WO2013111672A1

WO2013111672A1 - Touch-panel-equipped liquid crystal display device

Info

Publication number: WO2013111672A1
Application number: PCT/JP2013/050880
Authority: WO
Inventors: 啓史別宮; 梅田　博紀
Original assignee: コニカミノルタアドバンストレイヤー株式会社
Priority date: 2012-01-26
Filing date: 2013-01-18
Publication date: 2013-08-01
Also published as: CN104220965A; TWI491908B; JPWO2013111672A1; TW201346315A; JP5831559B2; CN104220965B

Abstract

The objective of the present invention is to provide: a touch-panel-equipped liquid crystal display device that has a shatterproof function with respect to glass substrate breakage and in which the occurrence of cracks in ITO electrodes is prevented; and a touch-panel-equipped liquid crystal display device that has excellent viewability even when the display is observed through polarizing sunglasses. This touch-panel-equipped liquid crystal display device is a touch-panel-equipped liquid crystal display device comprising a touch panel module and a liquid crystal display panel, and being characterized in that: the touch panel module includes a glass substrate on the outermost surface, a pair of transparent electroconductive films formed in a grid pattern in an X direction and a Y direction orthogonal thereto, and a glass shatterproofing film provided on the upper surface of the transparent electroconductive films; and the direction of the maximum elasticity modulus of the glass shatterproofing film is in a direction oblique to the X direction or the Y direction of said pair of transparent electroconductive films formed in a grid pattern.

Description

LCD with touch panel

The present invention relates to a liquid crystal display device with a touch panel used for a mobile phone or a tablet. More specifically, the present invention relates to a liquid crystal display device with a touch panel that prevents scattering of glass substrates from cracking and prevents generation of ITO electrode cracks.

2. Description of the Related Art In recent years, as various electronic devices such as mobile phones, portable terminals, and personal computers have become highly functional and diversified, touch panels have been actively used as one of input means to these electronic devices. . There are various types of touch panels, and there is a capacitive touch panel module as a touch panel that is light transmissive and can be attached to the front surface of a liquid crystal display panel of an electronic device via an adhesive layer.

Conventionally, a plastic plate with high light transmittance has been used on the surface of the information display section of the portable terminal device from the viewpoint of making the displayed information easy to see and preventing damage even if dropped. However, mobile terminal devices are required to be thinner and lighter, and there is a problem that the strength is insufficient when the plastic plate is made thinner. In order to solve this problem, a tempered glass substrate has recently been used on the surface of the information display unit.

However, when only the tempered glass substrate is used, there is a problem that the glass substrate is broken when the portable terminal device is dropped and the glass substrate is scattered. Therefore, a glass scattering prevention film that is bonded to the surface of a tempered glass substrate to prevent scattering is used. In general, polyethylene terephthalate (PET) film that is inexpensive and has an anti-scattering effect is used as a glass anti-scattering film, but since PET film generally has low adhesion to the adhesive layer, in order to improve adhesion, A PET film with an easy adhesion layer provided with a thin film called an easy adhesion layer is used.

In addition, the PET film may generate interference fringes due to the refractive index, and in order to improve this, a triacetyl cellulose film with an adhesive layer is bonded to the outermost surface of the glass substrate as a protective film, and the glass It has been studied to prevent scattering of the substrate (for example, see Patent Document 1).

On the other hand, in the capacitive touch panel module, an X electrode pattern extending in the X direction by a transparent conductive film and a Y electrode pattern extending in the Y direction by another transparent conductive film are formed on a transparent glass substrate. is there. The X electrode pattern and the Y electrode pattern come into contact with each other by touching with a finger on the surface of the touch panel, and a change in electrostatic capacitance at the position is detected by the X electrode pattern and the Y electrode pattern. The transparent conductive film generally uses ITO (tin-doped indium oxide) as an electrode.

The capacitive touch panel module having such a pair of transparent conductive films and having a touch surface made of a glass surface protects the electrode pattern because the ITO electrode pattern is vulnerable to impact. In addition, another glass substrate is laminated.

However, further weight reduction and securing of battery capacity space are required, and the capacitive touch panel module disclosed in Patent Document 2 includes a pair of transparent conductive films in directions orthogonal to each other and a glass substrate. Although it is a touch surface, only one glass substrate is used. Therefore, although there is an advantage that the whole is thin, there is a problem that only one glass substrate is used, and cracks are generated in the ITO electrode pattern due to the force applied during the manufacturing process.

JP 2011-209512 A JP 2011-186717 A

The present invention has been made in view of the above-mentioned problems and situations, and its solution is to provide a liquid crystal display device with a touch panel that has a glass scattering prevention function against cracks in the glass substrate and further prevents cracks in the ITO electrodes. Is to provide.

In order to solve the above problems, the present inventor, in the process of studying the cause of the above problems, the touch panel module is a pair of transparent conductive films formed in a lattice pattern on the outermost glass substrate and glass scattering on the upper surface. In addition to preventing glass scattering, the generation of cracks in the ITO electrode was prevented by having a prevention film, and the direction of the maximum elastic modulus of the glass scattering prevention film being oblique to the direction of formation of the transparent conductive film The inventors have found that a liquid crystal display device with a touch panel can be obtained, and have reached the present invention.

That is, the above-mentioned problem according to the present invention is solved by the following means.

1. A liquid crystal display device with a touch panel having a touch panel module and a liquid crystal display panel, wherein the touch panel module is an outermost glass substrate and a pair of transparent conductive films formed in a lattice shape in the X direction and the Y direction perpendicular thereto And a glass scattering prevention film on the upper surface thereof, and the direction of the maximum elastic modulus of the glass scattering prevention film is oblique to the X direction or the Y direction of the pair of transparent conductive films formed in the lattice shape A liquid crystal display device with a touch panel.

2. When the direction of the maximum elastic modulus of the glass scattering prevention film is 0 ° with respect to one of the X direction and the Y direction of the pair of transparent conductive films formed in the lattice shape, 2. The liquid crystal display device with a touch panel as set forth in claim 1, wherein the liquid crystal display device is in an oblique direction at an angle in a range of 70 ° or in a range of 110 to 160 °.

3. The liquid crystal display device with a touch panel according to claim 1 or 2, wherein the glass scattering prevention film has a hard coat layer containing an acrylic resin.

4. The in-plane retardation value Ro of the glass scattering prevention film is within a range of 0 to 100 nm in a measurement at a light wavelength of 590 nm under an environment of a temperature of 23 ° C. and a relative humidity of 55% RH. The liquid crystal display device with a touch panel as described in any one of Claim 3 to 3.

5. The in-plane retardation value Ro of the glass scattering prevention film is in the range of 105 to 160 nm when measured at a light wavelength of 590 nm in an environment of a temperature of 23 ° C. and a relative humidity of 55% RH. The phase axis is an oblique direction at an angle in the range of 20 to 70 ° or in the range of 110 to 160 ° with respect to the absorption axis of the polarizing plate of the liquid crystal display panel. A liquid crystal display device with a touch panel according to any one of items 1 to 3.

6. The liquid crystal display device with a touch panel according to any one of claims 1 to 5, wherein the glass scattering prevention film is a cellulose ester film.

7. The liquid crystal display device with a touch panel according to item 6, wherein the cellulose ester film contains cellulose diacetate having an acetyl group substitution degree in the range of 2.0 to 2.5.

By the above means of the present invention, it is possible to provide a liquid crystal display device with a touch panel that has a glass scattering prevention function against the crack of the glass substrate and further prevents the ITO electrode from cracking.

The expression mechanism or action mechanism of the effect of the present invention is not clear, but is presumed as follows.

A feature of the liquid crystal display device with a touch panel according to the present invention is a liquid crystal display device with a touch panel having a touch panel module and a liquid crystal display panel, and the touch panel module is placed on the outermost glass substrate in the X direction and Y orthogonal thereto. It has a pair of transparent conductive films formed in a lattice shape in the direction and a glass scattering prevention film on the upper surface thereof, and the direction of the maximum elastic modulus of the glass scattering prevention film is the X direction or Y direction in which the transparent conductive film is formed. By being oblique with respect to the direction, the various forces received by the ITO electrode during the manufacturing process can be dispersed and relaxed as if they were oblique, so that various glass substrates and transparent conductive films can be used. It is presumed that the generation of cracks in the ITO electrode can be effectively prevented by protecting from excessive force.

Schematic diagram of a liquid crystal display device with a touch panel of the present invention The schematic diagram which showed the relationship between the formation direction of the lattice-shaped transparent conductive film which concerns on this invention, and the direction of the maximum elasticity modulus of a glass scattering prevention film.

The liquid crystal display device with a touch panel according to the present invention is a liquid crystal display device with a touch panel having a touch panel module and a liquid crystal display panel, and the touch panel module is latticed in the outermost glass substrate and in the X direction and the Y direction perpendicular thereto. A pair of transparent conductive films formed in a shape and a glass scattering prevention film on the upper surface thereof, and the direction of the maximum elastic modulus of the glass scattering prevention film is the X direction or Y direction in which the transparent conductive film is formed. It is characterized by being oblique to the direction.

This feature is a technical feature common to the inventions according to claims 1 to 7.

As an embodiment of the present invention, when the maximum elastic modulus direction of the glass scattering prevention film is set to 0 ° in the X direction or the Y direction of the pair of transparent conductive films formed in the lattice shape, From the viewpoint of effectively preventing the generation of cracks in the ITO electrode, an oblique direction with an angle in the range of 20 to 70 ° or 110 to 160 ° with respect to the forming direction is preferable.

Further, from the viewpoint of both prevention of glass scattering and prevention of ITO cracking, the glass scattering prevention film having a hard coat layer containing an acrylic resin increases the strength of the film itself and further improves the effect of the present invention. can do.

In addition, when the in-plane retardation value Ro of the glass scattering prevention film was in the range of 0 to 100 nm when measured at a light wavelength of 590 nm under an environment of a temperature of 23 ° C. and a relative humidity of 55% RH, the display was observed with the naked eye. This is preferable because the visibility at the time is improved.

Further, the in-plane retardation value Ro of the glass scattering prevention film is in the range of 105 to 160 nm when measured at a light wavelength of 590 nm in an environment of a temperature of 23 ° C. and a relative humidity of 55% RH. When the phase axis is arranged in an oblique direction at an angle in the range of 20 to 70 °, or in the range of 110 to 160 ° with respect to the absorption axis of the polarizing plate of the liquid crystal display panel, display is performed with polarized sunglasses. The visibility when looking at can be greatly improved. This is a combination with a polarizing plate mounted on a liquid crystal display panel by giving a retardation value in the above range to the glass scattering prevention film according to the present invention and arranging it in an oblique direction with respect to the absorption axis of the polarizing plate. It becomes a circularly polarizing plate, and the visibility when wearing polarized sunglasses is improved.

Furthermore, the glass scattering prevention film of the touch panel module is preferably a cellulose ester film, and among them, the cellulose acetate having a degree of acetyl group substitution in the range of 2.0 to 2.5 imparts the retardation. This is also preferable from the viewpoint of improving visibility.

Hereinafter, the present invention, its components, and modes and modes for carrying out the present invention will be described in detail. In the present application, “˜” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.

<Liquid crystal display with touch panel>
An example of the configuration of a liquid crystal display device with a touch panel having the glass scattering prevention film of the present invention will be described with reference to FIGS.

FIG. 1 is a schematic diagram of a liquid crystal display device with a touch panel according to the present invention.

The touch panel module according to the present invention includes a glass substrate 1 from the surface side, a first electrode pattern 2 on one surface of the glass substrate, and a transparent formed on the surface so as to cover the first electrode pattern 2 An insulating film 3, a second electrode pattern 4 formed on the insulating film, arranged in the Y direction perpendicular to the X direction, which is the direction in which the first electrode pattern 2 extends, and the second electrode pattern 4 It has a pair of lattice-like transparent conductive films composed of a protective film 3 made of a transparent insulating film formed on the surface so as to cover. The surface of the glass substrate is a touch surface.

FIG. 2 is a schematic diagram showing the relationship between the formation direction of the lattice-like transparent conductive film according to the present invention and the direction of the maximum elastic modulus of the glass scattering prevention film.

The glass scattering prevention film 6 according to the present invention is bonded to the transparent conductive film to constitute a touch panel module T.

The direction 12 of the maximum elastic modulus of the glass scattering prevention film 6 according to the present invention is oblique with respect to one formation direction (11 or 12) in the X direction or the Y direction of the pair of transparent conductive films formed in the lattice shape. It is the feature that it is a direction. In the present invention, the “oblique direction” refers to a state where the transparent conductive film does not have an angle in the same direction with respect to one formation direction (11 or 12). By bonding in an oblique direction in this way, the force applied to the ITO electrode can be relaxed and the occurrence of cracks can be prevented together with the glass scattering prevention effect.

Further, the direction 12 of the maximum elastic modulus of the glass scattering prevention film 6 is set to 0 ° in one of the X-direction or Y-direction (11 or 12) of the pair of transparent conductive films formed in the lattice shape. Sometimes, it is preferable that the touch panel module T is constituted by being bonded to the transparent conductive film obliquely at an angle within a range of 20 to 70 ° or 110 to 160 ° with respect to the forming direction.

Bonding in an oblique direction at an angle within the above range is preferable because the glass scattering prevention effect and the ITO electrode cracking prevention effect are significantly improved. Further, the angle is preferably in the range of 35 to 60 °, or in the range of 125 to 150 °, from the viewpoint of enhancing the effect of crossing, particularly preferably 40 to 50 °. An angle within a range or within a range of 130-140 °.

Further, the touch panel module T is bonded to the liquid crystal display panel 9 through the adhesive layer 8. When a hard coat layer is provided on the glass scattering prevention film 6, the glass scattering prevention film having the hard coat layer 7 is obtained.

That is, the basic structure of the liquid crystal display device with a touch panel of the present invention is such that a glass substrate, a transparent conductive film, a glass scattering prevention film, an adhesive layer, and a liquid crystal display panel are bonded from the surface side. Yes.

Since the first purpose of using the glass scattering prevention film is to prevent scattering when the glass substrate is cracked, the thickness of the glass scattering prevention film according to the present invention is 10 to 10 in terms of prevention of scattering, weight reduction, and thinning. It is preferably within the range of 60 μm. More preferably, it is in the range of 20 to 50 μm.

First, each element other than the glass scattering prevention film according to the present invention will be described.

(Glass substrate)
Although the glass substrate which concerns on this invention consists of a sheet | seat of a tempered glass, if it is a glass substrate for flat panels, it will not specifically limit, Optical synthetic quartz glass, tempered glass, etc. are used. Conventionally, sheet resin sheets such as polyethylene terephthalate (PET) resin, polycarbonate resin (PC) and other engineering plastic resins, or cyclic olefin-based resins such as norbornene have been used from the viewpoint of weight reduction. There is a problem in terms of high quality and strength, and a sheet of tempered glass is used as it is exposed.

However, when only the tempered glass substrate is used, there is a problem that the glass substrate is broken when the portable terminal device is dropped and the glass substrate is scattered. Therefore, it has been studied to prevent the glass substrate from scattering by bonding a glass scattering prevention film film with an adhesive layer to the surface of the tempered glass substrate. For example, there is a technique for bonding a polyethylene terephthalate (PET) film that is inexpensive and has an anti-scattering effect or a triacetyl cellulose film as disclosed in Patent Document 1 to the surface. Since it is a glass scattering prevention film, it is not intended to prevent the ITO electrode from cracking with the glass scattering prevention effect which is the effect of the present invention.

(Transparent conductive film)
The transparent conductive film main body is of an electrostatic capacity type, and includes a first electrode pattern and a second electrode pattern formed on the substrate surface, and a transparent insulating film disposed between these electrode patterns. The transparent insulating film is not particularly limited, and for example, SiO ₂ is used.

