CN108369356A - special-shaped display device - Google Patents

Abstract

Display picture is that the liquid crystal display device of the shape different from rectangle and square has：IPS units and each polarizing film from IPS units described in sandwich.IPS units have：The common electrode (108) of the pixel electrode (110) and the strip being alternately arranged with pixel electrode (110) placed with strip in the display area P of 1 pixel.The thickness of each polarizing film is respectively 20 μm or more and 65 μm or less.Each polarizing film has polarizer and each optical film from polarizer described in sandwich.The value of Log (tan δ) in each optical film of each polarizing film between 40 DEG C to 100 DEG C is 1.8 or more.

Description

Special-shaped display device

Technical field

The present invention relates to the special-shaped display devices that display picture is the shape different from rectangle and square.

Background technology

In recent years, it with the various electronic equipment multifunctions such as mobile terminal, digital signature and diversification, is set to electronics In being introduced into of standby new value, show that the narrow frame of picture attracts attention.If the propulsion of narrow frame technology gone down, The design of electronic equipment can not only be improved, and can will easily show that the shape of picture changes into rectangle and pros Shape (hereinafter also referred to profiled shape) other than shape.Its reason is：Such as by that will show that required circuit, wiring configure (frame region for not being configured at the outside of display picture) and realizes narrow frame in display picture, therefore even if makes display picture Face is profiled shape, and the circuit etc. of signal that also can be needed for the driving by pixel out of display picture is supplied to display picture End.The display device for making display picture become profiled shape in this way is known as special-shaped display device herein.Abnormity is shown For device, especially in the instrument board of vehicle (instrument face plate), want to show in design in the field of feature Study its application.

On the other hand, as visual field angular width, the display device for the display for carrying out high image quality, it is known that IPS types (In Plane Switching liquid crystal display device) (referring for example to patent document 1).By the display picture for making the liquid crystal display device of IPS types Face is profiled shape, can expect the realization of the excellent special-shaped display device of visibility.

Existing technical literature

Patent document

Patent document 1：Japanese Unexamined Patent Publication 2015-114377 bulletins (with reference to claim 1, paragraph [0011], Fig. 1 etc.)

Invention content

The subject that the invention solves

In the case of constituting special-shaped display device, each polarizing film is rushed from sandwich IPS units with 2 polarizing films It is cut into shape, the i.e. profiled shape of display picture.At this point, if the thickness of polarizing film is thick, it is easy in polarizing film when being punched It cracks, it is thin that therefore, it is desirable to polarizing films.That is, from the viewpoint of improving cutting, it is desirable to keep polarizing film thinning.

But if keeping polarizing film thinning, the durability of polarizer reduces.That is, in the instrument board etc. of above-mentioned vehicle It is vehicle-mounted on the way, the sometimes interior condition that can become high temperature and humidity, the use environment as imagination and carried out damp and hot durable When experiment, if polarizing film is thin, the color of the polarizer dyed, which becomes easy, to fall off, polarizer deterioration.

It is reduced in order to avoid the durability of such polarizer, needs to make the dyeing of polarizer to thicken.But if make The dyeing of polariscope thickens, then the decrease in transmission of polarizer, shows that the brightness of image reduces.Therefore, it is intended that by IPS units Composition on work hard compensate display image brightness reduction.

In addition, for the polarizer (such as polyvinyl alcohol film) of polarizing film, by the change of the viscosity caused by temperature change Change big.Therefore, for 2 optical films of clamping polarizer, and if big by the variation of the viscosity caused by temperature, due to Temperature change cracks in polarizing film sometimes.

The present invention completes to solve the problem above-mentioned, and its purpose is to provide special-shaped display device, the abnormity is aobvious Crackle when showing device can inhibit for polarizing film to be punched into profiled shape and the crackle by the polarizing film caused by temperature change Generation, and even if in the case of the decrease in transmission of polarizer, by improving the transmissivity of IPS units, can also avoid Show the reduction of the brightness of image.

Means for solving the problems

The above-mentioned purpose of the present invention is realized by composition below.

The special-shaped display device that an aspect of of the present present invention is related to is the shape for showing picture and being different from rectangle and square The special-shaped display device of shape,

Have：IPS units and each polarizing film from the above-mentioned IPS units of sandwich,

Above-mentioned IPS units have：In the display area of 1 pixel with strip place pixel electrode and with above-mentioned picture The common electrode for the strip that plain electrode is alternately arranged,

The thickness of above-mentioned each polarizing film be respectively 20 μm or more and 65 μm hereinafter,

Above-mentioned each polarizing film has：Polarizer and each optical film from the above-mentioned polarizer of sandwich,

When by indicating that the loss angle tangent of the ratio between loss modulus and storage modulus is set as tan δ, above-mentioned each polarizing film it is each The value of Log (tan δ) in optical film between -40 DEG C to 100 DEG C is -1.8 or more.

The effect of invention

According to above-mentioned composition, polarizing film is 20 μm of thickness or more and 65 μm below slim, therefore even if that will polarize In the case that piece is punched into profiled shape, it can also inhibit the generation of crackle.In addition, for IPS units, in 1 pixel The common electrode of pixel electrode and strip with strip, these electrodes are placed with being alternately arranged in display area.As a result, with Such as common electrode is formed as planar and makes it that can be realized highly transmissive compared with the composition that the pixel electrode of strip is overlapped The IPS units of rate.Therefore, polarizing film is slim, even if making polarizer in the reduction in order to avoid the durability of polarizer In the case that dyeing thickens, that is, even if the IPS of high-transmission rate can be used if in the case of the decrease in transmission of polarizer Unit come avoid display image brightness reduction.In addition, in each optical film of each polarizing film, between -40 DEG C to 100 DEG C The value of Log (tan δ) is -1.8 or more, and the variation by the viscosity caused by temperature change is small, therefore can inhibit by temperature change The generation of the crackle of caused polarizing film.

Description of the drawings

Fig. 1 is an example i.e. plan view of liquid crystal display device for the special-shaped display device that embodiments of the present invention are related to.

Fig. 2 is the A-A ' lines of Fig. 1 to regarding sectional view.

Fig. 3 is the sectional view for indicating the detailed composition of IPS units possessed by above-mentioned liquid crystal display device.

Pixel electrode in the display area of 1 pixel of above-mentioned IPS units is is amplified the plan view that indicates by Fig. 4.

Fig. 5 is the sectional view of the pixel electrodes and common electrode in above-mentioned display area.

Fig. 6 is to indicate pixel electrode in reference example as present embodiment, 1 pixel display area and share The sectional view of the composition of electrode.

Fig. 7 is the sectional view for the manufacturing process for indicating above-mentioned IPS units.

Specific implementation mode

It is as follows if illustrated based on attached drawing for one embodiment of the present invention.It is explained, this specification In, in the case where numberical range is expressed as A~B, it is specified that for the value containing lower limit A and upper limit B in the numberical range.Give Illustrate, the present invention is not limited to contents below.

[liquid crystal display device]

Fig. 1 is the plan view of an example, that is, liquid crystal display device 1 of special-shaped display device of the present embodiment.Liquid crystal The display picture 1a of showing device 1 becomes the shape (profiled shape) other than rectangle and square.In Fig. 1, display picture 1a's Shape becomes the shape for combining multiple figures, more specifically, become the shape that 2 convex forms are combined in rectangle, Other than such shape, the shapes such as circle, ellipse, triangle, diamond shape, trapezoidal, star are also contemplated for.

Fig. 2 is the A-A ' lines of Fig. 1 to regarding sectional view.For liquid crystal display device 1, with the clamping of 2 polarizing films 3 and 4 with The driven IPS units of IPS modes 2 and constitute, and with the backlight 5 illuminated to IPS units 2.It is explained, for The detailed composition of IPS units 2 will be aftermentioned.In addition, the composition in present embodiment as shown below can be applied to containing FFS The liquid crystal display device of whole IPS modes of (Fringe Field Switching) mode.

For polarizing film 3, relative to IPS units 2, be located at viewable side (opposite side of backlight 5), containing polarizer 11, Protective film 12 and opposed film 13.For polarizer 11, defined rectilinearly polarized light is penetrated.For protective film 12, relatively In polarizer 11, it is located at the opposite side (viewable side) of IPS units 2.For opposed film 13, relative to polarizer 11, it is located at IPS 2 side of unit.That is, protective film 12 and opposed film 13 are the optical films from sandwich polarizer 11.Polarizing film 3 is in 13 side of opposed film It is Nian Jie with IPS units 2 via adhesive layer 6.It is explained, for polarizing film 3, relative to protective film 12, in polarizer 11 Opposite side can also have the functional layers such as hard conating, antiglare layer, anti-reflection layer, antistatic layer.

For polarizing film 4, relative to IPS units 2, it is located at 5 side of backlight, contains polarizer 21, protective film 22 and opposed Film 23.For polarizer 21, defined rectilinearly polarized light is penetrated, is configured in such a way that between axlemolecules are orthogonal with polarizer 11. For protective film 22, relative to polarizer 21, it is located at the opposite side (5 side of backlight) of IPS units 2.For opposed film 23, phase For polarizer 21, it is located at 2 side of IPS units.That is, protective film 22 and opposed film 23 are the optics from sandwich polarizer 21 Film.Polarizing film 4 is Nian Jie with IPS units 2 via adhesive layer 7 in 23 side of opposed film.

[about IPS units]

Fig. 3 is the sectional view for the detailed composition for indicating IPS units 2.For IPS units 2, in above-mentioned patent document In 1 composition, it is equivalent to and common electrode (opposite electrode) is formed as into strip.Hereinafter, the details to IPS units 2 carries out Explanation.

IPS units 2 are pressed from both sides liquid crystal layer 300 with TFT (Thin Film Transistor) substrates 100 and counter substrate 200 It holds and constitutes.TFT substrate 100 and counter substrate 200 are constituted such as the transparent substrate by glass, resin.

