, a silicone rubber roller having a surface coated with a thin film metal sleeve as described in Japanese patent application laid-open Nos. 03-124425, 08-224772, 07-100960, 10-272676, WO97/028950, 11-235747, 2002-36332, 2005-172940, and 2005-280217 can be used.
When the film is peeled from the cooling roll, it is preferable to prevent the deformation of the film by controlling the tension.
The steps after the peeling are the same as those in the solution casting method.
[ 5] touch panel module
The touch panel module according to the present invention is characterized in that the transparent conductive layer is formed on the optical compensation film according to the present invention, and the shape of the transparent electrode pattern is not particularly limited as long as it is a pattern that can be satisfactorily operated as a touch panel module (for example, an electrostatic capacitance type touch panel module), and examples thereof include the patterns described in japanese patent publication nos. 2011-511357, 2010-164938, 2008-310550, 2003-511799, and 2010-541109.
The touch panel module according to the present invention can be basically manufactured as follows: the transparent conductive layer patterned in the X axis or Y axis formed on the optical compensation film is laminated with the transparent conductive layer patterned in the Y axis or X axis formed on the optical compensation film or another protective film, and a polarizing plate, a protective film, and the like are laminated using an adhesive layer as appropriate, and a protective glass is provided on the outermost surface as needed. Further, the liquid crystal display device with a touch panel of the present invention can be manufactured by combining the touch panel with a VA mode liquid crystal display device.
[ 5.1 ] transparent conductive layer
The transparent conductive layer according to the present invention preferably has a sheet resistance value in the range of 0.01 to 150 Ω/□. More preferably, the resistance value of the transparent conductive layer is in the range of 0.1 to 100 Ω/□. When the resistance value of the transparent conductive layer is 0.01 Ω/□ or more, durability against environmental fluctuations such as high temperature and high humidity can be obtained, and when the resistance value is 150 Ω/□ or less, curling can be suppressed.
[ transparent conductive Material ]
The material of the transparent conductive layer according to the present invention is not particularly limited as long as the transparent conductive layer satisfies the above resistance value, and a transparent conductive material such as ITO (indium tin oxide) or IZO (indium zinc oxide) is preferably used. The transparent conductive layer using ITO is formed by a method using a wet process such as a coating method, an ink-jet method, a coating method, or a dipping method, a method using a dry process such as a vapor deposition method (resistance heating, EB method, or the like), a sputtering method, or a CVD method, and is preferably formed by a vapor deposition method.
After the transparent conductive layer is formed, heat treatment (also referred to as annealing) is preferably performed to reduce the resistance value of the transparent conductive layer. The heating temperature is 150-250 ℃, and the heating time is 1-60 minutes. When the cycloolefin resin is used as the base material, the heating temperature is preferably in the range of 150 to 180 ℃ and the heating time is preferably in the range of 5 to 30 minutes.
[ Metal nanowires ]
Further, a transparent conductive layer made of a thin metal wire (metal nanowire, metal mesh) is also preferably used.
The metal nanowire is a conductive substance which is made of metal, is needle-shaped or filiform in shape and has a nanometer size in diameter. The metal nanowires may be linear or curved. When the transparent conductive layer made of metal nanowires is used, the metal nanowires are in a mesh shape, and a good conductive path can be formed even with a small amount of metal nanowires, and a transparent conductive layer with low resistance can be obtained. Further, the metal nanowires are formed into a mesh shape, and openings are formed in the gaps of the mesh, whereby a transparent conductive film having high light transmittance can be obtained.
The ratio of the thickness d to the length L (aspect ratio: L/d) of the metal nanowire is preferably within a range of 10 to 100000, more preferably within a range of 50 to 100000, and particularly preferably within a range of 100 to 10000. When the metal nanowires having such a large aspect ratio are used, the metal nanowires cross well, and high conductivity can be exhibited with a small amount of the metal nanowires. As a result, a transparent conductive film having high light transmittance can be obtained.
In the present specification, the "thickness of the metal nanowire" means a diameter of the metal nanowire when the cross section of the metal nanowire is a circle, a short diameter of the metal nanowire when the metal nanowire is an ellipse, and a longest diagonal line when the metal nanowire is a polygon. The thickness and length of the metal nanowire can be confirmed by a scanning electron microscope or a transmission electron microscope.
The thickness of the metal nanowires is preferably less than 500nm, more preferably less than 200nm, particularly preferably in the range of 10 to 100nm, and most preferably in the range of 10 to 50 nm. In such a range, a transparent conductive layer having high light transmittance can be formed.
The length of the metal nanowire is preferably in the range of 2.5 to 1000 μm, more preferably in the range of 10 to 500 μm, and particularly preferably in the range of 20 to 100 μm. In such a range, a transparent conductive layer having high conductivity can be obtained.
As the metal constituting the metal nanowire, any appropriate metal can be used as long as it is a metal having high conductivity. Examples of the metal constituting the metal nanowire include silver, gold, copper, and nickel. Further, a material obtained by plating (e.g., gold plating) these metals may be used. Among them, silver or copper is preferable from the viewpoint of conductivity.
As the method for producing the metal nanowire, any appropriate method can be adopted. For example, a method of reducing silver nitrate in a solution; and a method of applying an applied voltage or current to the surface of the precursor from the distal end portion of the probe to draw the metal nanowire at the distal end portion of the probe, thereby continuously forming the metal nanowire. In a method of reducing silver nitrate in a solution, silver nanowires can be synthesized by performing liquid-phase reduction of a silver salt such as silver nitrate in the presence of a polyol such as ethylene glycol and polyvinylpyrrolidone.
Silver nanowires of uniform size can be mass-produced, for example, according to the methods described in Xia, Y.et., chem.Mater. (2002), 14, 4736-.
The transparent conductive layer can be formed by applying the composition for forming a transparent conductive layer containing the metal nanowires onto the optical compensation film or the protective film according to the present invention. More specifically, the transparent conductive layer can be formed by applying a dispersion (composition for forming a transparent conductive layer) in which the metal nanowires are dispersed in a solvent to the optical compensation film or the protective film and then drying the applied layer.