The first electrode pattern and the second electrode pattern are made of a transparent conductive material such as ITO (indium-tin oxide) or IZO (indium-zinc oxide), or a thin metal wire. In particular, ITO is used from the viewpoint of conductivity and transparency.

For example, the first electrode pattern is formed by arranging conductive patterns extending in the horizontal direction (X direction), and the second electrode pattern layer is formed by arranging electrode patterns extending in the vertical direction (Y direction), for example. Form. The conductive film can be provided by a method in which the substrate is masked in an electrode pattern shape and formed by an alkali etching process, or by performing predetermined laser irradiation on the substrate and continuously patterning the conductive film.

A take-out electrode (not shown) is arranged at the ends of the first electrode pattern and the second electrode pattern. When the user presses the glass substrate surface guide with a finger or a pen, the second electrode pattern comes into contact with the first electrode pattern on the glass substrate. The pressed position is detected by electrically detecting this contact through an extraction electrode at the end. On the 1st electrode pattern of a glass substrate, a dot-shaped spacer may be arrange | positioned as needed.

(LCD panel)
As the liquid crystal display panel, a reflection type, a transmission type, a transflective type liquid crystal display device, or a liquid crystal display device of various driving methods such as a TN type, STN type, OCB type, VA type, IPS type, ECB type, etc. is preferably used. .

A polarizing plate (not shown) is bonded to the surface of the liquid crystal cell on the surface of the liquid crystal display panel.

The polarizing plate is composed of a polarizing film and a polarizing plate protective film that protects it. The main component, a polarizing film, is an element that allows only light in a plane of polarization in a certain direction to pass. A typical polarizing film currently known is a polyvinyl alcohol-based polarizing film, which is a polyvinyl alcohol-based film. There are dyed iodine and dyed dichroic dye, but it is not limited to this.

For example, the polarizing film is formed by forming a polyvinyl alcohol aqueous solution and uniaxially stretching it and dyeing or dyeing and then uniaxially stretching, and then preferably performing a durability treatment with a boron compound. . A polarizing film with a thickness of 5 to 30 μm, preferably 8 to 15 μm, is preferably used.

The protective film is not particularly limited as long as it is a resin film, but a cellulose triacetate film is generally used from the viewpoint of productivity such as optical properties and bonding properties by saponification treatment. Commercially available polarizing plate protective films preferably used include KC8UX2MW, KC4UX, KC5UX, KC4UY, KC8UY, KC12UR, KC4UEW, KC8UCR-3, KC8UCR-4, KC8UCR-5, KC4FR-1, KC4FRK, Konica Minolta Advanced Layer Co., Ltd.).

The glass scattering prevention film according to the present invention is a λ / 4 plate whose in-plane retardation value Ro is in the range of 105 to 160 nm in the measurement at a light wavelength of 590 nm under the environment of a temperature of 23 ° C. and a relative humidity of 55% RH. The angle of the slow axis in the plane of the glass scattering prevention film is preferably in the range of 20 to 70 ° or in the range of 110 to 160 ° with respect to the direction of the absorption axis of the polarizing plate. In this case, the polarizing plate functions as a circularly polarizing plate. Thus, the visibility at the time of observing a display wearing polarized sunglasses is remarkably improved by adjusting the way of bonding of the glass scattering prevention film according to the present invention and the polarizing plate.

(Adhesive layer)
The pressure-sensitive adhesive used for the pressure-sensitive adhesive layer 5 and the pressure-sensitive adhesive layer 8 contains a thermosetting resin or an ultraviolet (UV) curable resin, and exhibits moderate viscoelasticity and pressure-sensitive adhesive properties as well as being optically transparent. Is preferred.

Specific adhesives include adhesives or adhesives such as acrylic copolymers, epoxy resins, polyurethanes, silicone polymers, polyethers, butyral resins, polyamide resins, polyvinyl alcohol resins, synthetic rubbers, etc. Can be mentioned. In the present invention, it is preferable that the adhesive is a film formed and cured by a thermosetting method, a photocuring method, or the like, and among them, an acrylic copolymer and an epoxy resin are most easily controlled in adhesive property and are transparent. It is excellent in properties, weather resistance, durability and the like, and can be preferably used.

The thickness of the pressure-sensitive adhesive layer is preferably in the range of 1 to 100 μm, more preferably in the range of 5 to 50 μm, and particularly preferably in the range of 5 to 30 μm. When coating, the adhesive generally has a viscosity at 25 ° C. in the range of 1000 to 6000 mPa · sec, preferably in the range of 2000 to 4000 mPa · sec, for example in the range of 3000 to 4000 mPa · sec. Here, the viscosity is, for example, a value read by using a B-type viscometer BH II manufactured by Tokimec (Tokyo Keiki) and rotating the rotor for 30 seconds after standing. The Young's modulus (E) of the adhesive resin after being completely cured is preferably in the range of 1 to 100 MPa, for example, in the range of 5 to 20 MPa.

As the storage elastic modulus of the pressure-sensitive adhesive, the storage elastic modulus at 25 ° C. is preferably in the range of 1.0 × 10 ⁴ to 1.0 × 10 ⁸ Pa, and 1.5 × 10 ⁵ to 1.0 × 10. More preferably, it is in the range of ⁷ Pa. When the storage elastic modulus of the adhesive is 1.0 × 10 ⁴ Pa or more, sufficient cutting processability and high pencil hardness are obtained, and when it is 1.0 × 10 ⁸ Pa or less, sufficient adhesive strength is obtained. The storage elastic modulus of the adhesive layer was measured by forming an adhesive layer molding composition on a polyethylene terephthalate film support, then peeling it off, and using this adhesive layer, a dynamic viscoelasticity measuring device (manufactured by Rheometric Co., Ltd.). The storage elastic modulus at 0 ° C. is measured in the temperature rising mode (temperature rising rate 5 ° C./min, frequency 10 Hz) by “ARES”).

Acrylic adhesives include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, n-hexyl (meth) acrylate, (meth)

acrylic

1 or 2 or more kinds of alkyl esters of 1 to 20 carbon atoms, such as 2-ethylbutyl acid, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, and the alkyl acrylate Copolymerization with functional monomers such as (meth) acrylic acid, itaconic acid, maleic acid, maleic anhydride, 2-hydroxyethyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate that can be copolymerized with esters In combination, isocyanate crosslinker, epoxy crosslinker, aziridine crosslinker, metal chelate crosslinker It includes a crosslinking agent that is reacted.

Examples of the epoxy resin adhesive include a resin composition obtained by modifying an ultraviolet light curable epoxy resin with a silicone elastomer and adding precipitated silica as an inorganic filler. For example, “NORLANDD optical adhesion” by Edmund Optics is available. Agent NOA68 "or" Super Elastic Resin "manufactured by Sony Chemical & Information Device Corporation can be used.

In order to accelerate photocuring of the pressure-sensitive adhesive, it is preferable to further contain a photopolymerization initiator. The blending amount of the photopolymerization initiator is preferably contained in a mass ratio in the range of photopolymerization initiator: adhesive = 20: 100 to 0.01: 100.

Specific examples of the photopolymerization initiator include alkylphenone series, acetophenone, benzophenone, hydroxybenzophenone, Michler ketone, α-amyloxime ester, thioxanthone, and derivatives thereof, but are not particularly limited thereto. It is not a thing. Commercially available products may be used, and preferred examples include Irgacure 184, Irgacure 907, and Irgacure 651 manufactured by BASF Japan.

As a method for providing the adhesive layer, it is preferable to provide the above-mentioned adhesive-containing composition by coating, for example, bar coating method, knife coating method, roll coating method, blade coating method, die coating method, gravure coating method, curtain coating method. Conventionally known methods such as

In the case of thermosetting, it is preferable to apply heating at 80 ° C. or higher in a dryer, and the heating time is appropriately set.

As a light source for UV curing treatment, any light source that generates ultraviolet rays can be used without limitation. 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.

Irradiation conditions vary depending on each lamp, but the irradiation amount of active rays is usually in the range of 50 to 1000 mJ / cm ² , preferably in the range of 50 to 300 mJ / cm ² . The heat treatment temperature after UV curing is preferably 80 ° C. or higher.

The glass scattering prevention film according to the present invention preferably has a refractive index in the range of 1.45 to 1.55 at a light wavelength of 589 nm measured according to JIS K7142-2008.

Also, the refractive index of the adhesive layer is preferably in the range of 1.40 to 1.55, more preferably in the range of 1.45 to 1.52. By making the refractive index of a glass scattering prevention film and an adhesion layer into the said range, the refractive index at the time of bonding to a glass substrate etc. is small, and it is excellent in an interference fringe.

The refractive index of the adhesive layer can be adjusted by, for example, a method of increasing the refractive index by containing an aromatic ring or a method of decreasing the refractive index by containing a fluorine atom.

In the present invention, it is preferable that a release sheet is laminated on the surface until the adhesive layer is provided on the glass scattering prevention film of the touch panel module and then bonded to the liquid crystal display panel.

Although various release sheets can be used as the release sheet, it is typically composed of a base sheet having peelability on the surface. Examples of the base sheet include films such as polyester resin, polyethylene resin, polypropylene resin, polystyrene resin, and polycarbonate resin, films in which fillers such as fillers are blended with these films, and synthetic paper. Moreover, paper base materials, such as glassine paper, clay coat paper, and quality paper, are mentioned.

In order to give the surface of the substrate sheet peelability, a release agent such as a thermosetting silicone resin or an ultraviolet curable silicone resin is attached to the surface by coating or the like. The coating amount of the release agent is preferably in the range of 0.03 to 3.0 g / m ² . The release sheet is laminated with the surface having the release agent in contact with the adhesive layer.

<Elastic modulus of glass scattering prevention film>
The elastic modulus of the glass scattering prevention film was measured by conditioning the sample for 24 hours in an environment of a temperature of 23 ° C. and a relative humidity of 55% RH, and following the method described in JIS K7127 The elastic modulus is obtained using Tensilon RTA-100. The shape of the test piece is No. 1 test piece, the test speed is 10 mm / min, and the maximum elastic modulus is the maximum elastic modulus obtained by measuring from 0 ° to 15 ° in any direction. And that direction is the direction of the maximum elastic modulus.

The maximum elastic modulus of the glass scattering prevention film used in the liquid crystal display device with a touch panel of the present invention is preferably 2000 MPa or more, preferably in the range of 3000 to 8000 MPa, and more preferably in the range of 3500 to 7000 MPa.

If the maximum elastic modulus is 2000 MPa or more, either or both of the glass scattering prevention effect and the ITO electrode cracking prevention effect are sufficient. If it is in the range of 2000 to 8000 MPa, the glass scattering prevention effect and the ITO electrode cracking prevention effect can be achieved sufficiently.

In order to give the maximum elastic modulus in the above preferred range to the glass scattering prevention film, it can be achieved by uniformly orienting the molecules of the resin used in one direction. Although it does not restrict | limit in particular in order to orientate the molecule | numerator of resin to be used uniformly in one direction, It is preferable to perform a extending | stretching process in the width direction, longitudinal direction, or diagonal direction of a film when manufacturing a resin film. . The direction of the maximum elastic modulus coincides with the direction of the stretching treatment.

<Glass scattering prevention film>
As the scattering prevention film according to the present invention, it is preferable to use a thermoplastic resin from the viewpoints of transparency and moldability. Detailed description will be given below.

(Thermoplastic resin)
In the present invention, the “thermoplastic resin” refers to a resin that becomes soft when heated to the glass transition temperature or the melting point and can be molded into a desired shape.

General thermoplastic resins include cellulose ester resin, polyethylene (PE resin), high density polyethylene resin, medium density polyethylene resin, low density polyethylene resin, polypropylene (PP) resin, polyvinyl chloride (PVC). Resin, polyvinylidene chloride resin, polystyrene (PS) resin, polyvinyl acetate (PVAc) resin, Teflon (registered trademark) (polytetrafluoroethylene, PTFE), ABS resin (acrylonitrile butadiene styrene resin), AS resin, acrylic resin ( PMMA) or the like can be used.

When strength and resistance to breakage are particularly required, polyamide (PA) resin, nylon, polyacetal (POM) resin, polycarbonate (PC) resin, modified polyphenylene ether (m-PPE, modified PPE, PPO) resin, poly Butylene terephthalate (PBT) resin, polyethylene terephthalate (PET) resin, glass fiber reinforced polyethylene terephthalate (GF-PET) resin, cyclic polyolefin (COP) resin, and the like can be used.

When higher heat distortion temperature and long-term use characteristics are required, polyphenylene sulfide (PPS) resin, polytetrafluoroethylene (PTFE) resin, polysulfone resin, polyether sulfone resin, amorphous polyarylate resin, liquid crystal A polymer, polyetheretherketone resin, thermoplastic polyimide (PI) resin, polyamideimide (PAI) resin, or the like can be used.

From the viewpoint of manifesting the effects of the present invention, the thermoplastic resin is preferably a resin selected from a polycarbonate resin, an acrylic resin, a polyolefin resin, and a cellulose ester resin. Among these, a film using a cellulose ester resin is preferable from the viewpoint of transparency, optical properties, and productivity.

Hereinafter, a particularly suitable resin in the present invention will be described in detail.

<Polycarbonate resin>
In the present invention, various known polycarbonate resins can be used. In the present invention, it is particularly preferable to use an aromatic polycarbonate. There is no restriction | limiting in particular about the said aromatic polycarbonate, and there will be no restriction | limiting in particular if it is an aromatic polycarbonate from which the various characteristics of a desired film are acquired.

In general, a polymer material collectively referred to as polycarbonate is a generic term for a polymer material in which a polycondensation reaction is used in its synthesis method and the main chain is linked by a carbonic acid bond. , Phosgene, diphenyl carbonate and the like obtained by polycondensation. Usually, an aromatic polycarbonate represented by a repeating unit having 2,2-bis (4-hydroxyphenyl) propane called bisphenol-A as a bisphenol component is preferably selected. Various bisphenol derivatives should be selected as appropriate. Thus, an aromatic polycarbonate copolymer can be constituted.

In addition to this bisphenol-A, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 9,9-bis (4-hydroxyphenyl) fluorene, 1,1 -Bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxyphenyl) -2-phenyl Ethane, 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, bis (4-hydroxyphenyl) diphenylmethane, bis (4-hydroxyphenyl) sulfide, bis ( 4-hydroxyphenyl) sulfone, 1,1-bis (4-hydroxyphenyl) -3,3,5-to It can be exemplified methyl cyclohexane.

It is also possible to use an aromatic polyester carbonate partially containing terephthalic acid and / or isophthalic acid components. By using such a structural unit as a part of the structural component of the aromatic polycarbonate composed of bisphenol-A, the properties of the aromatic polycarbonate, such as heat resistance and solubility, can be improved. The present invention is also effective for coalescence.

The viscosity average molecular weight of the aromatic polycarbonate used here is preferably 10,000 to 200,000. A viscosity average molecular weight of 20,000 to 120,000 is particularly preferred. When the viscosity average molecular weight is in the range of 10,000 to 200,000, the resulting film has sufficient mechanical strength, and the viscosity of the dope does not increase so much that the handleability is good. The viscosity average molecular weight can be measured by commercially available high performance liquid chromatography.

The glass transition temperature of the aromatic polycarbonate is preferably 200 ° C. or higher for obtaining a highly heat-resistant film, more preferably 230 ° C. or higher. These can be obtained by appropriately selecting the copolymerization component. The glass transition temperature can be measured with a DSC apparatus (differential scanning calorimetry apparatus), for example, a baseline determined by SII NanoTechnology Co., Ltd .: RDC220 under a temperature rising condition of 10 ° C./min. Is the temperature at which it begins to deviate.

The solvent used in the dope composition containing the aromatic polycarbonate is preferably a mixed solvent containing 4 to 14 parts by mass of methylene chloride and a linear or branched aliphatic alcohol having 1 to 6 carbon atoms.