First, the composition of 100 side of TFT substrate is illustrated.Gate electrode 101 is formed in TFT substrate 100.Gate electrode 101 with the metal layer of scan line same layer by forming.The insulating film 102 that gate electrode 101 is made of silicon nitride (SiN) covers. On insulating film 102, in the position opposed with gate electrode 101, semiconductor layer 103 is formed.Raceway groove of the semiconductor layer 103 containing TFT Portion.On the semiconductor layer 103, groove is clamped and forms source electrode 104 and drain electrode 105.Source electrode 104 and video signal line Connection, drain electrode 105 are connect with pixel electrode 110.Source electrode 104 and drain electrode 105 are formed by the metal layer of same layer.

TFT contain above-mentioned gate electrode 101, semiconductor layer 103, source electrode 104, drain electrode 105 and constitute.The TFT quilts Inorganic passivating film 106 is formed by by SIN to cover.Inorganic passivating film 106 protects the especially groove of TFT from impurity shadow It rings.On inorganic passivating film 106, the organic passivation film 107 of polyimide resin etc. is formed.Organic passivation film 107 is in protection TFT While also have and make the function of surface planarisation, therefore formed thick.On organic passivation film 107, common electrode 108 is formed Such as the passivating film 109 by formation such as SiN, polyimide resins.The common electrode 108 of the top of TFT is passivated film 109 and covers Lid.

Pixel electrode 110 is formed on passivating film 109, and via the through-hole 111 for being set to passivating film 109 and with TFT's Drain electrode 105 is connected.Video signal is supplied to pixel electrode 110 as a result,.Common electrode 108 and pixel electrode 110 are by conduct ITO (the Indium Tin Oxide) formation of the material of transparent conductive film, in addition, also can be by such as Japanese Unexamined Patent Publication 2011- In-Sn composite oxides described in No. 100749 bulletins are formed.For making what the liquid crystal molecule 301 of liquid crystal layer 300 was orientated to take It is formed in a manner of covering pixel electrode 110 to film 113.

Fig. 4 be by the display area P of 1 pixel (counter substrate 200 not by the area of 202 shading of aftermentioned black matrix Domain) in pixel electrode 110 amplification indicate plan view.It is explained, in the figure, for convenience's sake, is omitted shared The diagram of electrode 108 and passivating film 109.Will in orthogonal 2 directions in display picture 1a (referring to Fig.1) parallel face A direction be set as X-direction, other direction is set as Y-direction.The pixel electrode 110 be connected with drain electrode 105 is in 1 pixel Display area P lateral branches be it is multiple, extend along the X direction in each leisure display area P.Its result is in display area P Interior, pixel electrode 110 is formed as strip (striated).That is, pixel electrode 110 extends along the X direction, and stay in the Y direction It places in a row with interval.

Fig. 5 is the sectional view of the pixel electrode 110 and common electrode 108 in the display area P of 1 pixel.It is explained, In Fig. 5, for convenience's sake, the diagram of alignment films 113 is omitted.As shown in the figure like that, in the P of display area, passivation Film 109 is formed as strip in the P of display area.That is, passivating film 109 extends along the X direction on organic passivation film 107, and It places in a row in the Y direction spacedly.Therefore, organic passivation film 107 constitutes the base for supporting each passivating film 109 from below Bottom.

Above-mentioned pixel electrode 110 is located on the passivating film 109 of strip.In addition, above-mentioned common electrode 108 is organic blunt On change film 107 between adjacent passivating film 109, it is formed extended at both sides in the X direction.Therefore, common electrode 108 become along X-direction extends and is placed with being alternately arranged with pixel electrode 110 in the Y direction.That is, in the P of display area, pixel electricity Pole 110 is not be overlapped with common electrode 108, places with being staggered in the Y direction.

Fig. 6 is 110 and of pixel electrode indicated in reference example as present embodiment, 1 pixel display area P The sectional view of the composition of common electrode 108 corresponds to the composition of patent document 1.In patent document 1, on organic passivation film 107 Common electrode 108 is formed as into planar (full coat shape), after covering common electrode 108 with passivating film 109, in passivating film 109 On pixel electrode 110 is formed as into strip.Therefore, pixel electrode 110 is Chong Die with a part for common electrode 108.Thus, aobvious On showing in the P of region whether pixel electrode 110 is be overlapped with common electrode 108, the composition of the composition and patent document 1 of present embodiment It is different from each other.

Then, the composition of 200 side of counter substrate is illustrated.Inside (the liquid of counter substrate 200 shown in fig. 3 300 side of crystal layer), for each pixel, form the colour filter 201 of red (R), green (G), green (B).Moreover, in adjacent colour filter Black matrix 202 is formd between device 201 and 201.Black matrix 202 is that the photomask of shading is carried out to TFT, prevents photoelectric current from flowing to TFT。

Cover film 203 is formed in a manner of covering colour filter 201 and black matrix 202.Colour filter 201 and black matrix 202 Surface forms bumps, by the way that cover film 203 is arranged, makes surface planarisation.

The alignment films 114 of the initial stage orientation for determining liquid crystal are formed on cover film 203.It is explained, liquid crystal display Device 1 is IPS modes, therefore common electrode 108 is formed in 100 side of TFT substrate as described above, does not have in 200 side of counter substrate It to be formed.

In IPS units 2, conductive film, therefore the current potential of counter substrate 200 are not formed in the inside of counter substrate 200 Become unstable.In addition, invading liquid crystal layer 300 from external electromagnetic noise, image is had an impact.In order to avoid in this way Influence, be formed with surface conductance film 210 in the outside of counter substrate 200.

In the composition of above-mentioned IPS units 2, certain voltage is applied to common electrode 108, pixel electrode 110 is applied Add the voltage being consistent with video signal.If applying a voltage to pixel electrode 110, the liquid of power line, liquid crystal layer 300 is generated Brilliant molecule 301 is rotated up in the side of power line.The direction for controlling liquid crystal molecule 301 in this way, controls in liquid crystal layer 300 Thus image is shown in display picture 1a (referring to Fig.1) by the transmission (transmission of the light from backlight 5) of light.

As described above, in present embodiment, IPS units 2 have：It is placed with strip in the display area P of 1 pixel The common electrode 108 of pixel electrode 110 and the strip being alternately arranged with pixel electrode 110.In this composition, in viewing area In the P of domain, the light from backlight 5 penetrates any one of pixel electrode 110 and common electrode 108, without through the two.That is, In the P of display area, the repeating part of pixel electrode 110 and common electrode 108 is not present, light will not penetrate its repeating part. Pixel electrode 110 is penetrated compared with the composition of Fig. 6 of the repeating part of common electrode 108 with light as a result, can improve the saturating of light Penetrate rate.

In addition, in the P of display area, pixel electrode 110 is not be overlapped with common electrode 108, therefore to pixel electrode 110 and common electrode 108 apply voltage when, can inhibit generate liquid crystal molecule 301 orientation disorder, thus can also improve Cross the transmissivity of the light of liquid crystal layer 300.

That is, the composition of IPS units 2 according to the present embodiment, pixel electrode 110 is not present in the P of display area in (1) With the repeating part of common electrode 108, light will not penetrate its repeating part, and (2) can inhibit the orientation of liquid crystal molecule 301 disorderly Disorderly, therefore the IPS units 2 of high-transmission rate can be realized.

In addition, pixel electrode 110 is located on the passivating film 109 of strip, common electrode 108 is located at adjacent passivating film 109 And between 109, therefore in the display area P of 1 pixel, it can be reliably achieved pixel electrode 110 and common electrode 108 (in the Y direction) composition (composition that the two is not overlapped) being staggered.

It is explained, in figure 3, both inorganic passivating film 106 and organic passivation film 107 is set but it is also possible to be general Any one composition omitted.In this case, above-mentioned basal layer becomes in inorganic passivating film 106 and organic passivation film 107 Any one.In addition, in Fig. 3, the bottom gate for being provided with semiconductor layer 103 on gate electrode 101 in TFT substrate 100 is shown Composition of the composition of pole but it is also possible to be the top grid of setting gate electrode 101 on the semiconductor layer 103.

[manufacturing method of IPS units]

In present embodiment, other than forming common electrode 108 as described above with strip, can use with it is above-mentioned special Sharp document 1 same manufacturing method manufactures IPS units 2.Therefore, in the following, for the manufacturing method of IPS units 2, pair with The different part of patent document 1, i.e. 1 pixel the part of display area P particularly illustrate.

Fig. 7 is the sectional view for the manufacturing process for indicating IPS units 2.First, in the TFT being made of transparent substrates such as glass After being formed from gate electrode 101 to organic passivation film 107 with desired shape on substrate 100 (with reference to Fig. 3), in organic passivation film Passivating film 109 is formed on 107.Then, the ITO layer 110a full coats (ベ of pixel electrode 110 will be used to form on passivating film 109 タ Tu り), then, photoresist 401 is formed as into strip on ITO layer 110a.

Then, it regard the photoresist of strip 401 as mask, wet etching is carried out to ITO layer 110a, strip is consequently formed The pixel electrode 110 being made of ITO.Then, dry ecthing is carried out to passivation layer 109 and becomes strip.

Then, the ITO for being used to form common electrode 108 is sputtered, ITO layer is formed on organic passivation film 107 108a, then, the painting photoresist 402 on ITO layer 108a.

Then, it is handled by ashing, a part for photoresist 402 is decomposed, is removed, it then, will by wet etching A part of the ITO of composition ITO layer 108a and pixel electrode 110 on photoresist 401 remove.Finally, at by ashing Photoresist 401 and 402 is decomposed, is removed by reason.Thus the shared electricity of the pixel electrode 110 with strip and strip is obtained The IPS units 2 of pole 108.