Examples of the solvent include water, an alcohol solvent, a ketone solvent, an ether solvent, a hydrocarbon solvent, and an aromatic solvent. From the viewpoint of reducing the environmental load, water is preferably used.
The dispersion concentration of the metal nanowires in the composition for forming a transparent conductive layer containing the metal nanowires is preferably in the range of 0.1 to 1 mass%. In such a range, a transparent conductive layer having excellent conductivity and light transmittance can be formed.
The composition for forming a transparent conductive layer containing the metal nanowires may further contain any appropriate additive according to the purpose. Examples of the additive include an anticorrosive material for preventing corrosion of the metal nanowire and a surfactant for preventing aggregation of the metal nanowire. The kind, number and amount of the additives used may be appropriately set according to the purpose. The composition for forming a transparent conductive layer may contain any appropriate binder resin as needed, as long as the effects of the present invention can be obtained.
As a method for applying the composition for forming a transparent conductive layer containing the metal nanowires, any appropriate method can be used. Examples of the coating method include a spray coating method, a bar coating method, a roll coating method, a die coating method, an inkjet coating method, a screen coating method, a dip coating method, a relief printing method, a gravure printing method, and a gravure printing method.
As a method for drying the coating layer, any suitable drying method (for example, natural drying, air-blast drying, and heat drying) can be employed. For example, in the case of heat drying, the drying temperature is typically in the range of 100 to 200 ℃ and the drying time is typically in the range of 1 to 10 minutes.
After drying, heat treatment (also referred to as annealing) is preferably performed to reduce the resistance value of the transparent conductive layer. The heating temperature is 150-250 ℃, and the heating time is 1-60 minutes. When the cycloolefin resin is used as the base material, the heating temperature is preferably in the range of 150 to 180 ℃ and the heating time is preferably in the range of 5 to 30 minutes.
When the transparent conductive layer contains metal nanowires, the thickness of the transparent conductive layer is preferably in the range of 0.01 to 10 μm, more preferably in the range of 0.05 to 3 μm, and particularly preferably in the range of 0.1 to 1 μm. When the amount is in this range, a transparent conductive layer having excellent conductivity and light transmittance can be obtained.
When the transparent conductive layer includes metal nanowires, the total light transmittance of the transparent conductive layer is preferably 85% or more, more preferably 90% or more, and still more preferably 95% or more.
[ Metal netting ]
The transparent conductive layer including the metal mesh is formed by forming fine metal wires in a lattice pattern on the transparent base material. As the metal constituting the metal mesh, any appropriate metal can be used as long as it is a metal having high conductivity. Examples of the metal constituting the metal mesh include silver, gold, copper, and nickel. Further, a material obtained by plating (e.g., gold plating) these metals may be used. Among them, copper is preferable, and is also preferable from the viewpoint of preventing migration and suppressing disconnection at the time of key pressing.
The transparent conductive layer comprising the metal mesh may be formed by any suitable method. The transparent conductive layer can be obtained, for example, by applying a photosensitive composition containing a silver salt (composition for forming a transparent conductive layer) to the laminate, and then performing exposure treatment and development treatment to form a fine metal wire into a predetermined pattern. The transparent conductive layer may be obtained by printing a paste (composition for forming a transparent conductive layer) containing metal fine particles in a predetermined pattern.
The details of such a transparent conductive layer and a method for forming the same are described in, for example, japanese patent laid-open No. 2012-18634, the description of which is incorporated herein by reference. Further, another example of the transparent conductive layer made of a metal mesh and a method for forming the same is a transparent conductive layer and a method for forming the same described in japanese patent application laid-open No. 2003-331654.
When the transparent conductive layer includes a metal mesh, the thickness of the transparent conductive layer is preferably in the range of 0.1 to 30 μm, and more preferably in the range of 0.1 to 9 μm.
When the transparent conductive layer includes a metal mesh, the transmittance of the transparent conductive layer is preferably 80% or more, more preferably 85% or more, and further preferably 90% or more.
[ 5.2 ] adhesive layer
The adhesive layer used in the present invention preferably contains an adhesive that contains a thermosetting resin, an Ultraviolet (UV) curable resin, or a chemically curable resin, is optically transparent, and exhibits appropriate viscoelasticity and adhesive properties.
Specific examples of the binder include adhesives or pressure-sensitive adhesives such as acrylic copolymers, epoxy resins, polyurethanes, silicone polymers, polyethers, butyral resins, polyamide resins, polyvinyl alcohol resins, and synthetic rubbers. In the present invention, an adhesive which is cured by forming a film by a heat curing method, a photo curing method, a chemical reaction, or the like is preferable, and among them, an acrylic copolymer and an epoxy resin are most easily used because the adhesive properties are easily controlled and excellent in transparency, weather resistance, durability, and the like, and can be preferably used.
The binder may be a single liquid type, or may be a type in which 2 or more liquids are mixed before use. The binder may be a solvent system in which an organic solvent is used as a medium, an aqueous system such as an emulsion type, a colloidal dispersion type, or an aqueous solution type in which water is used as a main component, or a solvent-free type. The concentration of the binder solution may be appropriately determined depending on the film thickness after bonding, the coating machine, the coating conditions, and the like, and is usually 0.1 to 50% by mass.
The thickness of the adhesive layer may be suitably in the range of 0.1 to 100 μm, preferably 0.5 to 50 μm, and particularly preferably 0.5 to 30 μm. The viscosity of the binder at 25 ℃ in the coating is generally 1000 to 6000mPa/sec, preferably 2000 to 4000mPa/sec, for example 3000 to 4000 mPa/sec. Here, the viscosity is a value read by rotating a rotor for 30 seconds after standing using a B-type viscometer BH II manufactured by Tokimec (tokyo meter), for example. The Young's modulus (E) of the adhesive resin after complete curing is preferably 1 to 100MPa, for example, 5 to 20 MPa.