The mixing amount of the linear or branched aliphatic alcohol having 1 to 6 carbon atoms is preferably 4 to 12 parts by mass. By using such a mixed solvent, the web is peeled off at a higher residual solvent concentration than before, thereby suppressing the generation of strong static electricity when the web is peeled off, thereby causing damage to the belt, film streaks, unevenness, and minuteness. Scratches can be prevented from occurring.

The type of alcohol added is limited by the solvent used. It is a necessary condition that the alcohol and the solvent are compatible. These may be added alone or in combination of two or more. As the alcohol, a linear or branched aliphatic alcohol having 1 to 6, preferably 1 to 4, more preferably 2 to 4 carbon atoms is preferable. Specific examples include methanol, ethanol, isopropanol, and tert-butanol.

The solvent in the dope composition is mainly composed of the above methylene chloride and aliphatic alcohol, but other solvents can also be used. The remaining solvent is not particularly limited as long as it dissolves the aromatic polycarbonate at a high concentration and is compatible with alcohol, and further has a low boiling point. For example, as a solvent having a solubility in aromatic polycarbonate, in addition to methylene chloride, halogen solvents such as chloroform, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene, 1,3-dioxolane, 1, Examples include cyclic ether solvents such as 4-dioxane and tetrahydrofuran, and ketone solvents such as cyclohexanone.

The dope composition may be prepared by any method as long as a transparent solution having a low haze is obtained as a result. A predetermined amount of alcohol may be added to an aromatic polycarbonate solution previously dissolved in a solvent, or the aromatic polycarbonate may be dissolved in a mixed solvent containing alcohol. However, as described above, since alcohol is a poor solvent, the method of adding after the former may cause clouding of the dope due to the precipitation of the polymer. Therefore, the method of dissolving in the latter mixed solvent is preferable.

<acrylic resin>
The acrylic resin that can be used in the present invention includes a methacrylic resin. The resin is not particularly limited, but a resin having a range of 50 to 99% by mass of methyl methacrylate units and a range of 1 to 50% by mass of other monomer units copolymerizable therewith is preferable.

Examples of other copolymerizable monomers include alkyl methacrylates having 2 to 18 alkyl carbon atoms, alkyl acrylates having 1 to 18 carbon atoms, alkyl acrylates such as acrylic acid and methacrylic acid. Saturated acids, maleic acids, fumaric acids, divalent carboxylic acids containing unsaturated groups such as itaconic acid, aromatic vinyl compounds such as styrene, α-methylstyrene, and nucleus-substituted styrene, α, β- such as acrylonitrile, methacrylonitrile, etc. Examples thereof include unsaturated nitrile, maleic anhydride, maleimide, N-substituted maleimide, glutaric anhydride, and the like. These can be used alone or in combination of two or more.

Among these, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, s-butyl acrylate, 2-ethylhexyl acrylate, and the like are preferable from the viewpoint of thermal decomposition resistance and fluidity of the copolymer. n-Butyl acrylate is particularly preferably used.

The acrylic resin preferably has a weight average molecular weight (Mw) in the range of 80,000 to 1,000,000 from the viewpoint of mechanical strength as a film and fluidity when the film is produced. With this molecular weight, both heat resistance and brittleness can be achieved.

The weight average molecular weight of a resin such as an acrylic resin can be measured by gel permeation chromatography. The measurement conditions are as follows.

Solvent: Methylene chloride Column: Shodex K806, K805, K803G (Used by connecting three Showa Denko Co., Ltd.)
Column temperature: 25 ° C
Sample concentration: 0.1% by mass
Detector: RI Model 504 (manufactured by GL Science) Pump: L6000 (manufactured by Hitachi, Ltd.)
Flow rate: 1.0 ml / min
Calibration curve: Standard polystyrene STK standard polystyrene (manufactured by Tosoh Corp.) Mw = 2,800,000-500 calibration curves with 13 samples were used. The 13 samples are preferably used at approximately equal intervals.

The method for producing the acrylic resin is not particularly limited, and any known method such as suspension polymerization, emulsion polymerization, bulk polymerization, or solution polymerization may be used. Here, as a polymerization initiator, a normal peroxide type and an azo type can be used, and a redox type can also be used. The polymerization temperature may be in the range of 30 to 100 ° C. for suspension or emulsion polymerization, and in the range of 80 to 160 ° C. for bulk or solution polymerization. Furthermore, in order to control the reduced viscosity of the produced copolymer, polymerization can be carried out using alkyl mercaptan or the like as a chain transfer agent.

Commercially available acrylic resins can also be used. For example, Delpet 60N, 80N (Asahi Kasei Chemicals Co., Ltd.), Dianal BR52, BR80, BR83, BR85, BR88 (Mitsubishi Rayon Co., Ltd.), KT75 (Electrochemical Industry Co., Ltd.) and the like can be mentioned. .

<Polyolefin resin>
In the present invention, it is also preferable to use a polyethylene resin or the following cyclic olefin resin.

Examples of the cyclic olefin resin include norbornene resins, monocyclic olefin resins, cyclic conjugated diene resins, vinyl alicyclic hydrocarbon resins, and hydrides thereof. Among these, norbornene-based resins can be suitably used because of their good transparency and moldability.

Examples of the norbornene-based resin include a ring-opening polymer of a monomer having a norbornene structure, a ring-opening copolymer of a monomer having a norbornene structure and another monomer, a hydride thereof, and a norbornene structure. Examples thereof include addition polymers of monomers having a monomer, addition copolymers of monomers having a norbornene structure and other monomers, and hydrides thereof.

Among these, a ring-opening (co) polymer hydride of a monomer having a norbornene structure is particularly suitable from the viewpoints of transparency, moldability, heat resistance, low hygroscopicity, dimensional stability, lightness, and the like. Can be used.

As monomers having a norbornene structure, bicyclo [2.2.1] hept-2-ene (common name: norbornene), tricyclo [4.3.0.12,5] deca-3,7-diene ( Common name: dicyclopentadiene), 7,8-benzotricyclo [4.3.12,5] dec-3-ene (common name: methanotetrahydrofluorene), tetracyclo [4.4.0.12, 5.17,10] dodec-3-ene (common name: tetracyclododecene) and derivatives of these compounds (for example, those having a substituent in the ring). Here, examples of the substituent include an alkyl group, an alkylene group, and a polar group. In addition, these substituents may be the same or different and a plurality may be bonded to the ring. Monomers having a norbornene structure can be used singly or in combination of two or more.

Examples of the polar group include heteroatoms or atomic groups having heteroatoms. Examples of the hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, and a halogen atom. Specific examples of the polar group include a carboxy group, a carbonyloxycarbonyl group, an epoxy group, a hydroxy group, an oxy group, an ester group, a silanol group, a silyl group, an amino group, a nitrile group, and a sulfone group.

Other monomers capable of ring-opening copolymerization with monomers having a norbornene structure include monocyclic olefins such as cyclohexene, cycloheptene, and cyclooctene and derivatives thereof, cyclic conjugated dienes such as cyclohexadiene, cycloheptadiene, and the like. And derivatives thereof.

A ring-opening polymer of a monomer having a norbornene structure and a ring-opening copolymer of a monomer having a norbornene structure and another monomer copolymerizable with the monomer have a known ring-opening polymerization catalyst. It can be obtained by (co) polymerization in the presence.

Other monomers that can be copolymerized with a monomer having a norbornene structure include, for example, α-olefins having 2 to 20 carbon atoms such as ethylene, propylene, 1-butene and derivatives thereof; cyclobutene, cyclopentene, Examples thereof include cycloolefins such as cyclohexene and derivatives thereof; non-conjugated dienes such as 1,4-hexadiene, 4-methyl-1,4-hexadiene, and 5-methyl-1,4-hexadiene. These monomers can be used alone or in combination of two or more. Among these, α-olefin is preferable, and ethylene is more preferable.

An addition polymer of a monomer having a norbornene structure and an addition copolymer of another monomer copolymerizable with a monomer having a norbornene structure can be used in the presence of a known addition polymerization catalyst. It can be obtained by polymerization.

A hydrogenated product of a ring-opening polymer of a monomer having a norbornene structure, a hydrogenated product of a ring-opening copolymer of a monomer having a norbornene structure and another monomer capable of ring-opening copolymerization thereof, Hydrogenated products of addition polymers of monomers having a norbornene structure, and hydrogenated products of addition copolymers of monomers having a norbornene structure and other monomers capable of addition copolymerization with these A known hydrogenation catalyst containing a transition metal such as nickel or palladium is added to the polymer solution, and the carbon-carbon unsaturated bond is preferably hydrogenated by 90% or more.

Among norbornene-based resins, as a repeating unit, X: bicyclo [3.3.0] octane-2,4-diyl-ethylene structure and Y: tricyclo [4.3.0.12,5] decane-7, 9-diyl-ethylene structure, the content of these repeating units is 90% by mass or more with respect to the entire repeating units of the norbornene resin, and the content ratio of X and the content ratio of Y The ratio is preferably in the range of 100: 0 to 40:60 by mass ratio of X: Y. By using such a resin, it is possible to obtain an optical film that has no dimensional change in the long term and is excellent in stability of optical characteristics.

The molecular weight of the cyclic olefin resin used in the present invention is appropriately selected according to the purpose of use. The polyisoprene or polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography using cyclohexane as the solvent (toluene when the polymer resin does not dissolve) is usually in the range of 20000 to 150,000. The range is preferably 25,000 to 100,000, more preferably 30,000 to 80,000. When the weight average molecular weight is in such a range, the mechanical strength and molding processability of the film are highly balanced and suitable.

The glass transition temperature of the cyclic olefin resin may be appropriately selected according to the purpose of use. From the viewpoint of durability and stretch processability, it is preferably in the range of 130 to 160 ° C, more preferably in the range of 135 to 150 ° C.

The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the cyclic olefin resin is in the range of 1.2 to 3.5, preferably 1.5 to 3 in terms of relaxation time, productivity, and the like. Is in the range of 0.0, more preferably in the range of 1.8 to 2.7.

The cyclic olefin resin used in the present invention preferably has an absolute value of photoelastic coefficient of 10 × 10 ⁻¹² Pa ⁻¹ or less, more preferably 7 × 10 ⁻¹² Pa ⁻¹ or less, and more preferably 4 × 10 12 It is particularly preferably ⁻¹² Pa ⁻¹ or less. The photoelastic coefficient C is a value represented by C = Δn / σ where birefringence is Δn and stress is σ.

The method for producing the glass scattering prevention film according to the present invention using the above preferred thermoplastic resin is not particularly limited, and a cellulose ester film production method (solution casting method or melt flow) described below is used. It can be carried out in the same manner as in the elongation method.

<Cellulose ester film>
The glass scattering prevention film according to the present invention is preferably a film containing a cellulose ester resin, that is, a cellulose ester film from the viewpoints of transparency, optical properties, productivity, and processability.

(Cellulose ester resin)
The cellulose ester resin that can be used is at least one selected from cellulose (di, tri) acetate, cellulose propionate, cellulose butyrate, cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate phthalate, and cellulose phthalate. Preferably there is.

Among these, particularly preferable cellulose ester resins include cellulose (di, tri) acetate, cellulose acetate propionate and cellulose acetate butyrate.

The cellulose triacetate preferably has an acetyl group substitution degree in the range of 2.6 to 2.95, and more preferably cellulose triacetate with an acetyl group substitution degree in the range of 2.8 to 2.9.

Cellulose diacetate having an acetyl group substitution degree in the range of 2.0 to 2.5 has high stretchability and is preferably used. Commercially available products include L20, L30, L40, and L50 manufactured by Daicel Corporation, and Ca398-3, Ca398-6, Ca398-10, Ca398-30, and Ca394-60S manufactured by Eastman Chemical Japan Co., Ltd. .

Mixed lower fatty acid esters such as cellulose acetate propionate and cellulose acetate butyrate have an acyl group having 2 to 4 carbon atoms as a substituent, the substitution degree of acetyl group is X, and the substitution of propionyl group or butyryl group When the degree is Y, a cellulose resin containing a cellulose ester that simultaneously satisfies the following formulas (I) and (II) is preferable.

Formula (I) 2.6 ≦ X + Y ≦ 3.0
Formula (II) 1.0 ≦ X ≦ 2.5
In particular, cellulose acetate propionate is preferably used. Among them, 1.9 ≦ X ≦ 2.5 is satisfied, and 0.1 ≦ Y ≦ 0.9 is preferably satisfied. The portion not substituted with the acyl group is usually present as a hydroxy group. These can be synthesized by known methods. The method for measuring the substitution degree of the acyl group can be measured according to ASTM-D817-96.

Furthermore, the cellulose ester used in the present invention has a number average molecular weight (Mn) of 60000 or more and less than 180000, a ratio of weight average molecular weight (Mw) / number average molecular weight (Mn), and Mw / Mn of 1.5 to 5. 5 is preferably used, particularly preferably in the range of 2.0 to 5.0, more preferably in the range of 2.5 to 5.0, and still more preferably in the range of 3.0 to 5.0. The cellulose ester in the range is preferably used.

The number average molecular weight (Mn) and molecular weight distribution (Mw) of cellulose ester can be measured using high performance liquid chromatography. The measurement conditions are as follows.

Solvent: Methylene chloride Column: Shodex K806, K805, K803G (Used by connecting three Showa Denko Co., Ltd.)
Column temperature: 25 ° C
Sample concentration: 0.1% by mass
Detector: RI Model 504 (GL Science Co., Ltd.)
Pump: L6000 (manufactured by Hitachi, Ltd.)
Flow rate: 1.0 ml / min
Calibration curve: Standard polystyrene STK standard polystyrene (manufactured by Tosoh Co., Ltd.) Mw = 1000,000 to 500 calibration curves with 13 samples were used. The 13 samples are preferably used at approximately equal intervals.

The raw material cellulose of the cellulose ester used in the present invention may be wood pulp or cotton linter, and the wood pulp may be softwood or hardwood, but softwood is more preferable. A cotton linter is preferably used from the viewpoint of peelability during film formation. The cellulose ester made from these can be mixed suitably or can be used independently.

For example, the ratio of cellulose ester derived from cellulose linter: cellulose ester derived from wood pulp (coniferous): cellulose ester derived from wood pulp (hardwood) is 100: 0: 0, 90: 10: 0, 85: 15: 0, 50:50: 0, 20: 80: 0, 10: 90: 0, 0: 100: 0, 0: 0: 100, 80:10:10, 85: 0: 15, 40:30:30.

In the present invention, 1 g of cellulose ester resin is added to 20 ml of pure water (electric conductivity 0.1 μS / cm or less, pH 6.8), and the pH is 6 when stirred in a nitrogen atmosphere at 25 ° C. for 1 hr. Preferably, the electric conductivity is in the range of 1 to 100 μS / cm.

(Additive)
It is preferable to use a plasticizer in combination with the cellulose ester film in order to improve the fluidity and flexibility of the composition and to increase the elastic modulus by stretching.

Examples of the plasticizer include phthalate esters, fatty acid esters, trimellitic esters, phosphate esters, polyesters, sugar esters, acrylic polymers, and the like. Of these, polyester, sugar ester and acrylic polymer plasticizers are preferably used. Polyester plasticizers are superior in non-migration and extraction resistance compared to phthalate ester plasticizers such as dioctyl phthalate. It can be applied to a wide range of uses by selecting or using these plasticizers according to the use. The acrylic polymer is preferably a homopolymer or copolymer of acrylic acid or methacrylic acid alkyl ester. Examples of the acrylate monomer include methyl acrylate, ethyl acrylate, propyl acrylate (i-, n-), butyl acrylate (n-, i-, s-, t-), pentyl acrylate ( n-, i-, s-), hexyl acrylate (n-, i-), heptyl acrylate (n-, i-), octyl acrylate (n-, i-), nonyl acrylate (n-, i-), myristyl acrylate (n-, i-), acrylic acid (2-ethylhexyl), acrylic acid (ε-caprolactone), acrylic acid (2-hydroxyethyl), acrylic acid (2-hydroxypropyl), acrylic Acid (3-hydroxypropyl), acrylic acid (4-hydroxybutyl), acrylic acid (2-hydroxybutyl), acrylic acid (2-methoxyethyl), acrylic acid 2-ethoxyethyl), etc., or the acrylic acid ester may include those obtained by changing the methacrylic acid ester. The acrylic polymer is a homopolymer or copolymer of the above-mentioned monomers, but the acrylic acid methyl ester monomer unit preferably has 30% by mass or more, and the methacrylic acid methyl ester monomer unit has 40% by mass or more. preferable. In particular, a homopolymer of methyl acrylate or methyl methacrylate is preferred.