[details about polarizing film]

Then, to being illustrated from 2 polarizing film 3 of sandwich IPS units and 4 details.It is explained, polarizes Polarizer 21, protective film 22, the opposed film 23 of piece 4 are same as the polarizer of polarizing film 3 11, protective film 12, opposed film 13 It constitutes, therefore its details is illustrated by taking polarizing film 3 as an example below, omit the detailed description of polarizing film 4.

For polarizer 11, such as by being dyed to PVA (polyvinyl alcohol) film with dichroism pigment, carrying out high power Rate stretching obtains, and thickness is 15 μm hereinafter, preferably 5~7 μm.

Protective film 12 and opposed film 13 contain such as cellulose esters system resin, cyclic polyolefin resin (COP), gather to benzene two In formic acid glycol ester (PET) resin, acrylic resin at least any one and constitute.The thickness of polarizing film 3 be 20 μm with Upper and 65 μm or less (thickness of polarizing film 4 is also identical).Slim polarizing film 3 is constituted as a result, therefore even from display picture In the case that polarizing film 3 is punched to profiled shape by the shape of 1a (referring to Fig.1), it can also inhibit to generate in polarizing film 3 Crackle.

Particularly, the mechanical strength ratio COP of cellulose esters system resin is contour.Therefore, contain in protective film 12 and opposed film 13 In the case of having cellulose esters system resin and constituting, it can be reliably suppressed and be cracked in the punching of polarizing film 3.

In addition, according to the composition of above-mentioned IPS units 2, can realize the IPS units 2 of high-transmission rate, therefore even if for Avoid polarizing film 3 by it is slim in the case of the reduction of the durability of polarizer 11 that occurs make the dyeing of polarizer 11 In the case of thickening, the reduction of the brightness of display image can be also avoided.That is, if the dyeing of polarizer 11 is made to thicken, rise The decrease in transmission of polariscope 11, but the high-transmission rate due to that can realize IPS units 2, even if the transmissivity of polarizer 11 It reduces, the reduction of the brightness of display image can be also avoided by the high-transmission rate of IPS units 2.

In addition, in the present embodiment, it will indicate that the loss angle tangent of the ratio between loss modulus A and storage modulus B A/B are set For tan δ when, Log's (tan δ) in the optical film (protective film 12, opposed film 13) of polarizing film 3 between -40 DEG C to 100 DEG C Value is -1.8 or more (also identical for the optical film (protective film 22, opposed film 23) of polarizing film 4).It is explained, δ is equivalent to pair Phase delay when object produces strain to Surge chamber, in object relative to the strain of stress.

In above-mentioned temperature range, if the value of Log (tan δ) be -1.8 or more, so that it may with say optical film by temperature change The variation of caused viscosity (viscoplasticity) is small.Therefore, as polarizer 11, even if having used caused by temperature change In the case of the big PVA film of sticky variation, by changing small 12 He of protective film with by the viscosity caused by temperature change Polarizer 11 is clamped in opposed film 13, can also inhibit the generation of the crackle by the polarizing film caused by temperature change.

In addition, the optical film (protective film 12, opposed film 13) of polarizing film 3 preferably comprises the polyester of sealing end as plasticizer (also identical for the optical film (protective film 22, opposed film 23) of polarizing film 4).In this case, above-mentioned optical film can be made Phase difference caused by temperature change changes and the variation of viscosity becomes smaller, and optical characteristics (phase difference, viscosity) can be made to stablize.

Hereinafter, the details of each optical film to constituting polarizing film 3 and 4 illustrates.

[film base material]

(cellulose esters system resin)

The cellulose esters system resin that can be used as the film base material of the optical film of present embodiment is preferably selected from cellulose (two, three) acetic acid esters, cellulose propionate, cellulose butylate, cellulose acetate propionate, cellulose ethanoate butyric acid It is at least one kind of in ester, cellulose acetate phthalate and cellulose phthalate.By using in these extremely For few a kind of resin to make optical film, can be easily implemented the value of the Log (tan δ) between -40 DEG C to 100 DEG C becomes -1.8 Above optical film.

In these, as particularly preferred cellulose esters, cellulosic triacetate, cellulose propionate, fibre can be enumerated The plain butyrate of dimension, cellulose acetate propionate, cellulose acetate butyrate.

As mixed aliphatic ester, preferred cellulose acetate propionate, cellulose acetate butyrate it is rudimentary Aliphatic ester has the acyl group of carbon atom number 2~4 as substituent group, the degree of substitution of acetyl group is set as X, by propiono or butyryl When the degree of substitution of base is set as Y, preferably contain while meeting the celluosic resin of following formula (I)s and the cellulose esters of (II).

2.6≤X+Y≤3.0 formula (I)

1.0≤X≤2.5 formula (II)

Wherein, particularly preferably use cellulose acetate propionate, wherein preferably 1.9≤X≤2.5, be 0.1≤Y≤ 0.9.The part not replaced by above-mentioned acyl group exists usually as hydroxyl.They can use well known method to synthesize.

In turn, it is preferable to use the ratio between weight average molecular weight Mw and number-average molecular weight Mn for the cellulose esters used in present embodiment The cellulose esters that Mw/Mn is 1.5~5.5.2.0~5.0 are more preferably used, 2.5~5.0 is further preferably used, is particularly preferred Use 3.0~5.0 cellulose esters.

The raw cellulose of the cellulose esters used in present embodiment can be that wood pulp can also be velveteen.In addition, wooden It can also be broad leaf tree that slurry, which can be coniferous tree, more preferable coniferous tree.From film when fissility from the aspect of, it is preferable to use Velveteen.The cellulose esters made by them can suitably mix or be used alone.

For example, can be with the cellulose esters from velveteen：Cellulose esters from wood pulp (coniferous tree)：It is (wealthy from wood pulp The ratio of cellulose esters Ye Shu) becomes 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：Each cellulose esters is used in mixed way by 30 mode.

In the present embodiment, for cellulose esters system resin, 1g is put into pure water (the 0.1 μ S/cm of conductivity of 20ml Below, pH6.8), under 25 DEG C, 1hr, nitrogen atmosphere stir when pH be preferably 6~7, conductivity is preferably 1~100 μ S/cm.

(ester ring type olefin polymer system resin)

Ester ring type olefin polymer system resin (COP) can be used in the film base material of optical film as present embodiment.Alicyclic ring Formula olefin polymer system resin is with as saturated alicyclic hydrocarbon (cycloalkane) structure, unsaturated lipid cyclic hydrocarbon (cycloolefin) structure The polymer of ester ring type structure.To the carbon atom number that constitutes ester ring type structure, there is no particular restriction, usually 4~30, preferably 5 ~20, more preferable 5~15 ranges when, keep the characteristic of mechanical strength, heat resistance and mouldability highly balanced and it is preferred that.

But in present embodiment, as described above, from inhibiting by the generation of the crackle of the polarizing film caused by temperature change From the viewpoint of, the value of the Log (tan δ) between -40 DEG C to 100 DEG C is necessary for -1.8 or more.Such as JSR companies manufacture ア ー ト Application (G7810) is polymer of the side chain with polar group in COP, the Log's (tan δ) in above-mentioned temperature range Minimum value is -1.7, therefore is preferred for the optical film of present embodiment.It is explained, by above-mentioned ア ー ト Application Middle addition rubber particles can be such that the value of the Log (tan δ) in above-mentioned temperature range increases, make sticky caused by temperature change Variation further becomes smaller.As such rubber particles, such as ケ ミ カ Le ズ companies of Asahi Chemical Industry can be used to manufacture SRB215。

(zero phase difference film)

In each polarizing film, relative to polarizer, the optical film of IPS cell sides, i.e. opposed film, from the raising of display performance Viewpoint consider, preferably by following formula (i) indicate Ro be 0nm or more and 10nm or less, by following formula (ii) indicate Rt for- 10nm or more and+10nm zero phase difference films below.

Formula (i) Ro=(nx-ny) × d

Formula (ii) Rt={ (nx+ny)/2-nz } × d

(in formula, Ro indicates that the length of delay in direction in the face of film, Rt indicate that the length of delay of the thickness direction of film, nx indicate film The refractive index in the slow axis direction in face, ny indicate that the refractive index in the leading phase shaft direction in film surface, nz indicate the thickness direction of film Refractive index (refractive index in the environment of 23 DEG C, 55%RH, at wavelength 590nm measure), d indicates the thickness (nm) of film.)

This is because：In IPS modes, due to playing good display performance by liquid crystal cells itself in a manner of constituted, Therefore it is used as opposed film, compared with the phase difference film for assigning phase difference to transmitted light, uses zero phase for hardly assigning phase difference Potential difference film is easier the advantages of playing liquid crystal cells (raising of display performance).

Above-mentioned zero phase difference film can be realized by so that opposed film is contained delay depressant.As delay depressant, Such as it can use in the compound (A) with 1 furanose structure or pyranose structure or by 2 or more and 12 It is at least one kind of compound (B) being combined into furanose structure or pyranose structure below, by the whole of OH bases or Sugar ester made of a part is esterified with aliphatic acyl radical.

Wherein, as the above-mentioned sugar ester of delay depressant due to furanose structure or pyranose structure, chemistry Structure is similar with cellulose esters.Therefore, the interaction of above-mentioned sugar ester and cellulose esters is strong.Therefore, by realizing containing upper The zero phase difference film of the sugar ester and cellulose esters stated, even if zero phase difference film can be inhibited if zero phase difference film is thinned Mechanical strength reduces.