Examples of the acrylic binder include (meth) acrylic acid obtained by copolymerizing one or more kinds of alkyl acrylates having 1 to 20 carbon atoms such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylbutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, and decyl (meth) acrylate with (meth) acrylic acid copolymerizable with the above alkyl acrylates, and adhesives obtained by reacting a copolymer of functional monomers such as itaconic acid, maleic anhydride, 2-hydroxyethyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate with a crosslinking agent such as an isocyanate-based crosslinking agent, an epoxy-based crosslinking agent, an aziridine-based crosslinking agent, or a metal chelate-based crosslinking agent.
The epoxy Resin adhesive may be a Resin composition obtained by modifying an ultraviolet-curable epoxy Resin with a silicone elastomer and adding precipitated silica as an inorganic filler, and examples thereof include "NORLAND optical adhesive NOA 68" from Edmund Optics, and "optical elastomer Resin (Super View Resin)" from Sony Chemical & information device.
In order to promote the photocuring of the adhesive, it is preferable to further contain a photopolymerization initiator. The blending amount of the photopolymerization initiator is preferably determined by the following ratio in terms of mass: binder 20: 100-0.01: 100 contains.
Specific examples of the photopolymerization initiator include alkylphenone type, acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, α -amyl oxime ester, thioxanthone, and derivatives thereof, but are not particularly limited thereto. As these photopolymerization initiators, commercially available photopolymerization initiators can be used, and examples thereof include Irgacure 184, Irgacure 907, and Irgacure 651, which are available from BASF Japan, and the like.
The adhesive layer is preferably formed by applying a composition containing the above-mentioned binder, and examples thereof include conventionally known methods such as a bar coating method, a doctor blade coating method, a roll coating method, a blade coating method, a die coating method, a gravure coating method, a curtain coating method, and an ink jet method.
In the case of thermal curing, it is preferable to apply heating at 80 ℃ or higher in a dryer, and the heating time can be appropriately set.
The light source for the UV curing treatment may be used without limitation as long as it is a light source that generates ultraviolet rays. For example, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used.
The irradiation conditions are different for each lamp, and the irradiation amount of the active rays is usually 50 to 1000mJ/cm2Preferably 50 to 300mJ/cm2. The heat treatment temperature after UV curing is preferably 80 ℃.
After the adhesive layer is provided, a release sheet is preferably laminated on the surface until the adhesive layer is bonded to another member.
Various release sheets can be used, and typically, the release sheet is composed of a base sheet having releasability on the surface. Examples of the substrate sheet include films of polyester resin, polyethylene resin, polypropylene resin, polystyrene resin, polycarbonate resin, and the like, and films or synthetic papers obtained by blending fillers such as fillers in these films. Further, paper substrates such as cellophane, clay-coated paper, and high-quality paper can be mentioned.
[ 6 ] polarizing plate
The polarizing plate of the present invention comprises an optical compensation film having the transparent conductive layer on at least one surface, a polarizing plate, and a protective film in this order from the VA mode liquid crystal cell to the viewing side.
[ 6.1 ] polarizing plate
The polarizing plate is an element that passes only light having a polarization plane in a certain direction, and examples thereof include a polyvinyl alcohol-based polarizing film.
The polyvinyl alcohol-based polarizing film includes a film obtained by dyeing a polyvinyl alcohol-based film with iodine and a film obtained by dyeing a dichroic dye.
The polarizing plate may be obtained by uniaxially stretching a polyvinyl alcohol film and then dyeing it, or dyeing a polyvinyl alcohol film and then uniaxially stretching it, and preferably further subjecting it to a durability treatment with a boron compound.
The thickness of the polarizing plate is preferably within a range of 5 to 30 μm, and more preferably within a range of 5 to 15 μm.
As the polyvinyl alcohol film, ethylene-modified polyvinyl alcohol having an ethylene unit content of 1 to 4 mol%, a polymerization degree of 2000 to 4000 and a saponification degree of 99.0 to 99.99 mol% as described in, for example, Japanese patent application laid-open Nos. 2003-248123 and 2003-342322 is preferably used. Further, it is preferable to produce a polarizing plate by producing a polarizing plate by the method described in japanese patent laid-open publication nos. 2011-100161, 4691205, 4804589 and laminating the polarizing plate to the substrate film of the present invention.
[ 6.2 ] protective film
The film disposed on the side of the polarizing plate opposite to the side to which the optical compensation film is bonded is preferably a film that functions as a protective film of the polarizing plate.
As such a protective FILM, the above-mentioned optical compensation FILM can be used, and for example, commercially available cellulose ester FILMs (for example, Konica Minolta Tac KC8UX, KC5UX, KC4UX, KC8UCR3, KC4SR, KC4BR, KC4CR, KC4DR, KC4FR, KC4KR, KC8UY, KC6UY, KC4UY, KC4 UCR 9, KC8UE, KC8 UY-HA, KC2UA, KC4UA, KC6UAKC, 2UAH, KC4UAH, KC6UAH, kornia kokko corporation, fujit 40 Tac UZ, fujit T60UZ, fujit Tac 80, fujit 3680, futd 60, futd UL, futac UL, fujit UL, fijir UL, fijim UL, kojim).
Further, resin films such as polyethylene terephthalate, polyethylene naphthalate, and polycarbonate, and resin films such as polyarylate, polyethersulfone, polysulfone, fluorene ring-modified polycarbonate, alicyclic ring-modified polycarbonate, and acryl compound are exemplified. Among these resin substrates, films such as polyethylene terephthalate (abbreviated as PET), polybutylene terephthalate, polyethylene naphthalate (abbreviated as PEN), and polycarbonate (abbreviated as PC) are preferably used as the flexible resin substrate from the viewpoints of cost and easiness of obtaining.
The thickness of the protective film is not particularly limited, and may be about 10 to 200 μm, preferably within a range of 10 to 100 μm, and more preferably within a range of 10 to 70 μm.
Method for manufacturing [ 6.3 ] polarizing plate
Production of polarizing plate the optical compensation film and protective film according to the present invention are preferably bonded to a polarizing plate using a completely saponified polyvinyl alcohol aqueous solution (water paste) or the above adhesive. The optical compensation film according to the present invention is preferably provided on the liquid crystal cell side of the polarizing plate in the liquid crystal display device.