The polyester plasticizer is a reaction product of a monovalent or tetravalent carboxylic acid and a monovalent or hexavalent alcohol, and is mainly obtained by reacting a divalent carboxylic acid with a glycol. . Representative divalent carboxylic acids include glutaric acid, itaconic acid, adipic acid, phthalic acid, azelaic acid, sebacic acid and the like. The polyester plasticizer is preferably an aromatic terminal ester plasticizer. The aromatic terminal ester plasticizer is preferably an ester compound having a structure obtained by reacting phthalic acid, adipic acid, at least one benzene monocarboxylic acid and at least one alkylene glycol having 2 to 12 carbon atoms. As long as it has an adipic acid residue and a phthalic acid residue as the structure of such a compound, when an ester compound is produced, it may be reacted as an acid anhydride or esterified product of dicarboxylic acid.

Examples of the benzene monocarboxylic acid component include benzoic acid, para-tert-butylbenzoic acid, orthotoluic acid, metatoluic acid, p-toluic acid, dimethylbenzoic acid, ethylbenzoic acid, normal propylbenzoic acid, aminobenzoic acid, acetoxybenzoic acid and the like. Most preferred is benzoic acid. Moreover, these can each be used as a 1 type, or 2 or more types of mixture.

Examples of the alkylene glycol component having 2 to 12 carbon atoms include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,2-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 2,2-diethyl-1 , 3-propanediol (3,3-dimethylolpentane), 2-n-butyl-2-ethyl-1,3-propanediol (3,3-dimethylolheptane), 3-methyl-1,5-pentane Diol, 1,6-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexa Diol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-octadecane diol. Of these, 1,2-propylene glycol is particularly preferred. These glycols may be used as one kind or a mixture of two or more kinds.

The aromatic terminal ester plasticizer may be either an oligoester type or a polyester type, and the molecular weight is preferably in the range of 100 to 10,000, but is preferably in the range of 350 to 3000. The acid value is 1.5 mgKOH / g or less, the hydroxy (hydroxyl group) value is 25 mgKOH / g or less, more preferably the acid value is 0.5 mgKOH / g or less, and the hydroxy (hydroxyl group) value is 15 mgKOH / g or less.

Specific examples include, but are not limited to, the following compounds.

The sugar ester compound is an ester other than a cellulose ester, and is a compound obtained by esterifying all or part of the OH group of a sugar such as the following monosaccharide, disaccharide, trisaccharide or oligosaccharide. Specific examples include a compound represented by the general formula (1).

_(Wherein, R 1 ~ _{R 8} is a hydrogen atom, a substituted or unsubstituted alkylcarbonyl group having 2 to 22 carbon atoms, or a substituted or unsubstituted arylcarbonyl group having 2 to 22 carbon _{atoms, R} 1 ~ R ₈ may be the same or different.)
The compounds represented by the general formula (1) are shown below in more detail (compound 1-1 to compound 1-23), but are not limited thereto. In the table below, when the average degree of substitution is less than 8.0, any of R ₁ to R ₈ represents a hydrogen atom.

These plasticizers are preferably added in an amount of 0.5 to 30 parts by mass with respect to 100 parts by mass of the cellulose ester film.

(Phase difference adjusting agent)
In order to adjust the retardation of the cellulose ester film, for example, the compounds represented by the general formulas (I) to (IV) described in JP-A No. 2003-344655 and the general formula described in JP-A No. 2005-134484 are used. A retardation increasing agent such as a compound represented by the formula (IV) or a compound described in [Chemical Formula 1] to [Chemical Formula 11] of JP-A No. 2004-109657 may also be used. By using these phase difference adjusting agents, a desired phase difference can be obtained even under relatively gentle stretching conditions, and failures such as breakage can be reduced.

In the present invention, the retardation adjusting agent is preferably added in the range of 0.1 to 10% by mass, more preferably in the range of 0.5 to 5% by mass, and further in the range of 1 to 5% by mass. It is preferable to do. Two or more of these may be used in combination.

(Antioxidant)
The cellulose ester film also preferably contains an antioxidant.

Preferred antioxidants are phosphorous or phenolic, and it is more preferred to combine phosphorous and phenolic simultaneously.

Hereinafter, the antioxidant that can be suitably used in the present invention will be described.

<Phenolic antioxidant>
In the present invention, a phenolic antioxidant is preferably used, and a hindered phenol compound is particularly preferably used.

Specific examples of hindered phenol compounds include n-octadecyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) -propionate, n-octadecyl 3- (3,5-di-t-butyl- 4-hydroxyphenyl) -acetate, n-octadecyl 3,5-di-t-butyl-4-hydroxybenzoate, n-hexyl 3,5-di-t-butyl-4-hydroxyphenylbenzoate, n-dodecyl 3, 5-di-t-butyl-4-hydroxyphenylbenzoate, neo-dodecyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, dodecyl β (3,5-di-t-butyl- 4-hydroxyphenyl) propionate, ethyl α- (4-hydroxy-3,5-di-t-butylphenyl) isobutyrate, octa Decyl α- (4-hydroxy-3,5-di-t-butylphenyl) isobutyrate, octadecyl α- (4-hydroxy-3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2- (n -Octylthio) ethyl-3,5-di-t-butyl-4-hydroxy-benzoate, 2- (n-octylthio) ethyl 3,5-di-t-butyl-4-hydroxy-phenylacetate, 2- (n -Octadecylthio) ethyl-3,5-di-t-butyl-4-hydroxyphenyl acetate, 2- (n-octadecylthio) ethyl-3,5-di-t-butyl-4-hydroxy-benzoate, 2- (2-hydroxyethylthio) ethyl-3,5-di-t-butyl-4-hydroxybenzoate, diethyl glycol bis- (3,5-di-t- Butyl-4-hydroxy-phenyl) propionate, 2- (n-octadecylthio) ethyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, stearamide-N, N-bis- [ethylene 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], n-butylimino-N, N-bis- [ethylene 3- (3,5-di-tert-butyl-4-hydroxyphenyl) ) Propionate], 2- (2-stearoyloxyethylthio) ethyl-3,5-di-t-butyl-4-hydroxybenzoate, 2- (2-stearoyloxyethylthio) ethyl-7- (3-methyl- 5-t-butyl-4-hydroxyphenyl) heptanoate, 1,2-propylene glycol bis- [3- (3,5-di-t-butyl) -4-hydroxyphenyl) propionate], ethylene glycol bis- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], neopentylglycol bis- [3- (3,5-di-) t-butyl-4-hydroxyphenyl) propionate], ethylene glycol bis- (3,5-di-t-butyl-4-hydroxyphenyl acetate), glycerin-ln-octadecanoate-2,3-bis -(3,5-di-t-butyl-4-hydroxyphenyl acetate), pentaerythritol-tetrakis- [3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate], 1 , 1,1-trimethylolethane-tris- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propiyl Nate], sorbitol hexa- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2-hydroxyethyl-7- (3-methyl-5-tert-butyl-4-hydroxyphenyl) ) Propionate, 2-stearoyloxyethyl-7- (3-methyl-5-tert-butyl-4-hydroxyphenyl) heptanoate, 1,6-n-hexanediol-bis [(3 ', 5'-di-t -Butyl-4-hydroxyphenyl) propionate], pentaerythritol-tetrakis (3,5-di-t-butyl-4-hydroxyhydrocinnamate). The above type of hindered phenol compounds are commercially available from BASF Japan, for example, under the trade names “Irganox 1076” and “Irganox 1010”.

<Phosphorus antioxidant>
As the phosphorus-based antioxidant, phosphorus-based compounds such as phosphite, phosphonite, phosphinite, or tertiary phosphane can be used. A conventionally known compound can be used as the phosphorus compound. For example, Japanese Patent Application Laid-Open Nos. 2002-138188, 2005-344444, paragraph numbers 0022 to 0027, Japanese Patent Application Laid-Open No. 2004-182979, paragraphs 0023 to 0039, Japanese Patent Application Laid-Open Nos. 10-306175, 1-254744, and Japanese Patent Application Laid-Open No. -270892, JP-A-5-202078, JP-A-5-178870, JP-T-2004-504435, JP-T-2004-530759, and JP-A-2005-353229 Is preferred.

The addition amount of the phosphorus compound is usually in the range of 0.01 to 10 parts by mass, preferably in the range of 0.05 to 5 parts by mass, more preferably in the range of 0.1 to 3 parts by mass with respect to 100 parts by mass of the resin. It is a range.

As phosphorus compounds, in addition to the compounds represented by the above general formula, triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite Tris (2,4-di-t-butylphenyl) phosphite, 10- (3,5-di-t-butyl-4-hydroxybenzyl) -9,10-dihydro-9-oxa-10-phosphat Phenanthrene-10-oxide, 6- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-t-butyldibenz [d, f] [1 3.2] monophosphite compounds such as dioxaphosphine and tridecyl phosphite; 4,4'-butylidene- Diphosphite compounds such as bis (3-methyl-6-t-butylphenyl-di-tridecyl phosphite), 4,4'-isopropylidene-bis (phenyl-di-alkyl (C12-C15) phosphite); Triphenylphosphonite, tetrakis (2,4-di-tert-butylphenyl) [1,1-biphenyl] -4,4'-diylbisphosphonite, tetrakis (2,4-di-tert-butyl-5- Phosphonite compounds such as methylphenyl) [1,1-biphenyl] -4,4'-diylbisphosphonite; phosphinite compounds such as triphenylphosphinite and 2,6-dimethylphenyldiphenylphosphinite; triphenyl Phosphine compounds such as phosphine and tris (2,6-dimethoxyphenyl) phosphine; And the like.

Phosphorus compounds of the above type are, for example, from Sumitomo Chemical Co., Ltd. “Sumilizer GP”, from ADEKA Co., Ltd. “ADK STAB PEP-24G”, “ADK STAB PEP-36” and “ADK STAB 3010”, BASF Japan K.K. "IRGAFOS P-EPQ" and "GSY-P101" from Sakai Chemical Industry Co., Ltd.

(Other antioxidants)
Dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate, pentaerythrityltetrakis (3-laurylthiopropionate) Nate) and other sulfur-based antioxidants, 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [1- (2-hydroxy -3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, a heat resistant processing stabilizer such as 3,4-dihydro-2H-1 described in JP-B-08-27508 -Benzopyran compounds, 3,3'-spirodichroman compounds, 1,1-spiroindane compounds, morpholine, thiomorpho Emissions, thiomorpholine oxide, thiomorpholine dioxide, a compound having a piperazine skeleton partial structure, oxygen scavenger dialkoxy benzene type compound in JP-03-174150 describes the like. These antioxidant partial structures may be part of the polymer or regularly pendant into the polymer and introduced into part of the molecular structure of additives such as plasticizers, acid scavengers, and UV absorbers. It may be.

In the present invention, the antioxidant is preferably added in the range of 0.1 to 10% by mass, more preferably in the range of 0.5 to 5% by mass, and further in the range of 1 to 5% by mass. It is preferable. Two or more of these may be used in combination.

(Other additives)
The cellulose ester film according to the present invention may contain various compounds as additives in addition to the above-described compounds according to the purpose.

<Acid scavenger>
The acid scavenger preferably comprises an epoxy compound as an acid scavenger described in US Pat. No. 4,137,201. Epoxy compounds as such acid scavengers are known in the art and are derived by condensation of diglycidyl ethers of various polyglycols, particularly about 8-40 moles of ethylene oxide per mole of polyglycol. Glycol, diglycidyl ether of glycerol, metal epoxy compounds (such as those conventionally used in and together with vinyl chloride polymer compositions), epoxidized ether condensation products, diphenols of bisphenol A Glycidyl ether (ie, 4,4'-dihydroxydiphenyldimethylmethane), epoxidized unsaturated fatty acid ester (especially an ester of alkyl of about 2 to 2 carbon atoms of fatty acids of 2 to 22 carbon atoms such as butyl Epoxy stearate ), And various epoxidized long chain fatty acid triglycerides and the like (e.g., epoxidized vegetable oils and other unsaturated natural oils, which may be represented and exemplified by compositions such as epoxidized soybean oil, sometimes epoxidized natural) These are referred to as glycerides or unsaturated fatty acids and these fatty acids generally contain 12 to 22 carbon atoms)).

<Light stabilizer>
Light stabilizers include hindered amine light stabilizer (HALS) compounds, which are known compounds, such as US Pat. No. 4,619,956, columns 5-11 and US Pat. , 839,405, including 2,2,6,6-tetraalkylpiperidine compounds, or their acid addition salts or complexes of them with metal compounds, as described in columns 3 to 5 of US Pat. It is. Furthermore, the light stabilizer described in JP 2007-63311 A can be used.

<Ultraviolet absorber>
As the ultraviolet absorber, from the viewpoint of preventing deterioration due to ultraviolet rays, those having excellent absorption ability of ultraviolet rays having a wavelength of 370 nm or less and those having little absorption of visible light having a wavelength of 400 nm or more are preferable from the viewpoint of liquid crystal display properties. Examples include oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, nickel complex compounds, etc., but benzophenone compounds and less colored benzotriazole compounds preferable. Further, ultraviolet absorbers described in JP-A-10-182621 and JP-A-8-337574, and polymer ultraviolet absorbers described in JP-A-6-148430 may be used.

Specific examples of the benzotriazole compound 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-chlorobenzo Triazole, 2- (2′-hydroxy-3 ′-(3 ″, 4 ″, 5 ″, 6 ″ -tetrahydrophthalimidomethyl) -5′-methylphenyl) benzotriazole, 2,2-methylenebis (4- (1 , 1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol), 2- (2'-hydroxy-3 ' tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5 '-(2-octyloxycarbonylethyl) -phenyl) -5-chloro Benzotriazole, 2- (2′-hydroxy-3 ′-(1-methyl-1-phenylethyl) -5 ′-(1,1,3,3-tetramethylbutyl) -phenyl) benzotriazole, 2- ( 2H-benzotriazol-2-yl) -6- (linear and side chain dodecyl) -4-methylphenol, octyl-3- [3-tert-butyl-4-hydroxy-5- (chloro-2H-benzotriazole) -2-yl) phenyl] propionate and 2-ethylhexyl-3- [3-tert-butyl-4-hydroxy-5- (5-chloro-2H- Benzotriazole-2-yl) can be mentioned mixtures of phenyl] propionate, but not limited thereto.

As commercially available products, TINUVIN 326, TINUVIN 109, TINUVIN 171, TINUVIN 900, TINUVIN 928, TINUVIN 928, TINUVIN 360 (all manufactured by BASF Japan), LA31 (manufactured by ADEKA), Sumisorb 250 (manufactured by Sumitomo Chemical), and RUVA-100 (manufactured by Otsuka Chemical) are listed.

Specific examples of benzophenone compounds include 2,4-dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, bis (2-methoxy-4-hydroxy-) 5-benzoylphenylmethane) and the like, but are not limited thereto.

In the present invention, the ultraviolet absorber is preferably added in the range of 0.1 to 20% by mass, more preferably in the range of 0.5 to 10% by mass, and further in the range of 1 to 5% by mass. It is preferable. Two or more of these may be used in combination.