From reliably making from the viewpoint of the delay Ro in the direction and delay Rt of thickness direction becomes smaller in face, above-mentioned sugar ester is excellent It is selected as at least one kind of compound (B) being combined into 2 or more and 12 furanose structures or pyranose structure below In OH bases all or part of be esterified with aliphatic acyl radical made of compound.In addition, above-mentioned sugar ester is more preferably by 2 All or part of use of the OH bases at least one kind of compound (B) being combined into furanose structure or pyranose structure Compound made of acetyl esterification.As such sugar ester, such as acetyl sucrose can be enumerated.

[manufacturing method of optical film]

Then, the manufacturing method of the optical film of present embodiment is illustrated.In present embodiment, it can use usual The manufacturing methods such as inflation method, T-shaped mould head method, rolling process, cutting method, the tape casting, emulsion method, pressure sintering, but it is preferable to use streams Prolong method (solution curtain coating is film-made method or melting casting film method).

(solution curtain coating film method)

In solution curtain coating film method, by passing through process below successively, optical film can be made.

(1) dissolution process

The process be in the organic solvent based on the good solvent for thermoplastic resin in dissolution kettle by thermoplasticity Resin, heat-shrinkage material, other additives are dissolved while stirring and the process that forms rubber cement.In the dissolving of thermoplastic resin In, the method carried out under normal pressure, the method carried out below the boiling point of main solvent can be used, more than the boiling point of main solvent It is method that pressurization ground carries out, special using Japanese Unexamined Patent Publication 9-95544 bulletins, Japanese Unexamined Patent Publication 9-95557 bulletins or Japan It opens in the method for such hot-cold lysis method progress, Japanese Unexamined Patent Publication 11-21379 bulletins described in flat 9-95538 bulletins Record the various dissolving methods such as such method carried out under high pressure, pressurize particularly preferably more than the boiling point of main solvent into Capable method.

It can be mixed in above-mentioned rubber cement and return material.It is so-called to return material, refer to being produced when making film for the product for slightly crushing film The product of both sides cutaway raw, by film, the underproof master film due to scratch etc..It is mixed in rubber cement by the way that material will be returned It closes, is recycled so as to which material will be returned in the manufacture of film.

(2) it is cast process

The process is by liquid-feeding pump (such as compression type quantitative gear pump) by above-mentioned rubber cement liquor charging to casting head, from The process that above-mentioned rubber cement is cast to the casting position in metal support by the slit of casting head.As metal support, energy It is enough to use annular metal tape (such as stainless steel band), the metal drum etc. of rotation.

As casting head, the mouth mold part that can adjust die head shape of slit, be easy that film thickness is made to become uniform Aspect, sometimes using pressurization die head.There are rack type die, T-shaped mould head etc. in the die head that pressurizes, preferably uses.

The surface of metal support becomes minute surface.In order to improve film speed, can be arranged in metal support 2 with On pressurization die head, segmentation rubber cement amount carries out double-layer.Or it is also preferred that using the common curtain coating method for being cast multiple rubber cements simultaneously To obtain the film of stepped construction.

(3) solvent evaporization process

The process is by mesh (casting films (rubber cement film) for forming rubber cement curtain coating in metal support) in gold Belong to the process that evaporation of the solvent is heated, made on supporting mass.

When making evaporation of the solvent, there are the method from mesh cross air blasting and/or the back side from supporting mass to use a liquid to conduct heat Method, the method etc. conducted heat from surface and the back side using radiant heat, the drying efficiency of rear surface liquid heat-transferring method it is good and it is preferred that. In addition, it is also preferred that using the method for combining them.For the mesh after curtain coating, preferably in metal support 40~ It is made it dry under 100 DEG C of atmosphere.When maintaining above-mentioned temperature range, the warm air of above-mentioned temperature range is preferably blown into mesh Above, or using the means of infrared ray etc. mesh is heated.

(4) stripping process

The process be by the mesh of the evaporation of the solvent in metal support the stripping of stripping position process.It will stripping Mesh be sent into subsequent processing.From the viewpoint of the face quality, penetrability, fissility of mesh, preferably opened from curtain coating Begin to remove mesh from metal support within 30~120 seconds.

The temperature (exfoliation temperature) at stripping position in metal support is preferably 10~40 DEG C, more preferably 11~30 ℃。

The residual solvent amount of the mesh in metal support at the time of stripping according to the power of dry condition, The length etc. of metal support, the preferably range of 50~120 mass %.Mesh is shelled at the time of residual solvent amount is more From in the case of, mesh is excessively soft, then flatness is damaged when removing, and it is (linear to take out line caused by easy ting produce stripping tension Damage), vertical stripe, therefore take into account economic pace and quality to determine residual solvent amount when stripping.

It is explained, the residual solvent amount of mesh is defined by following formula.

Residual solvent amount (%)=(quality after the heat treatment of quality (the g)-mesh before the heat treatment of mesh (g))/(quality (g) after the heat treatment of mesh) × 100

Wherein, heat treatment when measuring residual solvent amount refers to heat treatment in 1 hour at 115 DEG C.

Stripping tension when removing mesh from metal support is usually 196~245N/m, and production is easy in stripping In the case of giving birth to fold, preferably removed with 190N/m tension below, the minimum tension that more preferably use can be removed~ 166.6N/m, it is secondly removed with minimum tension~137.2N/m.Particularly preferably removed with minimum tension~100N/m.

In present embodiment, the temperature at the stripping position in metal support is preferably set to become -50~40 DEG C, more preferably 10~40 DEG C, most preferably become 15~30 DEG C.

(5) dry and stretching process

The process be mesh is made after metal support stripping the mesh removed it is dry in drying device, And/or the process stretched using stenter stretching device.Multiple rollers are configured in drying device, by alternately passing through Each roller conveys mesh, to making mesh dry.In addition, in stenter stretching device, mesh is clamped with clip Both ends convey, and mesh stretched.

As the means for drying mesh in drying device, hot wind usually is blowed to the two sides of mesh, but Have instead of wind and irradiating microwaves are come the means that are heated.Excessively violent drying is easy to damage the flatness of the film of completion.By It is that 8 mass % or less are controlled, therefore be advisable using the drying of high temperature in residual solvent amount.On the whole, it dries substantially 40 It is carried out at~250 DEG C.Particularly preferably made it dry at 40~160 DEG C.

, it is preferable to use the left and right holding means using stenter can control solely in the case of using stenter stretching device The device of the holding length (to the distance for holding end since holding) of Site control film.In addition, in stretching process, in order to Improve flatness, it is also preferred that intentionally forming the zoning (region) with different temperatures.

In addition, it is also preferred that differential gap is arranged, so that each zoning is not interfered between different temperatures zoning.

It is explained, stretched operation may be partitioned into the multistage to implement, it is also preferred that implementing biaxial stretch-formed (curtain coating direction and cross Stretching to direction).In addition, in the case where carrying out biaxial stretch-formed, simultaneously biaxial drawing can be carried out, it also can be periodically real It applies.The stretching of so-called stage, such as can carry out the different stretching of draw direction successively, can also be will be unidirectional Draw segmented is the multistage, and applies the stretching of different directions in its either phase.That is, for example can be following such Stretching step.

It is pulled up in curtain coating side-stretches-being pulled up in curtain coating side-in a lateral direction and be pulled up in curtain coating side

Stretching-in a lateral direction stretches-being pulled up in curtain coating side-and is pulled up in curtain coating side in a lateral direction

It stretches in one direction in addition, also containing in biaxial stretch-formed at the same time, so that another party is mitigated tension and make its contraction Situation.The preferred stretching ratio of simultaneously biaxial drawing can be at 1.01 times~1.5 times on horizontal direction, longitudinal direction In the range of set.

The residual solvent amount of mesh when being stretched preferably 20~100 mass % when stretching beginning, and it is excellent Choosing is dried while imposing stretching, until the residual solvent amount of mesh becomes 10 mass % or less (more preferably 5 matter Measure % or less).

Preferably 30~160 DEG C of drying temperature when being stretched, more preferable 50~150 DEG C, most preferably 70~140 DEG C.

In stretching process, from the viewpoint of the homogeneity for improving film, the Temperature Distribution preferably in the horizontal direction of atmosphere It is upper uneven small.Specifically, within uneven preferably ± 5 DEG C of the temperature of the horizontal direction in stretching process, more preferably ± 2 DEG C with It is interior, within most preferably ± 1 DEG C.

(6) coiling process

The process is to use coiling machine to batch for the work of film after the residual solvent amount in mesh becomes 2 mass % or less Sequence.By making residual solvent amount become 0.4 mass % hereinafter, so as to obtain the good film of dimensional stability.Particularly preferably Film roll is taken with 0.00~0.10 mass %.

As method for coiling, general used method can be used, have and determine calibrated wrench method, determine tensammetry, is gradual change tensammetry, interior They can be distinguished and be used by the certain program tension control method etc. of portion's stress.

Optical film in present embodiment is preferably long size film, specifically, indicates the optics of 100m~5000m or so Film is the optical film usually in the form of web-like is provided.In addition, the width of film is preferably 1.3~4m, more preferably 1.4~ 2m。

(melting casting film method)

It, can be by making optical film by process below successively in melting casting film method.

＜ melts pellet manufacturing process ＞

For composition being used in melting extrusion, containing resin, preferably usually it is kneaded and is granulated in advance.

Granulation can be well known method, for example, by being constituted by the thermoplastic resin dried and by heat-shrinkage material etc. Additive supplied to extruder with feeder, be kneaded using the extruder of single screw rod, twin-screw, silk be extruded into from die head Pencil carries out water cooling or air-cooled, is cut and completed.

Raw material are dried before extrusion, this is important in the decomposition for prevent raw material.Especially fiber Plain ester is easy moisture absorption, therefore preferably 3 hours dry or more at 70~140 DEG C using dehumidifying air drier, vacuum drier, Moisture rate is set to become 200ppm hereinafter, becoming 100ppm or less in turn.