As a pretreatment step in the bonding, an easy adhesion treatment is preferably performed on the adhesion surface of the optical compensation film or the protective film to the polarizing plate, and examples of the easy adhesion treatment include saponification treatment, corona treatment, plasma treatment, and the like.
[ 7 ] other layers
The polarizing plate-integrated touch panel module according to the present invention may optionally include other layers as necessary. Examples of the other layer include a hard coat layer, an antistatic layer, an antiglare layer, an antireflection layer, and a color filter layer.
The hard coat layer may be formed to improve scratch resistance of the protective layer on the identification side, or may be formed on the surface of the optical compensation film as a protective layer when the transparent conductive layer is formed. The hard coat layer preferably contains an ultraviolet-curable urethane acrylate resin, an ultraviolet-curable polyester acrylate resin, an ultraviolet-curable epoxy acrylate resin, an ultraviolet-curable polyol acrylate resin, an ultraviolet-curable epoxy resin, or the like, and preferably contains an ultraviolet-curable acrylate resin.
The antistatic layer is formed by adding a material capable of making the square resistance value 1 × 1011Omega/□ or less, preferably 1X 1010Omega/□ or less, more preferably 1X 109Layers of material below Ω/□. Examples of the antistatic agent include metal oxides, surfactant-type antistatic agents, silicone-type antistatic agents, organoboron-type antistatic agents, polymer-type antistatic agents, antistatic polymer materials, and the like, and known conjugated polymers, ionic polymers, conductive polymers, and the like can be used.
[ 8 ] liquid crystal display device
The liquid crystal display device with a touch panel according to the present invention is characterized in that a VA mode (MVA, PVA) liquid crystal is used, and a liquid crystal display device with a touch panel having excellent front contrast, which is an advantage of the VA mode, can be provided. For the VA mode liquid crystal, a known liquid crystal can be used without limitation.
In a liquid crystal display device, 2 sheets of polarizing plates, i.e., a polarizing plate on the viewing side and a polarizing plate on the backlight side, are generally used by being bonded to a liquid crystal cell via an adhesive layer.
On the other hand, the polarizing plate on the backlight side is preferably a polarizing plate in which an optical compensation film, a polarizing plate, and a protective film are laminated in this order from the liquid crystal cell side, and as the optical compensation film, the optical compensation film of the present invention or another optical compensation film is preferably used. The other optical compensation film can be selected from the above-mentioned commercially available cellulose ester films and is preferably used. The protective film may be selected from the above-mentioned commercially available cellulose ester films, and is preferably used, and further, a polyester film, an acrylic film, a polycarbonate film, or the like may be used.
Examples
The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. In the examples, "part" or "%" is used, and "part by mass" or "% by mass" is used unless otherwise specified.
Example 1
The cellulose ester resin, the cycloolefin resin, the polyimide resin, the polyarylate resin, and the acrylic resin used in the examples were the resins listed below.
[ resin ]
Cycloolefin resin (COP): ARTON G7810, manufactured by JSR corporation
Cellulose Acetate Propionate (CAP): degree of substitution of acetyl group 1.5, degree of substitution of propionyl group 1.0, degree of substitution of total acyl group 2.5, weight average molecular weight 25 ten thousand)
Polyimide resin (PI): the polyimide-based resin was synthesized by the following method.
Polyimide resin a: polyimide having a structure represented by the formula (P1)
(polymerization of polyimide precursor)
Polyamic acid was produced using a reaction apparatus equipped with a separable flask made of stainless steel as a reaction vessel, 2 paddles as a stirring apparatus in the separable flask, and an apparatus having a cooling capacity of 20.9kJ/min as a cooling apparatus. In order to prevent the mixing of water during the polymerization reaction, the nitrogen dehydrated by silica gel was flowed at 0.05L/min to perform the polymerization reaction.
The separable flask was charged with 223.5g of N, N-Dimethylformamide (DMF) as a polymerization solvent, and 40.0g (0.125 mol) of Trifluoromethylbenzene (TFMB) was dissolved therein. To this solution, 55.5g (0.125 mol) of 1,1,1,3,3, 3-hexafluoro-2, 2-bis (3, 4-dicarboxyphenyl) propane dianhydride (6FDA) was added and stirred to be completely dissolved. After complete dissolution, the polymerization viscosity was increased to 80 pas by stirring. The viscosity of the polyamic acid solution was measured by keeping the polyamic acid solution at 23 ℃ for 1 hour, and measuring the viscosity at this time with a B-type viscometer at a spindle No.7 of 4 rpm. The concentrations of the aromatic diamine compound and the aromatic tetracarboxylic dianhydride added to the reaction solution were 30% by mass based on the total reaction solution.
(chemical imidization to polyimide resin)
DMF was added to the solution so that the solid content concentration became 15 mass%, and pyridine (pkBH +; 5.17)60g (molar ratio of imidization accelerator/amide group in polyamic acid: 3) was added as an imidization accelerator, and completely dispersed. To the dispersed solution was added 30.6g of acetic anhydride (molar ratio of the dehydrating agent to the amide group in the polyamic acid: 1.2) at a rate of 1g per minute, and the mixture was stirred for further 30 minutes. After stirring, the internal temperature was raised to 100 ℃ and 5 hours of superheated stirring was carried out.
(extraction of polyimide resin)
The solution of polyimide resin was put into a funnel having an aperture with a diameter of about 5mm, and dropped into 5L of methanol for extraction. In the extraction, methanol is extracted while being stirred at a high speed by a stirring blade rotating at 1500 revolutions or more. The polyimide resin in the solution dropped into the methanol solution in a fibrous form while adjusting the height between the funnel and the liquid surface of the methanol so that the diameter of the polyimide solution dropped is 1mm or less in the vicinity of the methanol interface may sometimes become fibrous, but by continuing the stirring, the polyimide resin once fibrous in the solution decomposes and breaks into fibers of 5mm or less in the solution.