<Matting agent>
In the cellulose ester film according to the present invention, it is preferable to add fine particles such as a matting agent from the viewpoint of improving the handleability and strength. Examples of the fine particles include fine particles of an inorganic compound or fine particles of an organic compound. The matting agent is preferably as fine as possible. Examples of the fine particles include silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, kaolin, talc, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, Examples thereof include inorganic fine particles such as magnesium silicate and calcium phosphate, and crosslinked polymer fine particles. Among these, silicon dioxide is preferable because it can reduce the haze of the resin substrate. In many cases, fine particles such as silicon dioxide are surface-treated with an organic material, but such particles are preferable because they can reduce the haze of the resin substrate.

Preferred organic materials for the surface treatment include halosilanes, alkoxysilanes, silazanes, siloxanes, and the like. The larger the average particle size of the fine particles, the greater the sliding effect, and the smaller the average particle size, the better the transparency.

Further, the average particle size of the secondary particles of the fine particles is in the range of 0.05 to 1.0 μm. The average particle size of the secondary particles of the fine particles is preferably in the range of 5 to 50 nm, more preferably in the range of 7 to 14 nm. These fine particles are preferably used in the cellulose ester film in order to produce irregularities in the range of 0.01 to 1.0 μm on the surface of the cellulose ester film. The content of fine particles in the cellulose ester is preferably in the range of 0.005 to 0.3% by mass with respect to the cellulose ester.

Examples of the silicon dioxide fine particles include Aerosil 200, 200V, 300, R972, R972V, R974, R202, R812, OX50, TT600, etc. manufactured by Nippon Aerosil Co., Ltd., preferably Aerosil 200V, R972. , R972V, R974, R202, R812. Two or more kinds of these fine particles may be used in combination. When using 2 or more types together, it can mix and use in arbitrary ratios. In this case, fine particles having different average particle sizes and materials, for example, Aerosil 200V and R972V can be used in a mass ratio of 0.1: 99.9 to 99.9: 0.1.

The presence of fine particles in the cellulose ester film used as the matting agent can be used for another purpose to improve the strength of the cellulose ester film.

<Manufacture of cellulose ester film by solution casting method>
About the manufacturing method of the glass scattering prevention film which concerns on this invention, a preferable film forming method is demonstrated taking a cellulose-ester film as an example. However, it is not limited to this. Film formation of polycarbonate resin, acrylic resin, and polyolefin resin can be performed in the same manner.

(1) Dissolution Step In this step, a cellulose ester resin, a heat-shrinkable material, and other additives are dissolved in an organic solvent mainly composed of a good solvent for the cellulose ester resin while stirring to form a dope.

For dissolving the cellulose ester resin, a method carried out at normal pressure, a method carried out below the boiling point of the main solvent, a method carried out under pressure above the boiling point of the main solvent, JP-A-9-95544, JP-A-9-95557 Alternatively, various dissolution methods such as a method using a cooling dissolution method as described in JP-A-9-95538 and a method using a high pressure as described in JP-A-11-21379 can be used. The method of pressurizing at a boiling point or higher is preferred.

Recycled material is a finely pulverized film, which is generated when the film is formed, cut off on both sides of the film, or the original film that has been speculated out due to scratches, etc. Reused.

(2) Casting process An endless metal belt that feeds the dope to a pressure die through a liquid feed pump (for example, a pressurized metering gear pump) and transfers it infinitely, such as a stainless steel belt, or a metal such as a rotating metal drum This is a step of casting the dope from the pressure die slit to the casting position on the support.

¡Pressure dies that can adjust the slit shape of the die base and make the film thickness uniform are preferred. Examples of the pressure die include a coat hanger die and a T die, and any of them is preferably used. The surface of the metal support is a mirror surface. In order to increase the film forming speed, two or more pressure dies may be provided on the metal support, and the dope amount may be divided and stacked. Or it is also preferable to obtain the film of a laminated structure by the co-casting method which casts several dope simultaneously.

(3) Solvent evaporation step In this step, the web (the dope is cast on the casting support and the formed dope film is called a web) is heated on the casting support to evaporate the solvent.

To evaporate the solvent, there are a method of blowing air from the web side and / or a method of transferring heat from the back side of the support by a liquid, a method of transferring heat from the front and back by radiant heat, etc. High efficiency and preferable. A method of combining them is also preferably used. The web on the support after casting is preferably dried on the support in an atmosphere of 40 to 100 ° C. In order to maintain the atmosphere at 40 to 100 ° C., it is preferable to apply hot air at this temperature to the upper surface of the web or heat by means such as infrared rays.

From the viewpoint of surface quality, moisture permeability, and peelability, it is preferable to peel the web from the support in the range of 30 to 120 seconds.

(4) Peeling process It is the process of peeling the web which the solvent evaporated on the metal support body in a peeling position. The peeled web is sent to the next process.

The temperature at the peeling position on the metal support is preferably in the range of 10 to 40 ° C, more preferably in the range of 11 to 30 ° C.

The amount of residual solvent at the time of peeling of the web on the metal support at the time of peeling is preferably 50 to 120% by mass depending on the strength of drying conditions, the length of the metal support, and the like. When peeling at a higher residual solvent amount, if the web is too soft, the flatness at the time of peeling is impaired, and slippage and vertical stripes are likely to occur due to the peeling tension. The amount of solvent is determined.

The amount of residual solvent in the web is defined by the following formula.

Residual solvent amount (%) = (mass before web heat treatment−mass after web heat treatment) / (mass after web heat treatment) × 100
Note that the heat treatment for measuring the residual solvent amount represents performing heat treatment at 115 ° C. for 1 hour.

The peeling tension at the time of peeling the metal support and the film is usually in the range of 196 to 245 N / m. However, if wrinkles easily occur at the time of peeling, it is preferable to peel with a tension of 190 N / m or less. Further, it is preferable to peel in the range of minimum tension capable of peeling to 166.6 N / m, and then in the range of minimum tension to 137.2 N / m, particularly preferably in the range of minimum tension to 100 N / m. That is.

In the present invention, the temperature at the peeling position on the metal support is preferably in the range of −50 to 40 ° C., more preferably in the range of 10 to 40 ° C., and most preferably in the range of 15 to 30 ° C. preferable.

(5) Drying and stretching step After peeling, using a drying device that alternately conveys the web through rollers arranged in the drying device and / or a tenter stretching device that clips and conveys both ends of the web with clips. , Dry the web.

The drying means is generally to blow hot air on both sides of the web, but there is also a means to heat by applying microwaves instead of wind. Too rapid drying tends to impair the flatness of the finished film. Drying at a high temperature is preferably performed from about 8% by mass or less of the residual solvent. Throughout, the drying is generally performed in the range of 40 to 250 ° C. It is particularly preferable to dry in the range of 40 to 160 ° C.

(Extension process)
In order to provide the maximum elastic modulus of the glass scattering prevention film according to the present invention in a desired direction, the width direction (TD direction) or the longitudinal direction (MD direction) or the longitudinal direction (MD direction) by a tenter method in which both ends of the web are gripped by clips or the like It is preferable to perform stretching in both directions and further in an oblique direction.

The stretching treatment not only gives the direction of the maximum elastic modulus of the glass scattering prevention film in a desired direction, but also gives the direction of the slow axis in the plane of the glass scattering prevention film in a direction parallel to the stretching direction. Can do.

The stretching temperature when stretching with a tenter is preferably performed at a temperature of Tg−20 ° C. or higher of the film. Specifically, in the case of a cellulose ester film, it is preferably performed within the range of 130 to 220 ° C. More preferably, it is carried out in the range of ˜210 ° C.

If it is too low, the film may break during stretching, while if it is too high, the orientation will be disturbed and the direction of the maximum elastic modulus will not be constant.

The glass transition temperature Tg of the film was measured at a rate of temperature increase of 20 ° C./min using a differential scanning calorimeter (DSC-7, manufactured by Perkin Elmer), and was determined in accordance with JIS K7121 (1987). The glass transition temperature (Tmg).

The stretching ratio is preferably 1.05 to 2.5 times in the width direction (TD stretching). The range is more preferably 1.1 to 2.0 times, and particularly preferably 1.2 to 1.5 times.

When stretching is performed with a tenter, it is preferable to control the residual solvent amount of the web, the residual solvent amount of the web is preferably in the range of 20 to 100% by mass at the start of the tenter, and the residual solvent amount of the web is 10% by mass. It is preferable to dry while applying a tenter until it becomes less than or equal to 5%, and more preferably less than or equal to 5% by weight.

In the case of stretching in the longitudinal direction (MD stretching), an inter-roller neck-in stretching method, a proximity roller stretching method, and the like can be given. Adopting the inter-roller neck-in stretching method is desirable because it has the advantage that the retardation can be easily controlled and defects such as scratches and wrinkles are less likely to occur in the retardation film.

The stretching ratio when stretching in the longitudinal direction is also preferably in the range of 1.01 to 2 times, and more preferably in the range of 1.05 to 1.5 times.

It is also preferable to relax the remaining strain by heat treatment (annealing) after stretching. The heat treatment is preferably performed in the range of 80 to 200 ° C, preferably in the range of 100 to 180 ° C, and more preferably in the range of 130 to 160 ° C. At this time, it is preferable to perform the heat treatment in the range of a heat transfer coefficient of 20 to 130 × 10 ³ J / m ² · hr. More preferably, it is in the range of 40 to 130 × 10 ³ J / m ² · hr, and most preferably in the range of 42 to 84 × 10 ³ J / m ² · hr.

This reduces the remaining strain and tends to make the direction of maximum elastic modulus uniform.

In the tenter process, it is preferable that the temperature distribution of the atmosphere is small from the viewpoint of improving the uniformity of the film. For example, the temperature distribution in the width direction in the tenter process is preferably within ± 5 ° C, more preferably within ± 2 ° C. Most preferably, it is within ± 1 ° C.

(6) Winding step This is a step of winding the film as a film with a winder after the residual solvent amount in the web is 2% by mass or less, and the dimensional stability is achieved by setting the residual solvent amount to 0.4% by mass or less. Can be obtained. In particular, it is preferable to wind in the range of 0.00 to 0.10% by mass.

As a winding method, a generally used one may be used, and there are a constant torque method, a constant tension method, a taper tension method, a program tension control method with a constant internal stress, etc., and these may be used properly.

The glass scattering prevention film, which is a cellulose ester film according to the present invention, is preferably a long film. Specifically, the film has a thickness of about 100 to 5000 m and is usually provided in a roll form. is there. The film width is preferably in the range of 1.3 to 4 m, more preferably in the range of 1.4 to 3 m.

<Manufacture of cellulose ester film by melt casting method>
The case where the cellulose ester film according to the present invention is produced by the melt casting method will be described.

<Melted pellet manufacturing process>
The composition containing a resin used for melt extrusion is usually preferably kneaded in advance and pelletized.

Pelletization may be performed by a known method. For example, an additive comprising a dried thermoplastic resin and a heat-shrinkable material is supplied to an extruder with a feeder and kneaded using a single-screw or twin-screw extruder, and then from a die. It can be formed by extruding into a strand, cooling with water or air, and cutting.

It is important to dry the raw materials before extruding them in order to prevent the raw materials from being decomposed. In particular, the cellulose ester is easy to absorb moisture, and therefore it is preferable to dry it in a dehumidifying hot air dryer or a vacuum dryer for 3 hours or more in the range of 70 to 140 ° C. to keep the moisture content to 200 ppm or less, and further to 100 ppm or less.

Additives may be supplied to the extruder or may be supplied by individual feeders. A small amount of an additive such as an antioxidant is preferably mixed in advance in order to mix uniformly.

The antioxidant may be mixed with each other, and if necessary, the antioxidant may be dissolved in a solvent, impregnated with a thermoplastic resin and mixed, or mixed by spraying. May be.

A vacuum nauter mixer or the like is preferable because drying and mixing can be performed simultaneously. Further, if the contact with air, such as the exit from the feeder unit or die, it is preferable that the atmosphere such as dehumidified air and dehumidified N ₂ gas.

The extruder is preferably processed at as low a temperature as possible so as to be able to be pelletized so that the shear force is suppressed and the resin does not deteriorate (molecular weight reduction, coloring, gel formation, etc.). For example, in the case of a twin screw extruder, it is preferable to rotate in the same direction using a deep groove type screw. From the uniformity of kneading, the meshing type is preferable.

Film formation is performed using the pellets obtained as described above. It is also possible to feed the raw material powder directly to the extruder with a feeder and form a film as it is without pelletization.

<Process of extruding the molten mixture from the die to the cooling roller>
First, using a single-screw or twin-screw type extruder, the melt temperature Tm when extruding the pellets is about 200-300 ° C, filtered through a leaf disk type filter, etc. to remove foreign matter, Coextruded into a film, solidified on a cooling roller, and cast while pressing with an elastic touch roller.

When introducing into the extruder from the supply hopper, it is preferable to prevent oxidative decomposition or the like under vacuum, reduced pressure, or inert gas atmosphere. Tm is the temperature of the die exit portion of the extruder.

∙ If foreign matter such as scratches or plasticizer aggregates adheres to the die, streaky defects may occur. Such defects are also referred to as die lines, but in order to reduce surface defects such as die lines, it is preferable to have a structure in which the resin retention portion is minimized in the piping from the extruder to the die. . It is preferable to use a die that has as few scratches as possible inside the lip.

The inner surface that comes into contact with the molten resin, such as an extruder or a die, is preferably subjected to surface treatment that makes it difficult for the molten resin to adhere to the surface by reducing the surface roughness or using a material with low surface energy. Specifically, a hard chrome plated or ceramic sprayed material is polished so that the surface roughness is 0.2 S or less.

There is no particular limitation on the cooling roller, but it is a roller having a structure in which a heat medium or a cooling medium whose temperature can be controlled flows with a highly rigid metal roller, and the size is not limited, but the film is melt extruded. The diameter of the cooling roller is usually about 100 mm to 1 m.

The surface material of the cooling roller includes carbon steel, stainless steel, aluminum, titanium and the like. Further, in order to increase the hardness of the surface or improve the releasability from the resin, it is preferable to perform a surface treatment such as hard chrome plating, nickel plating, amorphous chrome plating, or ceramic spraying.

The surface roughness of the cooling roller surface is preferably 0.1 μm or less in terms of Ra, and more preferably 0.05 μm or less. The smoother the roller surface, the smoother the surface of the resulting film. Of course, it is preferable that the surface processed is further polished to have the above-described surface roughness.

Examples of the elastic touch roller include JP-A-03-124425, JP-A-08-224772, JP-A-07-1000096, JP-A-10-272676, WO97 / 028950, JP-A-11-235747, JP2002-2002. As described in Japanese Patent No. 36332, Japanese Patent Application Laid-Open No. 2005-172940 and Japanese Patent Application Laid-Open No. 2005-280217, a thin-film metal sleeve-covered silicon rubber roller can be used.

When peeling the film from the cooling roller, it is preferable to control the tension to prevent deformation of the film.

The steps after the peeling step are the same as in the solution casting method.

<optical properties>
The glass scattering prevention film according to the present invention preferably has a total light transmittance of 90% or more, more preferably 93% or more. Moreover, as a realistic upper limit, it is about 99%. In order to achieve excellent transparency expressed by such total light transmittance, it is necessary not to introduce additives and copolymerization components that absorb visible light, or to remove foreign substances in the polymer by high-precision filtration. It is effective to reduce the diffusion and absorption of light inside the film.

In addition, the in-plane retardation value Ro of the glass scattering prevention film is in the range of 0 to 100 nm when measured at a light wavelength of 590 nm under an environment of a temperature of 23 ° C. and a relative humidity of 55% RH. It is preferable for improving the visibility when it is applied.

The thickness direction retardation value Rt is not particularly limited, but is preferably in the range of −10 to 100 nm.

Further, the in-plane retardation value Ro of the glass scattering prevention film is in the range of 105 to 160 nm in the measurement at a light wavelength of 590 nm under the environment of a temperature of 23 ° C. and a relative humidity of 55% RH. By arranging the direction of the slow axis obliquely with respect to the direction of the absorption axis of the polarizing plate, as described above, the visibility when wearing polarized sunglasses is significantly improved.