It for additive, can mix before supplying to extruder, can also be supplied respectively with independent feeder.With regard to grain For a small amount of additive such as son, antioxidant, in order to equably be mixed, preferably mixed in advance.

It for the mixing of antioxidant, can be mixed between solid, as needed, antioxidant can be dissolved in In solvent, it is made to be impregnated in thermoplastic resin and mix, or can sprayed to mix.

It can be carried out at the same time dry and mixing using vacuum nauta mixer etc., therefore preferably.In addition, with regard to feeder portion, For the part that outlet of die head etc. is contacted with air, preferably make its in dehumidified air, except wet N₂Under the atmosphere such as gas.

It for extruder, is preferably processed at low temperature as far as possible in the degree that can be granulated, to inhibit to shear Power so that resin does not deteriorate (molecular weight is reduced, coloured, gel generates etc.).For example, in the case of double screw extruder, It is preferable to use the screw rods of shallow/deep groove type, it is made to rotate in the same direction.Consider from the uniformity of mixing, preferably engagement type.

Film production is carried out using the pellet obtained above.Also it can not be granulated and the powder of raw material is directly used and is fed Device is supplied to extruder, directly carries out film production.

The process ＞ that ＜ squeezes out molten mixture from die head to chill roll

Make melting temperature Tm when extrusion using single screw rod, the extruder of double-screw type firstly, for the pellet of making It as 200~300 DEG C or so, is filtered with the filter etc. of leaf dish type, after foreign matter is removed, from T-shaped mould head film extrusion Shape cures on chill roll, is cast while being squeezed with Elastic Contact roller.

When being imported from feeding hopper to extruder, under being preferably set under vacuum or depressurizing, under non-active gas atmosphere, to prevent Only oxygenolysis etc..It is explained, Tm is the temperature of the die exit portion of extruder.

If the foreign matters such as coagulation of damage, plasticizer are attached to die head, the defect of striated is generated sometimes.It also will in this way Defect be known as die head line.In order to make the defect on the surfaces such as die head line become smaller, preferably become such as lower structure：From extruder Into the piping of die head, the delay portion of resin tails off as possible.It is preferably used in the inside of die head, scar etc. is not present in die lip as possible Die head.

For the inner face of extruder, die head etc. contacted with molten resin, surface roughness is preferably made to become smaller, using table Energy low material etc. in face implements molten resin and is difficult to the surface adhered to processing.Specifically, it can enumerate to having carried out hard-chrome plating It applies, the product of ceramic thermal spray has carried out grinding so that surface roughness becomes 0.2S inner faces below.

To chill roll, there is no particular restriction, as long as the metallic roll of high rigidity, have can temperature controlled thermal medium or cold Roller of the medium in the structure of internal flow.In addition, size to chill roll and being not limited, squeezed as long as being enough cooling melting The size of the film gone out.In general, a diameter of 100mm to 1m or so of chill roll.

For the Facing material of chill roll, carbon steel, stainless steel, aluminium, titanium etc. can be enumerated.In order to further increase surface Hardness or improve with the fissility of resin, hard chrome plating, nickel plating, Amorphous Chromium plating etc., ceramic thermal spray etc. is preferably implemented Surface treatment.

The surface roughness of cooling roller surface indicates with Ra, be preferably set to 0.1 μm hereinafter, be more preferably set as 0.05 μm with Under.Roller surface is more smooth, then the surface of the film obtained also can be more smooth.Certainly, the surface that can be machined to surface is further Grinding, makes surface roughness further become smaller.

As Elastic Contact roller, Japanese Unexamined Patent Publication 03-124425, Japanese Unexamined Patent Publication No. 08-224772, day can be used This Unexamined Patent 07-100960, Japanese Unexamined Patent Publication 10-272676, No. WO97/028950, Japanese Unexamined Patent Publication 11-235747 Number, described in Japanese Unexamined Patent Publication 2002-36332, Japanese Unexamined Patent Publication 2005-172940, Japanese Unexamined Patent Publication 2005-280217 bulletins Surface be the coating silica gel roller of film metal sleeve.

When from chill roll by film stripping, tension is preferably controlled to prevent the deformation of film.

[manufacturing method of composite resin membrane]

The optical film of present embodiment can be made of composite resin membrane.As the method for manufacture composite resin membrane, can adopt With common curtain coating method or coetrusion.

(common curtain coating method：Dual the tape casting)

Metal support in curtain coating (cast) process has preferably carried out the metal support of mirror finishing to surface, makees For metal support, it is preferable to use stainless steel band or with casting to surface carried out plating finishing rotary drum.The width of curtain coating Degree can be set as 1~4m.

The surface temperature for being cast the metal support of process is set as -50 DEG C~solvent and does not boil the temperature of foaming.Temperature The rate of drying of the high then mesh of degree can speed up, therefore preferably, but if excessively high, then mesh foaming sometimes or flatness Deterioration.As preferred bearing temperature, suitably determined in 0~100 DEG C, more preferable 5~30 DEG C.Alternatively, passing through progress It is cooling, make mesh gelation, is removed from rotary drum in the state of largely containing residual solvent, this is also preferred method.

To the method for temperature that controls metal support, there is no particular restriction, has the method for warm air or cold wind that blows, makes temperature The method of water and the backside contact of metal support.Using warm water, due to efficiently carrying out passage of heat, until metal The temperature of supporting mass is short and preferred as the regular hour.Using warm air, consider that the evaporation latent heat of solvent causes Mesh temperature reduce, sometimes use solvent boiling point more than warm air, be simultaneously used in ratio while being also prevented from foaming The wind of the high temperature of temperature of target.Particularly preferably from curtain coating up to removed during change supporting mass temperature and do The temperature of dry wind, is efficiently dried.

In the present embodiment, it is also preferred that the solution of acetylation of cellulose is divided into 2 times or more to be cast.

The rubber cement A of preparation is cast to stainless steel band by die head, further makes to be prepared in the mesh being cast Rubber cement B curtain coating is laminated by die head.The mesh being laminated is removed at pick-up point, is then dried in dry section And it batches.

For the composition of the composition as rubber cement A, rubber cement B, there is no particular restriction, acetylation of cellulose, cellulose nanometer The composition ratio of fiber and other additives, solvent can be used in any way.In addition, to the casting films of rubber cement A, rubber cement B Thickness is also not particularly limited.Also 3 times or more segmentation curtain coatings can be carried out.

(coetrusion)

In the present embodiment, the film of stepped construction can be also made by coetrusion.For example, can make surface layer/ The such film constituted in sandwich layer/surface layer.For example, for delustering agent, surface layer can be made more or be only put into surface layer.With regard to plasticising For agent, ultra-violet absorber, compared with surface layer, it can be more put into sandwich layer, also can only put it into sandwich layer.Separately Outside, also the type of plasticizer, ultra-violet absorber can be made to change in sandwich layer and surface layer, for example, it is low that surface layer can also contained Volatile plasticizer and/or ultra-violet absorber add plasticity excellent plasticizer or ultraviolet-absorbing in the core Excellent ultra-violet absorber.Surface layer can be different from the glass transition temperature of sandwich layer, preferably the glass transition temperature of sandwich layer Degree is lower than the glass transition temperature on surface layer.At this point, the glass transition temperature on both surface layer and sandwich layer can be also measured, it will The average value calculated by their volume fraction is defined as above-mentioned glass transition temperature Tg similarly to dispose.In addition, just molten For the viscosity of the fusant containing cellulose esters when melting curtain coating, and can be different in surface layer and sandwich layer, can be surface layer Viscosity ＞ sandwich layers viscosity, can also be the viscosity on viscosity >=surface layer of sandwich layer.

It is explained, so-called above-mentioned coetrusion, is following method：Using multiple extruders, by each extruder Resin to be laminated is heated into melting, from the outlet coextrusion of the slit-shaped of T-shaped mould head after making each resin collaborate, with cooling Roller is allowed to cool solidification, forms cast-sheet (unstretched state).As making molten resin interflow, squeeze from T-shaped mould head by sheet material The method gone out, after having the feed block method extended in manifold after making molten resin collaborate and extending molten resin with manifold respectively The branch manifold method for making it collaborate can be used.

[additive]

The optical film (film base material) of present embodiment preferably comprises antioxidant.Preferred antioxidant is phosphorus system or phenol System more preferably simultaneously combines phosphorus system and phenol system.Below in present embodiment can it is preferable to use antioxidant say It is bright.

＜ phenolic antioxidants ＞

, it is preferable to use the antioxidant of phenol system, particularly preferably uses hindered phenol compound in present embodiment.