The solid content was completely extracted by adding 5L of methanol to the cleaved resin solid content solution and taken out, and the solid content was washed with isopropanol by a Soxhlet extraction apparatus, then dried by heating at 100 ℃ by a vacuum drying apparatus, and taken out as a polyimide resin. The weight average molecular weight was 10 ten thousand.
Polyarylate-based resin (PA): the polyarylate resin was synthesized by the following method.
In a reaction vessel equipped with a stirrer, 100 parts by mass of 2, 2-bis (4-hydroxyphenyl) hexafluoropropane [ BisAF ] as a bisphenol component, 1.34 parts by mass of p-tert-butylphenol [ PTBP ] as a terminal-blocking agent, 25.4 parts by mass of sodium hydroxide [ NaOH ] as a base, 1.28 parts by mass of a 50 mass% aqueous solution of tri-n-butylbenzylammonium chloride [ TBBAC ] as a polymerization catalyst, and 0.5 part by mass of sodium dithionite as an antioxidant were dissolved in 1750 parts by mass of water (aqueous phase).
In addition, 89.1 parts by mass of diphenyl ether-4, 4' -diacyl chloride [ DEDC ] as an aromatic dicarboxylic acid component was dissolved in 1200 parts by mass of methylene chloride (organic phase).
The aqueous phase was stirred in advance, the organic phase was added to the aqueous phase with vigorous stirring, and interfacial polymerization was carried out at 15 ℃ for 2 hours. The molar ratio is set as BisAF: DEDC: PTBP: TBBAC: NaOH 98.5: 100.0: 3.0: 0.68: 210.
thereafter, the stirring was stopped, and the aqueous phase and the organic phase were separated by decantation. After removing the aqueous phase, 500 parts by mass of methylene chloride, 2000 parts by mass of pure water and 2 parts by mass of acetic acid were added to the organic phase to stop the reaction, and the mixture was stirred at 15 ℃ for 30 minutes. Thereafter, the organic phase was washed 10 times with pure water, and the organic phase was added to methanol to precipitate a polymer. The precipitated polymer was filtered and dried to obtain polyarylate resin having a weight average molecular weight of 11 ten thousand.
Cellulose Triacetate (TAC): degree of substitution of acetyl 2.85, weight average molecular weight 25 ten thousand)
Acrylic resin (Ac): DIANAL BR85 (manufactured by Mitsubishi Yangyang Co., Ltd., weight average molecular weight: 28 ten thousand)
[ additives ]
As additives, the following compounds were used for the phase difference increasing agent compounds a1 to a5, the polyester plasticizer B1, and the acrylic resin B2.
Polyester-based plasticizer B1: the polyester plasticizer was synthesized by the following procedure.
180g of ethylene glycol, 278g of phthalic anhydride, 91g of adipic acid, 610g of benzoic acid, and 0.191g of tetraisopropyl titanate as an esterification catalyst were charged in a 2L four-necked flask equipped with a thermometer, a stirrer, and a gradual cooling tube, and the temperature was gradually increased to 230 ℃ while stirring in a nitrogen stream. The polymerization degree was observed and the reaction was subjected to dehydration condensation. After the completion of the reaction, unreacted ethylene glycol was distilled off under reduced pressure at 200 ℃ to obtain polyester plasticizer B1. The acid value was 0.20 and the number average molecular weight was 450.
Acrylic resin B2: the acrylic resin was synthesized by the following procedure.
A polymerization reactor made of SUS and having an internal volume of 40 liters and equipped with a stirrer was charged with 24 liters of deionized water, and 30g of an aqueous solution of an anionic polymer compound as a dispersion stabilizer and 36g of sodium sulfate as a dispersion stabilizing aid were added and dissolved by stirring. In a separate vessel equipped with a stirrer, Methyl Methacrylate (MMA) and Acryloylmorpholine (ACMO) were charged so that MMA was 73.1 mass% and ACMO was 22.4 mass% (so that the total addition molar ratio was MMA/ACMO was 70/30), and 12g of 2, 2' -azobisisobutyronitrile as a polymerization initiator, 24g of n-octyl mercaptan as a chain transfer agent, and 24g of stearyl alcohol as a release agent were added to the monomer mixture and stirred to dissolve them. The monomer mixture obtained in this way and having the polymerization initiator, the chain transfer agent and the release agent dissolved therein was charged into the above SUS polymerization reactor having an internal volume of 40 liters (containing deionized water, the dispersion stabilizer and the dispersion stabilizing aid) equipped with a stirrer, and stirred at 175rpm for 15 minutes while being substituted with nitrogen. Thereafter, the mixture was heated to 80 ℃ to start the polymerization, and after the polymerization exothermic peak was completed, the mixture was heat-treated at 115 ℃ for 10 minutes to complete the polymerization. The obtained bead polymer was filtered, washed with water, and dried at 80 ℃ for 24hr to obtain Methyl Methacrylate (MMA) and Acryloylmorpholine (ACMO) acrylic resin B2 having a weight-average molecular weight of 6 ten thousand.
Example 1
< production of optical Compensation film 101 >
(preparation of Fine particle-containing additive solution)
4 parts by mass of fine particles (AEROSILR812, manufactured by AEROSIL Co., Ltd., primary average particle diameter: 7nm, apparent specific gravity 50g/L)
48 parts by mass of methylene chloride
48 parts by mass of ethanol
The above components were mixed with a dissolver under stirring for 50 minutes, and then dispersed with Manton Gaulin.
Further, the dispersion is carried out by an attritor so that the particle diameter of the secondary particles becomes a predetermined size. This was filtered through FINEMET NF manufactured by Nippon Seikagana to prepare a fine particle-added solution.
Next, a main cement 1 of the following composition was prepared. First, methylene chloride was added at a flow rate of 400kg/min and ethanol was added at a flow rate of 20kg/min in a pressurized dissolution tank. 3 minutes after the start of the solvent addition, a cycloolefin resin (COP) was charged into the pressure dissolution tank at a flow rate of 200kg/min while stirring. Next, 5 minutes after the start of the solvent addition, the microparticle-adding solution was added and completely dissolved while heating to 80 ℃ and stirring. The heating temperature is 5 ℃/min to raise from room temperature, after dissolving for 30 minutes, the temperature is lowered at 3 ℃/min.