Therefore, in order to simultaneously satisfy the crack prevention property of the ITO electrode, the glass scattering prevention property, and the visibility improvement when wearing polarized sunglasses, the direction of the maximum elastic modulus and the slow axis of the glass scattering prevention film according to the present invention. It is preferable that the direction is the same, and the formation direction of the transparent electrode according to the present invention is the same as the absorption axis direction of the polarizing plate. In this case, it is not necessary to arrange each bonding direction in a complicated manner, which is preferable from the viewpoint of ease of production.

In order to make the direction of the maximum elastic modulus of the glass scattering prevention film coincide with the direction of the slow axis, it is preferable to perform a stretching treatment as described above.

In this case, the retardation value Rt in the thickness direction is not particularly limited, but is preferably in the range of 20 to 400 nm, and more preferably in the range of 50 to 300 nm.

The phase difference values Ro and Rt are values defined by the following formulas (i) and (ii).

Formula (i): Ro = (n _x −n _y ) × d
Formula (ii): Rt = {(n _x + n _y ) / 2−n _z } × d
(Wherein, n _x is a refractive index in a slow axis direction in the substrate film surface, n _y is the refractive index in the direction perpendicular to the slow axis in the base film surface, the thickness of the n _z is a substrate film (The refractive index in the direction, d represents the thickness (nm) of the substrate film, respectively.)
For the measurement of the phase difference value, for example, KOBRA-21AWR (Oji Scientific Instruments Co., Ltd.) can be used.

The retardation value can be adjusted by the type of resin, the type and amount of additives such as the plasticizer described above, and the film thickness and stretching conditions of the film.

(Hard coat layer)
It is preferable that the glass scattering prevention film according to the present invention has a hard coat layer containing an acrylic resin in order to further improve the crack generation prevention property of the ITO electrode.

Hereinafter, the hard coat layer will be described.

<Active energy ray-curable resin>
Since the hard coat layer according to the present invention is preferably composed of, for example, an active energy ray curable resin, the hard coat layer composition in the present embodiment preferably includes an active energy ray curable acrylic resin. .

The active energy ray curable type refers to a resin that is cured through a crosslinking reaction or the like by irradiation with active rays such as ultraviolet rays or electron beams, and specifically, a resin having an ethylenically unsaturated group. More specifically, 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 is preferably used. Of these, ultraviolet curable acrylate resins are preferred.

As the ultraviolet curable acrylate resin, polyfunctional acrylate is preferable. The polyfunctional acrylate is preferably selected from the group consisting of pentaerythritol polyfunctional acrylate, dipentaerythritol polyfunctional acrylate, pentaerythritol polyfunctional methacrylate, and dipentaerythritol polyfunctional methacrylate. Here, the polyfunctional acrylate is a compound having two or more acryloyloxy groups or methacryloyloxy groups in the molecule.

Examples of the polyfunctional acrylate monomer include ethylene glycol diacrylate, diethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, and tetramethylolmethane triacrylate. , Tetramethylolmethane tetraacrylate, pentaglycerol triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, glycerin triacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaether Thritol hexaacrylate, tris (acryloyloxyethyl) isocyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, Tetramethylol methane trimethacrylate, tetramethylol methane tetramethacrylate, pentaglycerol trimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, glycerin trimethacrylate, dipentaerythritol trimethacrylate, dipentaerythritol tetra Methacrylate, dipentaerythritol penta methacrylate, dipentaerythritol hexa methacrylate, etc. isocyanurate derivatives of the active energy ray-curable are preferably exemplified. Commercially available products may be used as these polyfunctional acrylates, such as pentaerythritol tri / tetraacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., A-TMM-3L), pentaerythritol triacrylate (manufactured by Kyoeisha Chemical Co., Ltd., PE-3A). Etc. can be obtained. In addition, these compounds are used individually or in mixture of 2 or more types, respectively.

The isocyanurate derivative of the active energy ray-curable resin is not particularly limited as long as it has a structure in which one or more ethylenically unsaturated groups are bonded to the isocyanuric acid skeleton, but there are three in the same molecule. Compounds having the above ethylenically unsaturated groups and one or more isocyanurate rings are preferred.

As such an isocyanuric acid triacrylate compound, a commercially available product can be used, and examples thereof include A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd. Examples of commercially available isocyanuric acid diacrylate compounds include Aronix M-215 manufactured by Toagosei Co., Ltd. Examples of the mixture of the isocyanuric acid triacrylate compound and the isocyanuric acid diacrylate compound include Aronix M-315 and Aronix M-313 manufactured by Toagosei Co., Ltd. ε-Caprolactone-modified active energy ray-curable isocyanurate derivatives include ε-caprolactone-modified tris- (acryloxyethyl) isocyanurate, Shin-Nakamura Chemical Co., Ltd. A-9300-1CL, Toagosei Co., Ltd. Examples include, but are not limited to, Aronix M-327.

Further, monofunctional acrylate may be used as the active energy ray curable resin. Monofunctional acrylates include isobornyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, isostearyl acrylate, benzyl acrylate, ethyl carbitol acrylate, phenoxyethyl acrylate, lauryl acrylate, isooctyl acrylate, tetrahydrofurfuryl acrylate, behenyl Examples thereof include acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and cyclohexyl acrylate. Monofunctional acrylates can be obtained from Shin Nakamura Chemical Co., Ltd., Osaka Organic Chemical Industry Co., Ltd., and the like. These compounds are used alone or in combination of two or more. Moreover, oligomers, such as a dimer and a trimer of the said monomer, may be sufficient.

Furthermore, urethane acrylate may be used as the active energy ray curable resin. As the urethane acrylate, for example, commercially available products such as Beam Set 575CB manufactured by Arakawa Chemical Industry Co., Ltd. and UA-306H manufactured by Kyoeisha Chemical Co., Ltd. can be used.

The viscosity of the polyfunctional acrylate as described above is preferably 3000 mPa · s or less, more preferably 1500 mPa · s or less, at 25 ° C. Particularly preferably, it is 1000 mPa · s or less. Examples of such a low viscosity resin include glycerin triacrylate, pentaerythritol triacrylate, and pentaerythritol tetraacrylate. In addition, the said viscosity is the value measured on 25 degreeC conditions using the E-type viscosity meter.

The amount of the active energy ray-curable resin in the hard coat layer composition is usually in the range of 10 to 99 parts by mass, preferably in the range of 35 to 99 parts by mass, with the total composition being 100 parts by mass. is there. When the blending amount of the active energy ray-curable resin is small, it is difficult to sufficiently obtain the film strength of the hard coat layer. Moreover, when there are many compounding quantities, since malfunctions, such as a film thickness uniformity at the time of apply | coating with the well-known coating method mentioned later and an application | coating streak, are not preferable.

<Cationically polymerizable compound>
The hard coat layer may further contain a cationically polymerizable compound, and any cationic polymerizable compound can be used as long as it undergoes cationic polymerization by energy active ray irradiation or heat to form a resin. Specific examples include an epoxy group, a cyclic ether group, a cyclic acetal group, a cyclic lactone group, a cyclic thioether group, a spiro orthoester compound, and a vinyloxo group. Among them, a compound having a functional group such as an epoxy group or a vinyl ether group is preferably used in the present invention. Examples of the cationically polymerizable compound having an epoxy group or a vinyl ether group include phenyl glycidyl ether, ethylene glycol diglycidyl ether, glycerin diglycidyl ether, vinylcyclohexene dioxide, limonene dioxide, 3,4-epoxycyclohexylmethyl-3 ′. , 4'-epoxycyclohexanecarboxylate, bis- (6-methyl-3,4-epoxycyclohexyl) adipate, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, 1 , 4-cyclohexanedimethanol divinyl ether and the like. Moreover, a polymer compound can also be used as an epoxy compound.

When the cation polymerizable compound is contained in the hard coat layer composition, the amount of the cation polymerizable compound in the hard coat layer composition is usually 1 to 90 parts by mass when the entire composition is 100 parts by mass. The range is preferably 1 to 50 parts by mass.

<Fine particles>
The hard coat layer may contain fine particles. Examples of the fine particles include inorganic fine particles and organic fine particles. Inorganic fine particles include silica, titanium oxide, aluminum oxide, tin oxide, indium oxide, ITO, zinc oxide, zirconium oxide, magnesium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated Mention may be made of calcium silicate, aluminum silicate, magnesium silicate and calcium phosphate. As organic fine particles, polymethacrylic acid methyl acrylate resin powder, acrylic styrene resin powder, polymethyl methacrylate resin powder, silicon resin powder, polystyrene resin powder, polycarbonate resin powder, benzoguanamine resin powder, melamine resin powder, Examples thereof include polyolefin resin powder, polyester resin powder, polyamide resin powder, polyimide resin powder, and polyfluorinated ethylene resin powder. The average particle size of these fine particles is preferably in the range of 30 to 200 nm in view of the stability and clearness of the hard coat layer coating composition. The hard coat layer may contain two or more kinds of fine particles having different particle sizes.

<Other additives, manufacturing method of hard coat layer>
The hard coat layer preferably further contains a photopolymerization initiator in order to accelerate the curing of the active energy ray-curable resin. The blending amount of the photopolymerization initiator is preferably contained in a mass ratio of photopolymerization initiator: active energy ray-curable resin = 20: 100 to 0.01: 100.

Specific examples of the photopolymerization initiator include alkylphenone series, acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, α-amyloxime ester, thioxanthone, and derivatives thereof, but are not particularly limited thereto. It is not a thing. Commercially available products may be used, and preferred examples include Irgacure 184, Irgacure 907, and Irgacure 651 manufactured by BASF Japan.

The hard coat layer may contain an ultraviolet absorber similar to the above-described ultraviolet absorber.

Furthermore, the hard coat layer may be composed of two or more layers. When two or more hard coat layers are provided, the thickness of the hard coat layer in contact with the glass scattering prevention film is preferably in the range of 0.05 to 2 μm. Two or more layers may be formed as a simultaneous multilayer. The simultaneous multi-layer is to form a hard coat layer by applying two or more hard coat layers on a glass anti-scattering film without wet process. In order to laminate the second hard coat layer on the first hard coat layer without using a drying process, the layers are stacked one after another with an extrusion coater or simultaneously with a slot die having a plurality of slits. Can be done.

In addition, as a method for producing a hard coat layer, a hard coat layer coating composition diluted with a solvent that swells or partially dissolves a glass scattering prevention film is applied onto the glass scattering prevention film by the following method, dried, and cured. Is preferable from the viewpoint that interlayer adhesion between the hard coat layer and the glass scattering prevention film is easily obtained.

As the solvent that swells or partially dissolves the glass scattering prevention film, a solvent containing ketone and / or acetate is preferable. Specific examples of the ketone include methyl ethyl ketone, acetone, and cyclohexanone. Examples of the acetate ester include ethyl acetate, methyl acetate, and butyl acetate. The hard coat layer coating composition may contain an alcohol solvent as another solvent.

The coating amount of the hard coat layer coating composition is preferably in the range of 0.1 to 40 μm as a wet film thickness, and more preferably in the range of 0.5 to 30 μm. Further, the dry film thickness is preferably about 5 to 20 μm, preferably 7 to 12 μm.

The hard coat layer is a gravure coater, a dip coater, a reverse coater, a wire bar coater, a die (extrusion) coater, a hard coat coating composition that forms a hard coat layer is applied using a known coating method such as an inkjet method, After application, the film can be dried, irradiated with actinic radiation (also referred to as UV curing treatment), and further subjected to heat treatment after UV curing as necessary. The heat treatment temperature after UV curing is preferably 80 ° C. or higher, more preferably 100 ° C. or higher, and particularly preferably 120 ° C. or higher. By performing the heat treatment after UV curing at such a high temperature, the mechanical strength (rubbing resistance, pencil hardness) of the hard coat layer becomes better.

In the case of imparting antiglare properties to the hard coat layer, it is preferable to perform the drying temperature in the decreasing rate drying section at a high temperature treatment of 80 ° C. or higher. More preferably, the temperature in the decreasing rate drying section is 95 ° C. or higher and 130 ° C. or lower. By setting the temperature of the rate-decreasing drying section to a high temperature treatment, convection occurs in the coating resin during the formation of the hard coat layer. As a result, fine surface roughness tends to appear on the hard coat layer surface, and the arithmetic described later The average roughness Ra value is also preferable because it is easy to obtain.

In general, it is known that the drying process changes from a constant state to a gradually decreasing state when drying starts. The decreasing section is called the decreasing rate drying section. In the constant rate drying section, the amount of heat flowing in is all consumed for solvent evaporation on the coating film surface, and when the solvent on the coating film surface decreases, the evaporation surface moves from the surface to the inside and enters the decreasing rate drying section. Thereafter, the temperature of the coating film surface rises and approaches the hot air temperature, so that the temperature of the ultraviolet curable resin composition rises, the resin viscosity decreases, and the fluidity increases.

Irradiation conditions vary depending on each lamp, but the irradiation amount of active rays is usually in the range of 50 to 1000 mJ / cm ² , preferably in the range of 50 to 300 mJ / cm ² .

Further, when irradiating active rays, it is preferably performed while applying tension in the film transport direction, more preferably while applying tension in the width direction. The tension to be applied is usually in the range of 30 to 500 N / m, preferably in the range of 30 to 300 N / m. The method for applying the tension is not particularly limited, and the tension may be applied in the conveying direction on the back roller, or the tension may be applied in the width direction or biaxial direction by a tenter. Thereby, a film having further excellent flatness can be obtained.

The hard coat layer may contain a conductive agent for imparting antistatic properties, and preferred conductive agents include metal oxide particles or π-conjugated conductive polymers. An ionic liquid is also preferably used as the conductive compound.

The fluorine-siloxane graft polymer refers to a copolymer polymer obtained by grafting polysiloxane and / or organopolysiloxane containing siloxane and / or organosiloxane alone on at least a fluorine resin. Examples of commercially available products include ZX-022H, ZX-007C, ZX-049, ZX-047-D manufactured by Fuji Kasei Kogyo Co., Ltd.

The silicone-based surfactant is a surfactant obtained by substituting a part of the methyl group of the silicone oil with a hydrophilic group. Examples of the hydrophilic group include polyether, polyglycerin, pyrrolidone, betaine, sulfate, phosphate, and quaternary salt. Specific products of silicone surfactants include, for example, SH200, BY16-873, PRX413 (dimethylsilicone oil; manufactured by Toray Dow Corning Silicone Co., Ltd.), SH203, SH230, SF8416 (alkyl-modified silicone oil; Toray Dow) Corning Silicone Co., Ltd.), SF8417, BY16-208, BY16-209, BY16-849, BY16-872, FZ-2222, FZ-2207 (dimethylpolysiloxane / polyethylene oxide linear block copolymer; Nippon Unicar ( FZ series), KF-101, KF-102, KF-105 (epoxy-modified silicone oil; manufactured by Shin-Etsu Chemical Co., Ltd.), BYK-UV3500, BYK-UV3510, BYK-333, BYK-33 , BYK-337 (polyether-modified silicone oil, manufactured by BYK Japan KK), but like without limitation.

These components are preferably added in a range of 0.01 to 5% by mass with respect to the solid component in the coating solution.

(Surface shape of hard coat layer)
The surface of the hard coat layer according to the present invention has an arithmetic average roughness Ra in the range of 4 to 20 nm from the viewpoint of excellent antiblocking effect when wound with a long film, and excellent adhesion to the glass scattering prevention film and the adhesive layer. It is preferable.

Arithmetic average roughness Ra is a value measured with an optical interference surface roughness meter (RST / PLUS, manufactured by WYKO) based on JIS B0601: 1994.

Further, the uneven average interval Sm is preferably in the range of 3 to 40 μm. Further, the ratio (Ra / Sm) between the arithmetic average roughness Ra of the hard coat layer and the average irregularity spacing Sm of the hard coat layer coating surface of the glass scattering prevention film is 2 × 10 ⁻⁴ to 6 × 10 ^−3. It is preferable that it is the range of these.