In the concrete example of hindered phenol compound, contain 3- (3,5- di-tert-butyl -4- hydroxy phenyls)-propionic acid positive 18 Arrcostab, 3- (3,5- di-tert-butyl -4- hydroxy phenyls)-acetic acid n-octadecane base ester, 3,5- di-tert-butyl -4- hydroxy benzenes Formic acid n-octadecane base ester, the just own ester of 3,5- di-tert-butyl -4- hydroxy phenyls benzoic acid, 3,5- di-tert-butyl -4- hydroxyls Phenylbenzoic acid n-dodecane base ester, 3- (3,5- di-tert-butyl -4- hydroxy phenyls) new dodecyl ester of propionic acid, β (3,5- Di-tert-butyl -4- hydroxy phenyls) propionic acid dodecyl ester, α-(4- hydroxyl -3,5- di-tert -s butyl phenyl) ethyl isobutyrate, α-(4- hydroxyl -3,5- di-tert -s butyl phenyl) isobutyric acid stearyl, α-(4- hydroxyl -3,5- di-tert-butyl -4- hydroxyls Phenyl) propionic acid stearyl, 3,5- di-tert-butyl -4- hydroxy-benzoic acids 2- (n- pungent sulfenyl) ethyl ester, 2- (n- pungent sulphur Base) ethyl 3,5- di-tert-butyl -4- hydroxy-phenyl-acetic acids ester, 2- (n- octa-decylthio) ethyl 3,5- di-tert -s butyl - 4- hydroxyphenyl acetic acids ester, 2- (n- octa-decylthio) ethyl 3,5- di-tert-butyl -4- hydroxy-benzoic acids ester, 2- (2- hydroxyls Base ethylmercapto group) ethyl 3,5- di-tert -s butyl -4-HBA ester, diethylene glycol (DEG) be double-(3,5- di-tert-butyl -4- hydroxyls-benzene Base) propionic ester, 2- (n- octa-decylthio) ethyl 3- (3,5- di-tert-butyl -4- hydroxy phenyls) propionic ester, stearmide - N, N- be bis--and [ethylidene 3- (3,5- di-tert-butyl -4- hydroxy phenyls) propionic ester], n-butyl imino group-N, N- be bis--[sub- second Base 3- (3,5- di-tert-butyl -4- hydroxy phenyls) propionic ester], 2- (2- stearoyl-oxies ethylmercapto group) ethyl 3,5- di-tert-fourths Base -4-HBA ester, 2- (2- stearoyl-oxies ethylmercapto group) ethyl 7- (3- methyl -5- tert-butyl -4- hydroxy phenyls) heptan Acid esters, 1,2- propylene glycol pair-[3- (3,5- di-tert-butyl -4- hydroxy phenyls) propionic esters], ethylene glycol pair-[3- (3,5- bis- - Tert-butyl -4- hydroxy phenyls) propionic ester], neopentyl glycol it is double-[3- (3,5- di-tert-butyl -4- hydroxy phenyls) propionic ester], N- octadecane acid esters -2,3- couples ethylene glycol pair-(3,5- di-tert-butyl -4- hydroxyphenyl acetic acids ester), glycerine-l--(3,5- Di-tert-butyl -4- hydroxyphenyl acetic acids ester), pentaerythrite-four-[3- (3 ', 5 '--4 '-hydroxy phenyl of di-tert-butyl) third Acid esters], 1,1,1- trimethylolethanes-three-[3- (3,5- di-tert-butyl -4- hydroxy phenyls) propionic ester], sorbierite six - [3- (3,5- di-tert-butyl -4- hydroxy phenyls) propionic ester], 2- hydroxyethyls 7- (3- methyl -5- tert-butyl -4- hydroxy benzenes Base) propionic ester, 2- stearoyl-oxy ethyls 7- (3- methyl -5- tert-butyl -4- hydroxy phenyls) heptanoate, 1,6- it is n- oneself two Alcohol-bis- [(3 ', 5 '-di-tert-butyl -4- hydroxy phenyls) propionic esters], (the 3,5- di-tert-butyl -4- hydroxyls of pentaerythrite-four Hydrogenated cinnamate).The hindered phenol compound of the above-mentioned type is for example by チ バ ジ ャ パ Application (strain) " Irganox 1076 " is commercially available with the trade name of " Irganox 1010 ".

＜ phosphorous antioxidants ＞

As phosphorous antioxidant, phosphite ester (phosphite), phosphinate (phosphonite), secondary can be used The phosphorus series compounds such as phosphate (phosphinite) or tertiary phosphine (phosphane).As phosphorus series compound, can use current Until known compound.Such as preferred Japanese Unexamined Patent Publication 2002-138188, Japanese Unexamined Patent Publication 2005-344044 number sections fall serial number 0022~0027, Japanese Unexamined Patent Publication 2004-182979 number sections fall serial number 0023~0039, Japanese Unexamined Patent Publication 10-306175, Japan Unexamined Patent 1-254744, Japanese Unexamined Patent Publication 2-270892, Japanese Unexamined Patent Publication 5-202078, Japanese Unexamined Patent Publication 5-178870 Number, Japanese Unexamined Patent Application Publication 2004-504435, Japanese Unexamined Patent Application Publication 2004-530759 and Japanese Patent Application 2005-353229 bulletins say Phosphorus series compound described in bright book.

Relative to 100 mass parts of resin, the additive amount of phosphorus series compound is usually 0.01~10 mass parts, preferably 0.05 ~5 mass parts, more preferably 0.1~3 mass parts.

As phosphorus series compound, other than the compound indicated by above-mentioned general formula, triphenyl phosphite, two can be enumerated Phenyl isodecyl phosphite, phenyl diiso decyl phosphite ester, three (nonyl phenyl) phosphite esters, three (dinonylphenyls) are sub- Phosphate, three (2,4- di-tert -s butyl phenyl) phosphite esters, 10- (3,5- di-tert-butyl -4- hydroxybenzyls) -9,10- two Hydrogen -9- oxa- -10- phospho hetero phenanthrene -10- oxides, 6- [3- (3- tert-butyl -4- hydroxy-5-methyl bases phenyl) propoxyl group] -2,4, The list phosphite ester system such as tetra--tert-butyls of 8,10- dibenzo [d, f] [1.3.2] dioxaphosphepin cycloheptene, tridecyl phosphite Compound；4,4 '-butylidenes-bis- (3- methyl-6-terts-butyl phenyl-two-tridecyl phosphite), 4,4 '-isopropylidenes-bis- Diphosphites based compounds such as (phenyl-di-alkyl (C12~C15) phosphite esters)；Triphenyl phosphite, four (2,4- bis-- Tert-butyl phenyl) [1,1- biphenyl] -4,4 '-diyl biphosphinate, four (2,4- di-tert-butyl -5- aminomethyl phenyls) [1,1- Biphenyl] the phosphinates based compound such as -4,4 '-diyl biphosphinate；Hypophosphorous acid triphenylmethyl methacrylate, 2,6- 3,5-dimethylphenyl diphenyl The phosphinates based compound such as phosphinate；Phosphines based compounds such as triphenylphosphine, three (2,6- Dimethoxyphenyls) phosphines etc..

The phosphorus series compound of the above-mentioned type is for example by Sumitomo Chemical Co with " Sumilizer GP ", by strain formula meeting Society ADEKA uses " ADK STAB PEP-24G ", " ADK STAB PEP-36 " and " ADK STAB 3010 ", by チ バ ジ ャ パ Application Co., Ltd. uses trade name as " GSY-P101 " commercially available with " IRGAFOS P-EPQ ", by Sakai Chemical Industry Co., Ltd..

＜ others antioxidants ＞

In addition, 3,3 '-dilauryl thiodipropionates, 3,3 '-thio-2 acid, two myristin, 3,3 '-can be enumerated Sulfur antioxidants, the 2- tert-butyls-such as distearylthiodi-propionate, pentaerythrite four (3- laurylthiopropionates) 6- (3- tert-butyl -2- hydroxy-5-methyl bases benzyl) -4- aminomethyl phenyls acrylate, 2- [1- (2- hydroxyl -3,5- di-tert -s penta Base phenyl) ethyl] heat-resisting processing stabilizers, the Japanese Patent Publication 08-27508 such as -4,6- di-tert-amyl phenyl acrylates 3,4- dihydro -2H-1- chromenes based compound, 3,3 '-spiral shell, two chroman based compound, the 1,1- spiral shell indanes system chemical combination of record Object, morpholine, thiomorpholine, oxidation thiomorpholine, titanium dioxide thiomorpholine, the chemical combination with piperazine skeleton in part-structure Oxygen trapping agents such as the dialkoxy benzene compounds that object, Japanese Unexamined Patent Publication 03-174150 are recorded etc..The part of these antioxidants Structure can be a part for polymer or regularly be used as side chain in the polymer, can also introduce plasticizer, sour agent for capturing, In a part for the molecular structure of the additives such as ultra-violet absorber.

(other additives)

In film base material of the present embodiment, other than above-mentioned compound etc., it can be contained according to purpose each Kind compound etc. is used as additive.

＜ acid agent for capturing ＞

As sour agent for capturing, the conduct acid agent for capturing described in 4,137, No. 201 specifications of U.S. Patent No. is preferably comprised Epoxide.Such epoxide as sour agent for capturing is in this technical field it is known that contain various poly- second The diglycidyl ether of glycol, particularly spread out by the condensation of the ethylene oxide of about 8~40 moles of every 1 mole of polyethylene glycol etc. Raw diglycidyl ether of polyethylene glycol, glycerine etc., metal epoxide (such as in vinyl chloride polymer composition with And together with vinyl chloride polymer composition, used metal epoxide sharp so far), the condensation of epoxidation ether generates Diglycidyl ether (that is, 4,4 '-dihydroxydiphenyl dimethylmethanes), the epoxidation unsaturated fatty acid ester of object, bisphenol-A (especially ester (such as the epoxystearic acid fourth of the alkyl of 4~2 or so carbon atoms of the aliphatic acid of 2~22 carbon atoms Ester) etc.) and various epoxidation chain fatty acid triglycerides etc. (such as can be using compositions such as epoxidised soybean oils as generation Table illustrates, epoxidized vegetable oil and other unsaturated natural oils (are referred to as epoxidation natural glycerin ester or insatiable hunger sometimes And aliphatic acid, these aliphatic acid typically contain 12~22 carbon atoms)).

＜ light stabilizers ＞

As light stabilizer, hindered amine light stabilizer (HALS) compound can be enumerated, is known compound, such as Such as the 3rd~5 of No. 4,839,405 specifications in the 5th~11 column and U.S. Patent No. of No. 4,619,956 specifications of U.S. Patent No. the Described in column like that, contain 2,2,6,6- tetraalkylpiperidine compounds or their acid-addition salts or they and metal compound The complex compound of object.In turn, the light stabilizer described in Japanese Unexamined Patent Publication 2007-63311 bulletins can be used.