The mucilage viscosity is 10000CP, and the water content is 0.50%. The resultant was filtered at a filtration flow rate of 300L/m using an Anji filter paper No.244 (filtration accuracy 0.005mm) manufactured by Anji Filter paper Co., Ltd2H, filtration pressure 1.0X 106Pa, and filtering to prepare a main mucilage 1.
Composition of main mucilage 1
Cycloolefin resin (COP): ARTON G7810, 100 parts by mass manufactured by JSR K.K
Dichloromethane 200 parts by mass
10 parts by mass of ethanol
3 parts by mass of particulate additive solution
Next, the above dope was uniformly cast onto a stainless steel tape support at a temperature of 33 ℃ with a width of 1500mm using an endless belt casting apparatus. The temperature of the stainless steel belt was controlled to 30 ℃.
On the stainless steel tape support, the solvent was evaporated to a residual solvent amount of 75% in the cast (cast) film, and then peeled from the stainless steel tape support at a peel tension of 130N/m.
The peeled cycloolefin resin film was stretched by 20% in the width direction by using a tenter while applying heat of 160 ℃. The residual solvent at the start of stretching was 15%. Next, the drying is completed while conveying the drying zone by a plurality of rollers. The drying temperature was 130 ℃ and the conveying tension was 100N/m. After drying, the film was cut into a width of 1.5m, knurled at both ends of the film to have a width of 10mm and a height of 10 μm, and wound into a roll to obtain an optical compensation film 101 having a dry film thickness of 45 μm.
< production of optical Compensation film 102 >
An optical compensation film 102 was produced in the same manner as in the production of the optical compensation film 101, except that the following main dope 2 was prepared and used, and the film thickness was 10 μm.
Composition of main mucilage 2
The stretch ratio was adjusted so that the optical compensation film had the phase difference values shown in table 1.
< production of base Material film A103-108 >
Optical compensation films 103 to 108 were produced in the same manner as in table 1 except that the type, amount and thickness of the additive were changed in the production of the optical compensation film 102.
< production of optical Compensation film 109 >
An optical compensation film 109 was produced in the same manner as in the production of the optical compensation film 101, except that the following main dope 3 was prepared and used.
Composition of main mucilage 3
< production of optical Compensation film 110 >
An optical compensation film 110 was produced in the same manner as in the production of the optical compensation film 109 except that 5 parts by mass of the additive a2 was added and the film thickness was changed by adjusting the stretching ratio so as to obtain the retardation value described in table 1.
< production of optical Compensation film 111 >
The optical compensation film 110 is produced in the same manner as in the production of the optical compensation film 101, except that the following main dope 4 is prepared and used.
Composition of main mucilage 4
< production of optical Compensation film 112 >
An optical compensation film 112 was produced in the same manner as in the production of the optical compensation film 111 except that 2 parts by mass of the additive a2 was added and the stretching ratio was adjusted so that the optical compensation film could have the retardation values described in table 1, thereby changing the film thickness.
< production of optical Compensation film 113 >
An optical compensation film 113 was produced in the same manner as in the production of the optical compensation film 101, except that the following main dope 5 was prepared and used.
Composition of main mucilage 5
< production of optical Compensation film 114 >
An optical compensation film 114 was produced in the same manner as in the production of the optical compensation film 113, except that 2 parts by mass of the additive a2 was added and the stretching ratio was adjusted so that the optical compensation film could have the retardation values described in table 1, thereby changing the film thickness.
< production of optical Compensation film 115 >
The optical compensation film 115 was produced in the same manner as in the production of the optical compensation film 102, except that the following main dope 6 was prepared and used, and the film thickness was set to 45 μm.
Composition of main mucilage 6
The stretch ratio was adjusted so as to be the phase difference value shown in table 1.
< production of optical Compensation film 116 >
An optical compensation film 116 was produced in the same manner as in the production of the optical compensation film 110, except that the following main dope 7 was prepared and used, and the film thickness was set to 45 μm.
Composition of main mucilage 7
< production of optical Compensation film 117 >
An optical compensation film 117 was produced in the same manner as in the production of the optical compensation film 101, except that the film was stretched 5% in each of the longitudinal direction and the width direction and the film thickness was set to 45 μm.
< production of optical Compensation film 118 >
An optical compensation film 118 was produced in the same manner as in the production of the optical compensation film 116, except that the following main dope 8 was prepared and used, and the film thickness was set to 45 μm by stretching 5% in each of the longitudinal direction and the width direction.
Composition of main mucilage 8
< production of optical Compensation film 119 >
An optical compensation film 118 was produced in the same manner as in the production of the optical compensation film 116, except that the following main dope 9 was prepared and used, and the film thickness was set to 45 μm.
Composition of main mucilage 9
Acrylic resin (Ac): 100 parts by mass of DIANAL BR85 (manufactured by Mitsubishi Yangyang Co., Ltd.)
Dichloromethane 200 parts by mass
10 parts by mass of ethanol
3 parts by mass of particulate additive solution
< production of transparent conductive layer >
The silver nanowires used were synthesized by dissolving silver sulfate in ethylene glycol in the presence of polyvinylpyrrolidone (PVP) and reducing the silver sulfate after the method using a polyol described in y.sun, b.gates, b.mayers, & y.xia, "crystallization silver nanowire by soft solution processing", Nanoletters, (2002), 2(2)165 to 168. That is, nanowires synthesized by the modified polyol method described in cambrios technologies Corporation U.S. provisional application No. 60/815627 are used in the present invention.
A silver nanowire aqueous dispersion composition (ClearOhmTM, Ink-AAQ manufactured by Cambrios Technologies Corporation) containing 0.5 wt%/v of silver nanowires having a short axis diameter of about 70 to 80nm and an aspect ratio of 100 or more as metal nanowires forming a transparent conductive layer in an aqueous medium is applied to one surface of optical compensation films 101 to 119 so that the thickness after drying is 1.5 μm by using a slit die coater, dried, and applied under a pressure of 2000kN/m2And performing pressurization treatment to form the transparent conductive layer.