Sm can be measured with an optical interference surface roughness meter (RST / PLUS, manufactured by WYKO) based on the provisions of JIS B0601: 1994, similarly to the arithmetic average roughness Ra.

In order to set the arithmetic average roughness Ra within the above range, a method of forming protrusions on the surface by pressing a mold, a method of forming surface irregularities by mixing resins having different SP values (solubility parameters), spinodal decomposition, A method of forming protrusions by nucleation or the like can be used.

In addition, as the mold roller used for forming the protrusions, those having fine irregularities and those having fine irregularities can be appropriately selected and applied, and patterns, mats, lenticular lenses, and spherical irregularities are regularly or randomly arranged. Can be used.

Further, the haze value of the hard coat film of the present invention is preferably 1% or less from the standpoint of clearness in that sufficient brightness and high contrast can be obtained.

<Functional layer>
The glass scattering prevention film according to the present invention can be provided with functional layers such as a backcoat layer, an antireflection layer, and an antiglare layer in addition to the hard coat layer.

(Back coat layer)
You may provide a backcoat layer in the surface on the opposite side to the side which provided the hard-coat layer of the glass scattering prevention film which concerns on this invention in order to prevent a curl and blocking.

In terms of curling and blocking prevention, the back coat layer includes silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, tin oxide, indium oxide, Particles such as zinc oxide, ITO, hydrated calcium silicate, aluminum silicate, magnesium silicate and calcium phosphate can be added.

The particles contained in the backcoat layer are preferably in the range of 0.1 to 50% by mass with respect to the binder. When the back coat layer is provided, the increase in haze is preferably 0.5% or less, and particularly preferably 0.1% or less. As the binder, a cellulose ester resin is preferable. Moreover, it is preferable that the coating composition for forming the backcoat layer contains a solvent for alcohols, ketones and / or acetate ester sugars.

(Antireflection layer)
The glass scattering prevention film according to the present invention can be used as an antireflection film having an external light antireflection function by coating an antireflection layer on the hard coat layer.

The antireflection layer is preferably laminated in consideration of the refractive index, the film thickness, the number of layers, the layer order, and the like so that the reflectance is reduced by optical interference. The antireflection layer is composed of a low refractive index layer having a lower refractive index than the protective film as the support, or a combination of a high refractive index layer and a low refractive index layer having a higher refractive index than the protective film as the support. Preferably it is. Particularly preferably, it is an antireflection layer composed of three or more refractive index layers. Three layers having different refractive indexes from the support side are divided into medium refractive index layers (high refractive index layers having a higher refractive index than the support). Are preferably laminated in the order of a layer having a lower refractive index) / a high refractive index layer / a low refractive index layer. Alternatively, an antireflection layer having a layer structure of four or more layers in which two or more high refractive index layers and two or more low refractive index layers are alternately laminated is also preferably used.

As the layer structure of the antireflection film, the following structure can be considered, but it is not limited to this.

Glass scattering prevention film / hard coat layer / low refractive index layer Glass scattering prevention film / hard coat layer / medium refractive index layer / low refractive index layer Glass scattering prevention film / hard coat layer / medium refractive index layer / high refractive index layer / Low refractive index layer Glass scattering prevention film / hard coat layer / high refractive index layer (conductive layer) / low refractive index layer (low refractive index layer)
The low refractive index layer preferably contains silica-based fine particles, and the refractive index is preferably in the range of 1.30 to 1.45 when measured at 23 ° C. and wavelength of 550 nm.

The film thickness of the low refractive index layer is preferably in the range of 5 nm to 0.5 μm, more preferably in the range of 10 nm to 0.3 μm, and most preferably in the range of 30 nm to 0.2 μm.

The composition for forming a low refractive index layer preferably contains at least one kind of particles having an outer shell layer and porous or hollow inside as silica-based fine particles. In particular, the particles having the outer shell layer and porous or hollow inside are preferably hollow silica-based fine particles.

The composition for forming a low refractive index layer may contain an organosilicon compound represented by the following general formula (OSi-1) or a hydrolyzate thereof, or a polycondensate thereof.

General formula (OSi-1): Si (OR) ₄
In the organosilicon compound represented by the general formula, R represents an alkyl group having 1 to 4 carbon atoms. Specifically, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane and the like are preferably used.

In addition, a silane coupling agent, a curing agent, a surfactant and the like may be added as necessary. Further, it may contain a thermosetting and / or photocurable compound mainly containing a fluorine-containing compound containing a fluorine atom in a range of 35 to 80% by mass and containing a crosslinkable or polymerizable functional group. Specifically, a fluorine-containing polymer or a fluorine-containing sol-gel compound is used. Examples of the fluorine-containing polymer include hydrolysates and dehydration condensates of perfluoroalkyl group-containing silane compounds [eg (heptadecafluoro-1,1,2,2-tetrahydrodecyl) triethoxysilane], and fluorine-containing monomers. Examples thereof include fluorine-containing copolymers having units and cross-linking reactive units as constituent units. In addition, you may add a solvent, a silane coupling agent, a hardening | curing agent, surfactant, etc. as needed.

(High refractive index layer)
The refractive index of the high refractive index layer is preferably adjusted to a range of 1.4 to 2.2 by measuring at 23 ° C. and a wavelength of 550 nm. The thickness of the high refractive index layer is preferably in the range of 5 nm to 1 μm, more preferably in the range of 10 nm to 0.2 μm, and most preferably in the range of 30 nm to 0.1 μm. The means for adjusting the refractive index can be achieved by adding metal oxide fine particles and the like. Metal oxide The metal oxide fine particles used preferably have a refractive index in the range of 1.80 to 2.60, and more preferably in the range of 1.85 to 2.50.

The kind of metal oxide fine particles is not particularly limited, and Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P and S A metal oxide having at least one element selected from the group consisting of Al, In, Sn, Sb, Nb, a halogen element, Ta and the like is doped with a minute amount of atoms. May be. A mixture of these may also be used. In the present invention, at least one metal oxide fine particle selected from among zirconium oxide, antimony oxide, tin oxide, zinc oxide, indium-tin oxide (ITO), antimony-doped tin oxide (ATO), and zinc antimonate is used. It is particularly preferable to use it as the main component. In particular, it is preferable to contain zinc antimonate particles.

The average particle diameter of primary particles of these metal oxide fine particles is in the range of 10 to 200 nm, particularly preferably in the range of 10 to 150 nm. The average particle diameter of the metal oxide fine particles can be measured from an electron micrograph taken with a scanning electron microscope (SEM) or the like. You may measure by the particle size distribution meter etc. which utilize a dynamic light scattering method, a static light scattering method, etc. If the particle size is too small, aggregation tends to occur and the dispersibility deteriorates. If the particle size is too large, the haze is remarkably increased. The shape of the metal oxide fine particles is preferably a rice grain shape, a spherical shape, a cubic shape, a spindle shape, a needle shape, or an indefinite shape.

The metal oxide fine particles may be surface-treated with an organic compound. By modifying the surface of the metal oxide fine particles with an organic compound, the dispersion stability in an organic solvent is improved, the dispersion particle size can be easily controlled, and aggregation and sedimentation over time can be suppressed. . Therefore, the surface modification amount with a preferable organic compound is in the range of 0.1 to 5% by mass, more preferably in the range of 0.5 to 3% by mass with respect to the metal oxide particles. Examples of the organic compound used for the surface treatment include polyols, alkanolamines, stearic acid, silane coupling agents, and titanate coupling agents. Of these, silane coupling agents are preferred. Two or more kinds of surface treatments may be combined. The high refractive index layer may contain a π-conjugated conductive polymer. The π-conjugated conductive polymer can be used as long as it is an organic polymer having a main chain composed of a π-conjugated system. Examples thereof include polythiophenes, polypyrroles, polyanilines, polyphenylenes, polyacetylenes, polyphenylene vinylenes, polyacenes, polythiophene vinylenes, and copolymers thereof. From the viewpoint of ease of polymerization and stability, polythiophenes, polyanilines, and polyacetylenes are preferable.

The π-conjugated conductive polymer can provide sufficient conductivity and solubility in a binder resin even if it is not substituted, but in order to further improve conductivity and solubility, an alkyl group, a carboxy group, a sulfo group, an alkoxy group. A functional group such as a group, a hydroxy group, or a cyano group may be introduced.

Moreover, you may contain an ionic compound. Examples of the ionic compound include imidazolium-based, pyridium-based, alicyclic amine-based, aliphatic amine-based, aliphatic phosphonium-based cations and inorganic ion-based compounds such as BF ₄ ⁻ and PF ₆ ⁻ , CF ₃ SO ₂ ^{−, and the like.} , (CF ₃ SO ₂ ) ₂ N ⁻ , CF ₃ CO ₂ ^—, etc. The ratio of the polymer to the binder is preferably in the range of 10 to 400 parts by weight with respect to 100 parts by weight of the polymer, and particularly preferably in the range of 100 to 200 parts by weight of the binder with respect to 100 parts by weight of the polymer. .

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "part" or "%" is used in an Example, unless otherwise indicated, "part by mass" or "mass%" is represented.

Example 1
<Production of touch panel module>
An ITO film having a thickness of 20 nm was formed on the tempered glass by a sputtering method, and a first electrode pattern in the X direction was formed by etching.

Next, SiO ₂ is formed as an insulating layer disposed between the electrode patterns by sputtering to a thickness of 200 nm, and an ITO film is formed thereon by sputtering so as to have a thickness of 20 nm. Then, the second electrode pattern in the Y direction was formed in a lattice shape by etching. Further thereon, SiO ₂ was deposited as an insulating layer to a thickness of 200 nm by sputtering.

The electrode pattern in the X direction and the Y direction of the formed ITO was connected to a control circuit via a lead wire prepared by applying and sintering Ag paste, respectively.

Next, a glass scattering prevention film (cellulose ester film A1) produced under the following conditions was cut out and bonded onto the second electrode pattern via an adhesive layer to produce touch panel module 1.

At that time, the X direction of the electrode pattern was set to 0 °, and the direction of the maximum elastic modulus of the glass scattering prevention film was bonded so as to have an angle shown in Table 1.

<Production of glass scattering prevention film>
<Cellulose ester resin>
Hereinafter, the types and contents of the cellulose ester resins used in the examples are as follows.

CE-1: Cellulose diacetate (acetyl group substitution degree 2.45, Mw 300,000)
CE-2: Cellulose triacetate (acetyl group substitution degree 2.88, Mw 320,000)
CE-3: cellulose acetate propionate (acetyl group substitution degree 1.9, propionyl group substitution degree 0.55, Mw 280,000)
<Preparation of cellulose ester film A1>
<Fine particle dispersion 1>
Silica fine particles (Aerosil R972V manufactured by Nippon Aerosil Co., Ltd.)
11 parts by mass Ethanol 89 parts by mass The above was stirred and mixed with a dissolver for 50 minutes, and then dispersed with Manton Gorin.

<Fine particle addition liquid 1> The fine particle dispersion liquid 1 was slowly added to the dissolution tank containing methylene chloride while sufficiently stirring. Further, the particles were dispersed by an attritor so that the secondary particles had a predetermined particle size. This was filtered through Finemet NF manufactured by Nippon Seisen Co., Ltd. to prepare a fine particle additive solution 1.

Methylene chloride 99 parts by mass Fine particle dispersion 1 5 parts by mass <Main dope A>
A main dope A having the following composition was prepared. First, methylene chloride and ethanol were added to the pressure dissolution tank. Next, cellulose acetate was added to the pressurized dissolution tank containing the solvent while stirring. This was completely dissolved with heating and stirring. This was designated as Azumi Filter Paper No. The main dope A was prepared by filtration using 244.

Methylene chloride 340 parts by mass Ethanol 64 parts by mass CE-1 Cellulose diacetate (average acetyl group substitution degree 2.45, Mw 300,000) 100 parts by mass Polyester compound AP-16 6 parts by mass Sugar ester compound 1-3 6 parts by mass Fine particles 1 part by mass or more of additive solution 1 was put into a sealed container and dissolved while stirring to prepare a dope. Then, using an endless belt casting apparatus, the dope was cast uniformly on a stainless steel belt support at a temperature of 33 ° C. and a width of 1500 mm. The temperature of the stainless steel belt was controlled at 30 ° C.

On the stainless steel belt support, the solvent was evaporated until the amount of residual solvent in the cast (cast) film reached 75%, and then peeled off from the stainless steel belt support with a peeling tension of 130 N / m.

The peeled cellulose ester film was stretched 15% in the width direction using a tenter while applying heat at 160 ° C. The residual solvent at the start of stretching was 15%. Next, drying was completed while the drying zone was conveyed by a number of rollers. The drying temperature was 130 ° C. and the transport tension was 100 N / m. After drying, it was slit into a width of 1.5 m, a knurling process with a width of 10 mm and a height of 10 μm was applied to both ends of the film, wound into a roll, and a cellulose ester film A1 having a dry film thickness of 40 μm was obtained. The winding length was 5000 m.

The direction of the maximum elastic modulus of the cellulose ester film A1 was measured by the following measurement method, and as a result, was the width direction as in the stretching direction.

Further, as a result of measuring the phase difference by the following measuring method, the in-plane phase difference Ro was 50 nm, and the slow axis was in the width direction as in the stretching direction.

<Preparation of cellulose ester films A2 to A5>
Cellulose ester films A2 to A5 were prepared in the same manner as the cellulose ester film A1, except that the resin (type and degree of substitution) and the draw ratio were changed as described in Table 1.

<Production of COP film>
<Synthesis of polymer resin having alicyclic structure>
Under an ethylene atmosphere, toluene and a phenylnorbornene-toluene solution were put in an autoclave having a volume of 1.6 l so that the phenylnorbornene concentration was 20 mol / l and the total liquid volume was 640 ml. Methylaluminoxane (manufactured by Albemarle, MAO 20% toluene solution) was added with 5.88 mmol and methylene (cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride 1.5 μmol based on Al, ethylene was introduced and pressure was added. Was kept at 0.2 MPa for 60 minutes at 80 ° C.

After completion of the reaction, ethylene was depressurized while allowing to cool and the system was replaced with nitrogen. Thereafter, 3.0 g of silica (manufactured by Fuji Silysia Co., grade: G-3 particle size: 50 μm) with the adsorbed water content adjusted to 10% by mass was added and reacted for 1 hour. The reaction solution was placed in a pressure filter (Advantech Toyo Co., Ltd., model KST-90-UH) set with filter paper (5C, 90 mm) and Celite (Wako Pure Chemical Industries, Ltd.), and pressure filtered with nitrogen for polymerization. The liquid was collected. The polymerization solution was dropped dropwise in 5 times amount of acetone and deposited to obtain a polymer resin COP1 having an alicyclic structure. COP1 had a weight average molecular weight of 142,000 and a glass transition temperature of 140 ° C.

The polymer resin COP1 having an alicyclic structure synthesized above is dried for 2 hours at 70 ° C. using a hot air dryer in which air is circulated to remove moisture, and then resin melt kneaded with a 65 mmφ screw A COP film having a film thickness of 100 μm was extruded using a T-die film melt extrusion molding machine (T-die width 500 mm) having a machine under molding conditions of a molten resin temperature of 240 ° C. and a T-die temperature of 240 ° C.

Next, the peeled COP film was stretched 90% in the width direction using a tenter while applying heat at 200 ° C. Next, drying was completed while the drying zone was conveyed by a number of rollers. The drying temperature was 130 ° C. and the transport tension was 100 N / m. After drying, the film was slit to a width of 1.5 m, a knurling process having a width of 10 mm and a height of 10 μm was applied to both ends of the film, wound into a roll, and a COP film having a dry film thickness of 40 μm was obtained. The winding length was 5000 m.