＜ ultra-violet absorbers ＞

As ultra-violet absorber, from the viewpoint of preventing UV-induced deterioration, optimal wavelength 370nm is below The absorbability of ultraviolet light is excellent, and from the viewpoint of liquid crystal display, the suction of the visible light of optimal wavelength 400nm or more Receive few ultra-violet absorber.Such as dihydroxy benaophenonel based compound, benzotriazole based compound, salicylic acid can be enumerated Ester based compound, benzophenone based compound, cyanoacrylate based compound, nickel complex salt based compound etc., but preferred hexichol The few benzotriazole based compound of ketone based compound, coloring.In addition, it is possible to use Japanese Unexamined Patent Publication 10-182621 bulletins, The high score of ultra-violet absorber, the record of Japanese Unexamined Patent Publication 6-148430 bulletins that Japanese Unexamined Patent Publication 8-337574 bulletins are recorded Sub- ultra-violet absorber.

As the concrete example of benzotriazole based compound, 2- (2 '--5 '-aminomethyl phenyl of hydroxyl) benzotriazole, 2- can be enumerated (2 '-hydroxyls -3 ', 5 '-di-tert-butyl phenyls) benzotriazole, 2- (2 '--3 '-tert-butyls -5 of hydroxyl '-aminomethyl phenyl) benzo Triazole, 2- (2 '-hydroxyls -3 ', 5 '-di-tert-butyl phenyls) -5- chlorobenzotriazoles, 2- [2 '-hydroxyls -3 '-(3 ", 4 ", 5 ", 6 "-tetrahydrochysene phthalimidomethyl) -5 '-aminomethyl phenyl] benzotriazole, 2,2- di-2-ethylhexylphosphine oxides (4- (1,1,3,3- tetra- Methyl butyl) -6- (2H- benzotriazole -2- bases) phenol), 2- (2 '--3 '-tert-butyls -5 of hydroxyl '-aminomethyl phenyl) -5- chlorobenzenes And triazole, 2- (2 '--3 '-tert-butyls -5 of hydroxyl '-(2- octoxycarbonylethyls)-phenyl) -5- chlorobenzotriazoles, 2- (2 ' - Hydroxyl -3 '-(1- methyl-1s-phenylethyl) -5 '-(1,1,3,3- tetramethyl butyl)-phenyl) benzotriazole, 2- (2H- benzos Triazole -2- bases) -6- (straight chain and side chain dodecyl) -4- methylphenols, 3- [3- tert-butyl -4- hydroxyls -5- (chloro- 2H- benzene And triazole -2- bases) phenyl] octyl propionate and 3- [3- tert-butyl -4- hydroxyls -5- (the chloro- 2H- benzotriazole -2- bases of 5-) phenyl] The mixture etc. of propionic acid 2- ethylhexyls, but it is not limited to these.

In addition, as commercially available product, チ ヌ ビ Application (TINUVIN) 326, チ ヌ ビ Application (TINUVIN) 109, チ can be enumerated ヌビン(TINUVIN)171、チヌビン(TINUVIN)900、チヌビン(TINUVIN)928、チヌビン (TINUVIN) 360 (being the manufacture of チ バ ジ ャ パ Application company), LA31 (manufacture of ADEKA companies), (Sumitomos Sumisorb250 Chemical company manufacture), RUVA-100 (great mound chemistry manufacture).

As the concrete example of benzophenone based compound, 2,4-DihydroxyBenzophenone, 2,2 '-dihydroxies can be enumerated Base -4- methoxy benzophenones, 2- hydroxyl -4- methoxyl group -5- diphenylsulfones ketone, bis- (2- methoxyl group -4- hydroxyl -5- benzene first Aminosulfonylphenyl methane) etc., but it is not limited to these.

In present embodiment, ultra-violet absorber preferably adds 0.1~20 mass %, more preferably adds 0.5~10 matter % is measured, 1~5 mass % is further preferably added.Two or more in them can be used in combination.

＜ delustering agents ＞

The particles such as delustering agent can be added in the film base material of present embodiment, as particle, can enumerate inorganic compound Particle or organic compound particle.As particle, such as silica, titanium dioxide, aluminium oxide, oxidation can be enumerated The inorganic particles such as zirconium, calcium carbonate, kaolin, talcum, firing calcium silicates, afwillite, alumina silicate, magnesium silicate, calcium phosphate are handed over Linked polymer particle.Wherein, since silica can reduce the mist degree of resin substrate, preferably.As silica Particle mostly uses organic matter and is surface-treated, and such silica can reduce the mist degree of resin substrate, therefore preferably.

As preferred organic matter in surface treatment, halogenated silanes class, alkoxyl silicone alkanes, silazane, silicon can be enumerated Oxygen alkane etc..Then sliding effect is big greatly for the average grain diameter of particle, and on the other hand, average grain diameter is small then transparent excellent.

In addition, the range that the average grain diameter of the offspring of particle is 0.05~1.0 μm.The offspring of preferred particle Average grain diameter preferably 5~50nm, more preferably 7~14nm.In cellulose ester membrane, in order in cellulose ester membrane Surface Creation 0.01~1.0 μm of bumps are, it is preferable to use these particles.For the content in the cellulose esters of particle, relative to cellulose Ester, preferably 0.005~0.3 mass %.

As the particle of silica, the ア エ ロ ジ Le of Japanese ア エ ロ ジ Le (strain) system can be enumerated (AEROSIL) 200,200V, 300, R972, R972V, R974, R202, R812, OX50, TT600 etc., preferably ア エ ロ ジ Le 200V、R972、R972V、R974、R202、R812.For these particles, two or more may be used.It is two kinds or more In the case of, it can be mixed with arbitrary ratio to use.In this case, it is indicated with mass ratio, it can be with 0.1：99.9~ 99.9：0.1 range uses the different particle such as ア エ ロ ジ Le 200V and R972V of average grain diameter, material.

For the presence for functioning as the particle in the base material of above-mentioned delustering agent, as other purpose, it also can be used in carrying The intensity of high base material.

(plasticizer)

Optical film preferably comprises plasticizer.As plasticizer, preferably petchem.

It as petchem, is not particularly limited, such as can use and be spread out by dicarboxylic acids or their ester formative The condensation reaction of biology and glycol obtains, end becomes the polymer (hereinafter referred to as " polyester polyols of hydroxyl (hydroxy) Alcohol ") or the polyester polyol end the closed polymer of hydroxyl monocarboxylic acid (hereinafter also referred to " polyester of sealing end " or Person is referred to as " end capped polyesters ").Be explained, in this specification, so-called ester formative derivative, be dicarboxylic acids carboxylate, Dicarboxylic acid chloride, dicarboxylic acids acid anhydrides.

The optical film of present embodiment is used as plasticizer by containing the polyester of sealing end, to inhibit the temperature change of film to draw The phase difference risen changes and the variation of sticky (tan δ), and optical characteristics (phase difference, viscosity) is stablized.

As the concrete example of petchem, the ester based compound indicated by the following general formula (A) can be enumerated.

B-(G-A)n-G-B···(A)

(in formula, B is hydroxyl, benzene monocarboxylic acid residue or aliphatic monocarboxylic acid residue, and G is the aklylene glycol of carbon number 2~18 The oxyalkylene diol residue that the aryl-diol residue or carbon number of residue or carbon number 6~12 are 4~12, A are the Asia of carbon number 4~12 Aryl dicarboxylic acid's residue of alkyl dicarboxylic aid's residue or carbon number 6~16, the integer that n is 1 or more.)

In above-mentioned general formula (A), B is that the compound of hydroxyl is equivalent to polyester polyol, and B is benzene monocarboxylic acid residue or aliphatic The compound of monocarboxylic acid residue is equivalent to end capped polyesters.By general formula (A) indicate petchem by with common Polyester Plasticizer is similarly obtained by the reaction.

As the aliphatic monocarboxylic acid ingredient of the petchem indicated by general formula (A), for example, it is preferable to which carbon number 3 is below Aliphatic monocarboxylic acid can enumerate acetic acid, propionic acid, butyric acid (butyric acid), they can respectively use a kind or as two or more Mixture use.

As the benzene monocarboxylic acid ingredient of the petchem indicated by general formula (A), such as there is benzoic acid, to tert-butyl benzene first Acid, o-toluic acid, m-methyl benzoic acid, p-methylbenzoic acid, mesitylenic acid, ethyl benzoate, n-propylbenzene first Acid, aminobenzoic acid, acetoxy-benzoic acid, aliphatic acid etc., they can respectively use a kind or as of more than two kinds Mixture uses.Particularly preferably contain benzoic acid or p-methylbenzoic acid.

The aklylene glycol ingredient of carbon number 2~18 as the petchem indicated by general formula (A), there is ethylene glycol, 1, 2- propylene glycol (1,2- propylene glycol), 1,3- propylene glycol (1,3- propylene glycol), 1,2- butanediols, 1,3 butylene glycol, 1,2- propylene glycol, 2- methyl-1,3-propanediols, 1,4- butanediols, 2,3- butanediols, 1,5- pentanediols, 2,2- dimethyl -1,3- propylene glycol (new penta Glycol), 1,2- rings pentanediol, 1,3- rings pentanediol, 1,4- cyclohexanediols, 2,2- diethyl -1,3- propylene glycol (3,3- dihydroxy first Base pentane), 2- n-butyl -2- ethyl -1,3- propylene glycol (3,3- dihydroxymethyls heptane), 3- methyl-1s, 5- pentanediols, 1,6- Hexylene glycol, 2,2,4- trimethyl -1,3- pentanediols, 2- ethyl -1,3- hexylene glycols, 2- methyl-1s, 8- ethohexadiols, 1,9- nonyls two Alcohol, 1,10- decanediols, 1,12- octacosanols etc., for these glycol, using a kind of or mixed as two kinds or more Object is closed to use.Wherein, preferably ethylene glycol, diethylene glycol (DEG), 1,2-PD, 2- methyl-1s, 3-propanediol, more preferably ethylene glycol, Diethylene glycol (DEG), 1,2-PD.It is particularly, excellent in compatibility due to the aklylene glycol of carbon number 2~12 and cellulose esters, It is preferred that.The more preferably aklylene glycol of carbon number 2~6, the further preferably aklylene glycol of carbon number 2~4.