Next, a transparent conductive layer was formed on the other surface of the optical compensation film in the same manner as described above, and then, heat treatment (annealing treatment) was performed at 150 ℃ for 30 minutes for lowering the resistance value.
< production of polarizing plate and polarizing plate-integrated touch panel module: refer to FIG. 2
A rolled polyvinyl alcohol film having a thickness of 80 μm was continuously stretched 5 times in an aqueous iodine solution, and dried to obtain a polarizing plate having a thickness of 20 μm.
Next, the polarizer thus produced was sandwiched between the side of the optical compensation films 101 to 119 thus produced on which the transparent conductive layer was provided and Konica Minolta TacKC4UA (manufactured by Konica Minolta corporation) as a protective film, and was bonded to the side of the optical compensation films 101 to 119 through the following ultraviolet curable adhesive solution, thereby producing polarizing plate integrated touch panel modules 101 to 119.
[ preparation of ultraviolet-curing adhesive liquid 1 ]
The following components were mixed and deaerated to prepare an ultraviolet-curable adhesive liquid 1. The triaryl sulfonium hexafluorophosphate salt was mixed as a 50% propylene carbonate solution, and the amount of solid components of the triaryl sulfonium hexafluorophosphate salt is shown below.
The polarizing plate was produced by applying a corona discharge treatment to the surfaces of the optical compensation film and the protective film at a corona output intensity of 2.0kW and a linear speed of 18 m/min, and applying the ultraviolet-curable adhesive liquid 1 prepared above to the corona discharge treated surface so that the cured film thickness was about 3 μm by a bar coater to form an ultraviolet-curable adhesive layer.
The polarizing plate was irradiated from the side of the protective film with ultraviolet rays having a conveyor belt (D bulb manufactured by Fusion UV Systems Co., Ltd.) to give an integrated light amount of 750mJ/cm2The ultraviolet-curable adhesive layer is cured by irradiating ultraviolet rays.
Production of touch panel-equipped liquid crystal display device having polarizing plate-integrated touch panel module: refer to FIG. 2
The polarizing plate-integrated touch panel module including the optical compensation films 101 to 116 manufactured as described above was bonded to a self-made VA mode liquid crystal cell with the optical compensation film side of the polarizing plate, and liquid crystal display devices 101 to 116 with a touch panel were manufactured.
The polarizing plate-integrated touch panel module including the optical compensation films 117 to 119 produced as described above was carefully peeled off from a commercially available IPS mode liquid crystal display device with a touch panel, and the optical compensation film side of the polarizing plate was bonded to the IPS mode liquid crystal cell to produce the liquid crystal display devices 117 to 119 with a touch panel.
A polarizing plate composed of an optical compensation film (Konica Minolta Tac KC8UCR 3)/a polarizer/protective film (Konica Minolta Tac KC4UA, both manufactured by Konica Minolta corporation) was bonded to the surface opposite to the liquid crystal cell via an adhesive layer so that the optical compensation film side was the liquid crystal cell side.
Evaluation
[ 1 ] phase difference value of optical compensation film
The in-plane retardation value Ro and the retardation value Rt in the thickness direction of the optical compensation film were measured in three dimensions using an automatic birefringence meter Axo Scan (Axo Scan Mueller Matrix Polarimeter, manufactured by AxoMetrix Co., Ltd.) at a wavelength of light of 590nm under an environment of 23 ℃ and 55% RH, and the obtained refractive index n was measured according to the following formulas (i) and (ii)x、ny、nzAnd (6) calculating.
Formula (i): ro ═ nx－ny)×d(nm)
Formula (ii): rt { (n)x+ny)/2－nz}×d(nm)
[ in formulae (i) and (ii), nxThe refractive index in the in-plane direction of the film in the direction x in which the refractive index is maximum is shown. n isyThe refractive index in the in-plane direction of the film in the direction y orthogonal to the direction x is shown. n iszWhich represents the refractive index in the thickness direction z of the film. d represents the thickness (nm) of the film. Angle (c)
[2 ] phase difference value variation of optical compensation film
The optical compensation film sample was left in an oven at 150 ℃ for 1 hour and heat-treated, and the fluctuation of the retardation value before and after the change was determined by the following equation.
Variation in retardation value Ro or Rt { (Ro value or Rt value after heat treatment-Ro value or Rt value before heat treatment)/(Ro value or Rt value before heat treatment) } × 100 (%)
[3 ] glass transition temperature of optical Compensation film
The glass transition temperature Tg is determined by measurement in accordance with JIS K-7121 using, for example, a differential scanning calorimeter DSC220 manufactured by Seiko Instruments. A DSC curve was prepared by fixing a10 mg sample of the optical compensation film, raising the temperature from room temperature to 250 ℃ at 20 ℃/min under a nitrogen flow rate of 50ml/min and holding the temperature for 10 minutes (1 st scan), then lowering the temperature to 30 ℃ at 20 ℃/min and holding the temperature for 10 minutes (2 nd scan), and further raising the temperature to 250 ℃ at 20 ℃/min (3 rd scan), and the glass transition temperature Tg was determined from the DSC curve of the 3 rd scan obtained.
[ 4] front contrast
The respective front contrast ratios of the manufactured liquid crystal display devices 101 to 119 with a touch panel were measured. The front contrast was measured by an EZ-contrast measuring device (product of ELDIM corporation) and the light quantity was measured for white display and black display to determine the ratio.
The composition of the optical compensation film and the evaluation results are shown in table 1.
As is clear from table 1, the VA mode liquid crystal display devices with a touch panel using the optical compensation films 101 to 114 according to the present invention have a superior front contrast ratio as compared with the IPS mode liquid crystal display devices 117 to 119.
In addition, the optical compensation films 115 and 116 having a glass transition temperature Tg of less than 155 ℃ have a low contrast ratio compared to the IPS mode liquid crystal display device because the retardation value varies greatly and the front contrast ratio is inferior.