The direction of the maximum elastic modulus of the COP film was measured by the following measurement method, and as a result, it was in the width direction as in the stretching direction.

Further, as a result of measuring the retardation of the COP film by the following measuring method, the in-plane retardation value Ro was 135 nm, and the slow axis was in the width direction.

<PC film>
In a reactor equipped with a thermometer, a stirrer, and a reflux condenser, 152400 parts of ion-exchanged water and 84320 parts of 25% aqueous sodium hydroxide solution were added, and 9,9-bis (4-hydroxy-3 having a purity of 99.8% by HPLC analysis. -Methylphenyl) fluorene (hereinafter abbreviated as “biscresol fluorene”) 34848 parts, 2,2-bis (4-hydroxyphenyl) propane 9008 parts (hereinafter abbreviated as “bisphenol A”) and After dissolving 88 parts of hydrosulfite, 178400 parts of methylene chloride was added, and 18248 parts of phosgene was blown in at a temperature of 15 to 25 ° C. with stirring for 60 minutes. After the completion of phosgene blowing, a solution obtained by dissolving 177.8 parts of p-tert-butylphenol in 2640 parts of methylene chloride and 10560 parts of a 25% aqueous sodium hydroxide solution were added. After emulsification, 32 parts of triethylamine was added and the mixture was added at 28 to 33 ° C. The reaction was terminated by stirring for a period of time. After completion of the reaction, the product is diluted with methylene chloride, washed with water, acidified with hydrochloric acid and washed with water. When the conductivity of the aqueous phase is almost the same as that of ion-exchanged water, the methylene chloride phase is concentrated and dehydrated to obtain polycarbonate. A solution with a concentration of 20% was obtained. The polycarbonate (copolymer A) obtained by removing the solvent from this solution had a molar ratio of biscresol fluorene to bisphenol A of 70:30 (polymer yield 97%). In addition, this polymer had an intrinsic viscosity of 0.674 and a Tg of 226 ° C.

25 parts by mass of the polycarbonate was dissolved with stirring at 25 ° C. with respect to 75 parts by mass of a mixed solvent of methylene chloride and ethanol containing 4 parts by mass of ethanol to obtain a transparent and viscous dope. The dope was cast on a 100 m stainless steel belt, which was blown with dry air and the dew point was controlled to 12 ° C. or less, and was peeled off. The residual solvent concentration at that time was 35%. From the fact that the peelability was good and the charge was small, no peeling step or peeling streaks were observed on the film surface by visual observation. Thereafter, when the residual solvent concentration was 2%, the film was stretched twice in the width direction and then dried while maintaining the width. Then, it dried until the residual solvent density | concentration became 1% or less, and obtained the PC film with a width | variety of 1.5 m and a dry film thickness of 40 micrometers. The winding length was 5200 m.

The direction of the maximum elastic modulus of the PC film was measured by the following measurement method, and as a result, it was in the width direction as in the stretching direction.

The retardation of the PC film was measured by the following measurement method. As a result, the in-plane retardation Ro was 140 nm, and the slow axis was in the width direction.

<PET film>
<Polyester A>
To 100 parts by mass of dimethyl terephthalate and 64 parts by mass of ethylene glycol, 0.1 part by mass of calcium acetate hydrate was added, and transesterification was performed by a conventional method. The obtained product was mixed with ethylene glycol solution of 5-sodium sulfodi (β-hydroxyethyl) isophthalic acid (concentration 35% by mass) (7 mol% / total dicarboxylic acid component), polyethylene glycol (number average molecular weight 3000). 5.8 parts by mass (5% by mass / generated polyester), 0.05 parts by mass of antimony trioxide, and 0.13 parts by mass of trimethyl phosphate. Next, the temperature was gradually raised and the pressure was reduced, and polymerization was carried out at 280 ° C. and 40 Pa to obtain polyester A. The intrinsic viscosity was determined according to the method shown below. As a result, the intrinsic viscosity was 0.50.

The intrinsic viscosity was calculated according to the following procedure using an Ubbelohde viscometer. Using a mixed solvent of phenol and 1,1,2,2-tetrachloroethane having a mass ratio of about 55:45 (adjusted to a flow time of 42.0 ± 0.1 seconds), the sample was dissolved to a concentration of 0.2 , 0.6, 1.0 (g / dl) solution (temperature 20 ° C.). The specific viscosity (ηsp) at each concentration (C) was determined by an Ubbelohde viscometer, and the equation [ηsp / C] was extrapolated to a concentration of zero (C → 0) to determine the intrinsic viscosity [η]. The unit of intrinsic viscosity [η] is dl / g.

The polyester A pellets were vacuum-dried at 150 ° C. for 8 hours, melt-extruded at 285 ° C. using an extruder, closely adhered to a 30 ° C. cooling drum while electrostatically applied, and cooled and solidified to obtain an unstretched sheet. It was. This unstretched sheet was stretched 2.0 times in the longitudinal direction at 90 ° C. using a roller-type longitudinal stretching machine. The temperature difference between the front and back surfaces was within 5 ° C.

The obtained uniaxially stretched film was stretched 1.2 times in the transverse direction at 100 ° C. using a tenter-type transverse stretching machine. Next, heat treatment was performed at 70 ° C. for 2 seconds, heat-fixed at 150 ° C. for the first heat setting zone for 10 seconds, heat-fixed for 15 seconds at the second heat setting zone at 180 ° C., and then 2% in the width direction at 160 ° C. A PET film having a width of 1.5 m and a dry film thickness of 60 μm was prepared by performing relaxation treatment. The winding length was 5000 m.

The direction of the maximum elastic modulus of the PET film was measured by the following measurement method, and as a result, it was in the longitudinal direction as in the stretching direction.

Moreover, as a result of measuring the retardation of the PET film by the following measurement method, the in-plane retardation value Ro was 130 nm, and the slow axis was in the longitudinal direction.

Touch panel modules 2 to 16 were produced in the same manner using the produced cellulose ester films A2 to A5, COP film, PC film, and PET film.

<Production of liquid crystal display panel>
The liquid crystal display panel was carefully peeled off from the commercially available liquid crystal display device with a touch panel.

Further, when the direction of the absorption axis of the polarizing plate bonded to the liquid crystal display device was measured, it was parallel to the transparent electrode forming direction (X direction) of the touch panel module.

Next, the produced touch panel module 1 is bonded to a liquid crystal display panel through the following adhesive so that the transparent electrode forming direction (X direction) is the same direction, and the liquid crystal display device 1 with a touch panel is produced. did.

SVR1240 manufactured by Sony Chemical & Information Device Co. was applied to the surface of the touch panel module film.

Next, the touch panel module was bonded to the liquid crystal display panel via the applied SVR 1240 and temporarily fixed by irradiating a part of it with ultraviolet rays. After inspecting for bubbles at the interface, the entire surface was irradiated with ultraviolet rays and completely cured, and the touch panel module and the liquid crystal display panel were permanently fixed to produce a liquid crystal display device 1 with a touch panel.

Similarly, the touch panel modules 2 to 16 produced using the cellulose ester films A2 to A5, COP film, PC film, and PET film in Table 1 were bonded to the liquid crystal display panels, respectively. 16 was produced.

<Evaluation of glass scattering prevention film>
[Evaluation of elastic modulus]
The elastic modulus of the glass scattering prevention film was measured by conditioning the sample for 24 hours in an environment of 23 ° C. and 55% RH, and according to the method described in JIS K7127, Tensilon RTA manufactured by Orientec Co., Ltd. Elastic modulus was determined using -100. The shape of the test piece is No. 1 test piece, the test speed is 10 mm / min, and the maximum elastic modulus is the maximum elastic modulus obtained by measuring from 0 ° to 15 ° in any direction. Further, the direction was defined as the direction of the maximum elastic modulus.

[Evaluation of phase difference]
(Slow axis direction)
The average refractive index in the plane at an optical wavelength of 590 nm was measured under an environment of a temperature of 23 ° C. and a relative humidity of 55% RH with an Abbe refractometer (1T) to determine the direction of the slow axis.

(Phase difference: measurement of retardation)
The in-plane retardation value Ro was obtained by the following equation.

Formula (i): Ro = (n _x −n _y ) × d (nm)
Here, d is the thickness of the film (nm), _(refractive index in a slow axis direction) refractive index n _x, a n y _(refractive index of the direction perpendicular to the slow axis in the film plane).

The retardation value Ro was measured using an automatic birefringence meter KOBRA-21AWR (Oji Scientific Instruments).

<Evaluation of LCD with touch panel>
(1) Evaluation of crack prevention property of ITO electrode 1000 liquid crystal display devices with a touch panel were continuously produced, the occurrence of ITO cracks was visually evaluated, and the generation ratio was measured.

◎: Less than 1% ○: 1% or more and less than 3% △: 3% or more and less than 5% ×: 5% or more The production tolerance is ◯ or more.
(2) Glass scattering prevention property After bonding cellulose ester films A1 to A5, COP film, PC film, and PET film as glass scattering prevention films on a glass plate having a length of 150 mm, a width of 170 mm, and a thickness of 1 mm, respectively, A laminated body composed of this glass plate and a glass scattering prevention film on a 10-mm-thick stand, the glass scattering prevention film faces upward (the direction opposite to the above-mentioned stage), and from one end in the long side direction of the laminated body Place the 10mm part (one end) in an arched state, drop an iron ball with a diameter of 31.75mm from a height of 30cm to the one end, and visually observe the scattering of the glass. Observed.

This test was repeated 20 times. When the film was not torn at all, it was evaluated as ○, when the film was torn within 3 times in 20 times, and when the film was torn 4 times or more in 20 times as x. In evaluation of x, it cannot be used as a glass scattering prevention film.

From the contents of Table 1, the liquid crystal display devices 1 to 10 with a touch panel according to the present invention are superior in preventing the ITO electrode from cracking and preventing glass scattering compared to the liquid crystal display devices 11 to 16 with a touch panel of the comparative example. It can be seen that it is excellent.

The liquid crystal display device 4 with a touch panel according to the present invention was slightly inferior in preventing glass scattering because the angle for bonding the direction of the maximum elastic modulus of the glass scattering preventing film was 105 °.

Example 2
<Coating of hard coat layer>
Extrusion coater obtained by filtering the following hard coat layer composition 1 with a polypropylene filter having a pore size of 0.4 μm on the surface of each of the produced cellulose ester films A1 to A5, COP film, PC film, and PET film After drying at a temperature of 80 ° C. and applying a nitrogen purge so that the atmosphere has an oxygen concentration of 1.0% by volume or less, the irradiation part is irradiated at an illuminance of 100 mW / cm ² using an ultraviolet lamp. The coating layer is cured with an amount of 0.25 J / cm ² , a hard coat layer 1 having a dry film thickness of 3 μm is formed and wound, and roll-shaped hard coat films A1H to A5H, COP film H, PC film H, PET Film H was produced.

<Hard coat layer composition 1>
The following materials were stirred and mixed to obtain hard coat layer coating composition 1.

Pentaerythritol tri / tetraacrylate (NK Ester A-TMM-3L, manufactured by Shin-Nakamura Chemical Co., Ltd.) 50 parts by mass Urethane acrylate (Beam Set 575CB, manufactured by Arakawa Chemical Industries, Ltd.) 50 parts by mass Irgacure 184 (BASF Japan) 2 parts by weight Polyether-modified polydimethylsiloxane (BYK-UV3510, manufactured by Big Chemie Japan) 1 part by weight Cyclohexanone 10 parts by weight Methyl ethyl ketone 93 parts by weight Hard coat films A1H to A5H, COP film H , PC film H, and PET film H were used to produce a touch panel module in the same manner as in the liquid crystal display devices 1 to 16 with a touch panel of Example 1, and the liquid crystal display via SVR 1240 It was stuck to the panel.

Using the prepared hard coat films A1H to A5H, COP film H, PC film H, and PET film H, liquid crystal display devices 1b to 16b with a touch panel were prepared in the same manner as in Example 1, and the ITO electrode used in Example 1 was prepared. Evaluation of cracking prevention property was performed. As a result, the liquid crystal display devices 11b to 16b with the touch panel of the comparative example did not improve the prevention of cracking of the ITO electrode, but the liquid crystal display devices 1b to 10b with the touch panel of the present invention were good in Example 1. The results were all the results of ◎, and it was found that the protective property against the ITO electrode was further improved by coating the hard coat layer.

Example 3
Using the liquid crystal display devices 1 to 13 with a touch panel prepared in Example 1, the liquid crystal display portion was observed without wearing polarized sunglasses.

When the liquid crystal display unit was observed by wearing polarized sunglasses, the liquid crystal display devices with a touch panel 11 to 13 of the comparative example had poor visibility, but the liquid crystal display devices with a

touch panel

1, 2, and 6 to 10 of the present invention were used. Since the retardation value of the glass scattering prevention film is within a preferable range and is bonded to the liquid crystal display panel at a preferable angle, the image has good visibility without being lost. In the liquid crystal display devices 3 to 5 with a touch panel of the present invention, the visibility of sunglasses was somewhat inferior because the retardation value of the glass scattering prevention film was insufficient.
(3) Polarized sunglasses visibility evaluation ◎: Good visibility ○: Good visibility, but the image may be chipped depending on the angle △: The angle at which the image is chipped is slightly large ×: The angle at which the image is chipped is large, and the visibility is high Bad

The liquid crystal display device with a touch panel of the present invention has a function to prevent scattering of the glass substrate, and further includes a glass scattering prevention film for preventing the ITO electrode from cracking. A liquid crystal display device can be provided.

DESCRIPTION OF SYMBOLS 1 Glass substrate 2 1st electrode pattern 3 Insulating layer 4 2nd electrode pattern 5 Adhesion layer 6 Glass scattering prevention film 7 Hard-coat layer T Touch panel module 8 Adhesion layer 9 Liquid crystal display panel 10 1st electrode pattern (X direction)
11 Second electrode pattern (Y direction)
12 Maximum elastic modulus direction of glass shatterproof film

Claims

A liquid crystal display device with a touch panel having a touch panel module and a liquid crystal display panel, wherein the touch panel module is an outermost glass substrate and a pair of transparent conductive films formed in a lattice shape in the X direction and the Y direction perpendicular thereto And a glass scattering prevention film on the upper surface thereof, and the direction of the maximum elastic modulus of the glass scattering prevention film is oblique to the X direction or the Y direction of the pair of transparent conductive films formed in the lattice shape A liquid crystal display device with a touch panel.
When the direction of the maximum elastic modulus of the glass scattering prevention film is 0 ° with respect to one of the X direction and the Y direction of the pair of transparent conductive films formed in the lattice shape, 2. The liquid crystal display device with a touch panel according to claim 1, wherein the liquid crystal display device is in an oblique direction at an angle within a range of 70 ° or within a range of 110 to 160 °.
The liquid crystal display device with a touch panel according to claim 1 or 2, wherein the glass scattering prevention film has a hard coat layer containing an acrylic resin.
The in-plane retardation value Ro of the glass scattering prevention film is in the range of 0 to 100 nm in a measurement at a light wavelength of 590 nm under an environment of a temperature of 23 ° C. and a relative humidity of 55% RH. The liquid crystal display device with a touch panel as described in any one of Claims 1-3.
The in-plane retardation value Ro of the glass scattering prevention film is in the range of 105 to 160 nm when measured at a light wavelength of 590 nm in an environment of a temperature of 23 ° C. and a relative humidity of 55% RH. The phase axis is an oblique direction at an angle in the range of 20 to 70 ° or in the range of 110 to 160 ° with respect to the absorption axis of the polarizing plate of the liquid crystal display panel. 4. A liquid crystal display device with a touch panel according to any one of items 3 to 3.
The liquid crystal display device with a touch panel according to any one of claims 1 to 5, wherein the glass scattering prevention film is a cellulose ester film.
The liquid crystal display device with a touch panel according to claim 6, wherein the cellulose ester film contains cellulose diacetate having an acetyl group substitution degree in the range of 2.0 to 2.5.