Example 2
< manufacture of touch Panel Module >
The optical compensation films 104, 110, 112, and 114 according to the present invention prepared in example 1 were each formed with an ITO film as a transparent conductive layer by sputtering to a thickness of 20nm on one surface, and were etched to form the 1 st electrode pattern in the X direction.
Next, as an insulating layer disposed between the electrode patterns, SiO was deposited to a thickness of 200nm by sputtering2Film formation, on which an ITO film was formed by sputtering to a thickness of 20nm, and patterning in the Y direction by etchingIn the 2 nd electrode pattern. Further, SiO was deposited thereon to a thickness of 200nm by sputtering2The insulating layer is formed. Next, heat treatment (annealing treatment) was performed at 150 ℃ for 30 minutes to reduce the resistance value, and optical compensation films 201 to 204 each including a transparent conductive layer corresponding to each of the optical compensation films 104, 110, 112, and 114 were produced.
< production of polarizing plate and polarizing plate-integrated touch panel module: FIG. 6
The polarizers produced in example 1 were sandwiched between the side of the optical compensation films 201 to 204 on which the transparent conductive layer was provided and Konica Minolta KC4UA (manufactured by Konica Minolta corporation) as a protective film, and were bonded to each other through the ultraviolet-curable adhesive liquid 1 of example 1, thereby producing polarizing plate integrated touch panel modules 201 to 204.
Production of touch panel-equipped liquid crystal display device having polarizing plate-integrated touch panel module: FIG. 6
The polarizing plate-integrated touch panel modules 201 to 204 including the optical compensation films 201 to 204 thus produced were bonded to a self-made VA mode liquid crystal cell on the side of the optical compensation film on which the transparent conductive layer was not formed, to produce touch panel-equipped liquid crystal display devices 201 to 204.
A polarizing plate composed of an optical compensation film (Konica Minolta Tac KC8UCR 3)/a polarizer/protective film (Konica Minolta Tac KC4UA, both manufactured by Konica Minolta corporation) was bonded to the surface opposite to the liquid crystal cell via an adhesive layer so that the optical compensation film side became the liquid crystal cell side.
As a result of measuring the front contrast of the touch panel-equipped liquid crystal display devices 201 to 204 provided with the polarizing plate integrated touch panel module manufactured in the same manner as in example 1, it was found that the contrast ratios were all 7500: a VA mode liquid crystal display device with a touch panel having an excellent contrast can be obtained by reproducing example 1.
Industrial applicability
The touch panel-equipped liquid crystal display device of the present invention includes the optical compensation film having the transparent conductive layer on at least one surface thereof according to the present invention, the polarizing plate, and the protective film in this order, and thus can provide a touch panel-equipped liquid crystal display device having a VA mode liquid crystal cell that is thin and excellent in front contrast.
Description of the symbols
1 liquid crystal cell
2 polarizing plate
T1 protective film
T2 optical compensation film
P1 polarizing plate (identification side)
3 adhesive layer
4 conductive layer substrate film
5 transparent conductive layer
6 protective layer
7 front panel
T touch panel module
T3 optical compensation film
T4 protective film
P2 polarizing plate (backlight side)
10 comparative example liquid crystal display device with touch panel
20 liquid crystal display device with touch panel of the invention
Claims (4)
1. A liquid crystal display device with a touch panel, comprising a touch panel module integrated with a polarizing plate having a transparent conductive layer on the identification side of a VA mode liquid crystal cell,
the touch panel module integrated with a polarizing plate having the transparent conductive layer comprises an optical compensation film having a transparent conductive layer on at least one surface, a polarizer, and a protective film in this order from the VA mode liquid crystal cell to the viewing side, and
the glass transition temperature Tg of the optical compensation film is within the range of 155-250 ℃;
the optical compensation film contains any one of a cycloolefin resin, a polyimide resin, and a polyarylate resin;
the optical compensation film has a variation of a retardation value Ro in an in-plane direction within a range of + -3.0% and a variation of a retardation value Rt in a thickness direction within a range of + -4.0% when heat-treated at 150 ℃ for 1 hour.
2. The liquid crystal display device with a touch panel according to claim 1, wherein the optical compensation film has a thickness in a range of 10 to 40 μm.
3. The touch-panel-equipped liquid crystal display device according to claim 1 or 2, wherein the optical compensation film contains a nitrogen-containing heterocyclic compound having a structure represented by the following general formula (3) as a phase difference increasing agent,
general formula (3)
Wherein A represents a pyrazole ring, Ar1And Ar2Each represents an aromatic hydrocarbon ring or an aromatic heterocyclic ring, which may have a substituent, R1Represents a hydrogen atom, an alkyl group, an acyl group, a sulfonyl group, an alkoxycarbonyl group or an aryloxycarbonyl group, q represents 1 or 2, and n and m each represent an integer of 1 to 3.
4. A method for manufacturing a liquid crystal display device with a touch panel according to any one of claims 1 to 3, comprising:
forming the transparent conductive layer on at least one surface of the optical compensation film, and then performing heat treatment at 150 ℃ or higher;
a step of manufacturing a polarizing plate-integrated touch panel module by bonding the optical compensation film having the transparent conductive layer formed thereon and the protective film with a polarizer interposed therebetween; and
and a step of bonding the optical compensation film side of the polarizing plate-integrated touch panel module to the VA-mode liquid crystal cell.
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| CN108735349B (en) * | 2018-04-27 | 2020-03-31 | 东南大学 | Silver nanowire transparent conductive film containing ionic liquid and preparation method thereof |
| KR101973155B1 (en) * | 2018-12-10 | 2019-04-26 | (주)딥스원에듀 | Dot film, multi-layers optic sheet and smart electric board |
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Also Published As
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| KR102011587B1 (en) | 2019-08-16 |
| WO2016181756A1 (en) | 2016-11-17 |
| JP6627869B2 (en) | 2020-01-08 |
| CN107533253A (en) | 2018-01-02 |
| KR20170125098A (en) | 2017-11-13 |
| JPWO2016181756A1 (en) | 2018-03-01 |
| KR102057017B1 (en) | 2019-12-17 |
| KR20190096444A (en) | 2019-08-19 |
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