The oxyalkylene diol component of carbon number 4~12 as the petchem indicated by general formula (A), such as have two sweet Alcohol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol etc. form one kind or as two kinds or more for these glycol Mixture use.

The aryl-diol of carbon number 6~12 as the petchem indicated by general formula (A), such as have Isosorbide-5-Nitrae-hexamethylene two The cyclic diols classes such as alcohol, 1,4-CHDM, hexamethylene diethanol, Isosorbide-5-Nitrae-benzene dimethanol can for these glycol A kind of or mixture as two kinds or more is formed to use.

The alkylene dicarboxylic acids ingredient of carbon number 4~12 as the petchem indicated by general formula (A), such as have amber Acid, maleic acid, fumaric acid, glutaric acid, adipic acid, azelaic acid, decanedioic acid, dodecanedicarboxylic acid etc., each use a kind of Or it is used as two kinds or more of mixture.

Aryl dicarboxylic acid's ingredient of carbon number 6~16 as the petchem indicated by general formula (A), there is O-phthalic Acid, terephthalic acid (TPA), M-phthalic acid, 1,5- naphthalenedicarboxylic acids, 1,4- naphthalenedicarboxylic acids, 2,3- naphthalenedicarboxylic acids, 2,6- naphthalenedicarboxylic acids, 2,7- naphthalenedicarboxylic acids, 1,8- naphthalenedicarboxylic acids, 2,6- anthracene dioctyl phthalate etc..Above-mentioned aryl dicarboxylic acid can have substitution on aromatic ring Base.As substituent group, the aryl of the straight chain of carbon number 1~6 or the alkyl of branch-like, alkoxy, carbon number 6~12 can be enumerated.

In general formula (A), in the case where B is hydroxyl, that is, in the case that petchem is polyester polyol, A is preferred For aryl dicarboxylic acid's residue of carbon number 10~16.Such as it can use with fragrance such as benzene ring structure, naphthalene ring, anthracyclic structures The dicarboxylic acids of race's ring structures as specific aryl dicarboxylic acid's ingredient, such as can enumerate phthalic acid, isophthalic diformazan Acid, terephthalic acid (TPA), 1,4- naphthalenedicarboxylic acids, 2,3- naphthalenedicarboxylic acids, 2,6- naphthalenedicarboxylic acids, 2,7- naphthalenedicarboxylic acids, 1,8- naphthalene diformazans Acid, 2,6- anthracene dioctyl phthalate.Preferably 1,4- naphthalenedicarboxylic acids, 2,3- naphthalenedicarboxylic acids, 2,6- naphthalenedicarboxylic acids, 2,7- naphthalenedicarboxylic acids, 1, 8- naphthalenedicarboxylic acids, more preferably 2,3- naphthalenedicarboxylic acids, 2,6-naphthalenedicarboxylic acid, particularly preferably 2,6-naphthalenedicarboxylic acid.They can Using a kind or be two kinds or more.

For above-mentioned polyester polyol, the model of the average out to 10~16 of the carbon number of the dicarboxylic acids used preferably as raw material It encloses.If 10 or more the average out to of the carbon number of dicarboxylic acids, the excellent in dimensional stability of cellulose ester membrane, if carbon number is averaged For 16 hereinafter, then excellent in compatibility with cellulose esters, the transparency of cellulose ester membrane is significantly excellent.As dicarboxylic acids, preferably The average out to 10~14 of carbon number, the average out to 10~12 of more preferable carbon number.

The average of the carbon number of the dicarboxylic acids of above-mentioned polyester polyol polymerize to obtain polyester polyols using single dicarboxylic acids The carbon number for meaning the dicarboxylic acids in the case of alcohol, in the case where polymerizeing to obtain polyester polyol using dicarboxylic acids of more than two kinds Mean the total of the product of the carbon number of each dicarboxylic acids and the mole fraction of the dicarboxylic acids.

It, can be by the above-mentioned aryl two with 10~16 carbon atoms if the average out to 10~16 of above-mentioned carbon number Carboxylic acid is used in combination with the dicarboxylic acids other than it.As can dicarboxylic acids, the preferred dicarboxylic acids with 4~9 carbon atoms, Such as can enumerate succinic acid, glutaric acid, adipic acid, maleic acid, phthalic acid, M-phthalic acid, terephthalic acid (TPA), it Carboxylate, acyl chlorides, acid anhydrides.

The concrete example for the dicarboxylic acids that the carbon number of polyester polyol described below is 10~16, but never limited in present embodiment Due to these.

(1) 2,6- naphthalenedicarboxylic acids

(2) 2,3- naphthalenedicarboxylic acids

(3) 2,6- anthracenes dioctyl phthalate

(4) 2,6- naphthalenedicarboxylic acids：Succinic acid (75：25~99：1 molar ratio)

(5) 2,6- naphthalenedicarboxylic acids：Terephthalic acid (TPA) (50：50~99：1 molar ratio)

(6) 2,3- naphthalenedicarboxylic acids：Succinic acid (75：25~99：1 molar ratio)

(7) 2,3- naphthalenedicarboxylic acids：Terephthalic acid (TPA) (50：50~99：1 molar ratio)

(8) 2,6- anthracenes dioctyl phthalate：Succinic acid (50：50~99：1 molar ratio)

(9) 2,6- anthracenes dioctyl phthalate：Terephthalic acid (TPA) (25：75~99：1 molar ratio)

(10) 2,6- naphthalenedicarboxylic acids：Adipic acid (67：33~99：1 molar ratio)

(11) 2,3- naphthalenedicarboxylic acids：Adipic acid (67：33~99：1 molar ratio)

(12) 2,6- anthracenes dioctyl phthalate：Adipic acid (40：60~99：1 molar ratio)

As the petchem that can be used in present embodiment, other than above-mentioned polyester polyol, from chemical combination From the viewpoint of the water solubility of object, orientation, it is also preferred that the use of octanol-water partition coefficient (logP (B)) being 0 or more and less than 7 Compound.

Polyester polyol can be by as needed in the presence of esterification catalyst, for example in 180~250 DEG C of temperature The ester formative derivative of dicarboxylic acids or they is set (to be equivalent to logical in range, with 10~25 hours, using known customary way The ingredient of the A of formula (A)) it carries out esterification with glycol (ingredient for being equivalent to the G of general formula (A)) and manufactures.

Carry out esterification when, can be used toluene, dimethylbenzene equal solvent, it is preferably solvent-free or used as raw material use Method of the glycol as solvent.

As above-mentioned esterification catalyst, such as tetraisopropyl titanate, butyl titanate, p- toluenesulfonic acid, oxygen can be used Change dibutyl tin etc..For above-mentioned esterification catalyst, relative to dicarboxylic acids or the total amount 100 of their ester formative derivative Mass parts are, it is preferable to use 0.01~0.5 mass parts.

Molar ratio when the ester formative derivative of dicarboxylic acids or they being made to be reacted with glycol must be the terminal groups of polyester As the molar ratio of hydroxyl (hydroxy), it is accordingly, with respect to dicarboxylic acids or 1 mole of their ester formative derivative, glycol 1.1~10 moles.Preferably, relative to 1 mole of dicarboxylic acids or their ester formative derivative, glycol is 1.5~7 moles, It is highly preferred that relative to 1 mole of dicarboxylic acids or their ester formative derivative, glycol is 2~5 moles.

The terminal groups of above-mentioned polyester polyol are hydroxyl (hydroxy), but in polyester polyol, also may be used as by-product Compound containing carboxyl terminal.But the carboxyl terminal in polyester polyol makes humidity stability reduce, therefore preferably it contains It measures low.And specifically, it is preferable to acid value 5.0mgKOH/g hereinafter, more preferably 1.0mgKOH/g hereinafter, further preferably 0.5mgKOH/g or less.It is explained, " acid value " mentioned here refers to (there is acid contained in sample 1g in sample Carboxyl) neutralize necessary to potassium hydroxide milligram number.Acid value can be according to JIS K0070：1992 are measured.

The above-mentioned preferred hydroxyl of polyester polyol (hydroxy) value (OHV) is 35mg/g or more and 220mg/g models below It encloses.Hydroxyl (hydroxy) value mentioned here refers in order to which neutralize will be contained in sample 1g when the acetylation of OH bases and hydroxyl (hydroxy) the milligram number of the potassium hydroxide needed for the acetic acid combined.Hydroxyl (hydroxy) value is by using acetic anhydride by sample In the acetylation of OH bases, with potassium hydroxide solution not used acetic acid is titrated, by the titration value of the acetic anhydride with initial stage Difference find out.

Hydroxyl (hydroxy) content of above-mentioned polyester polyol is preferably 70% or more.Hydroxyl (hydroxy) is poor In the case of, the tendency of the compatibility reduction with polyester polyol and cellulose esters.Therefore, hydroxyl (hydroxy) content is preferred 70% or more, more preferably 90% or more, further preferably 99% or more.In present embodiment, hydroxyl (hydroxy) content For 50% compound below since one of terminal groups are replaced by the group other than hydroxyl (hydroxy), do not contain In polyester polyol.

Above-mentioned hydroxyl (hydroxy) content can be found out according to following formulas (B).

Y/X × 100=hydroxyls (hydroxy) content (%) (B)

X：Hydroxyl (hydroxy) value (OHV) of above-mentioned polyester polyol

Y：1/ (number-average molecular weight (Mn)) × 56 × 2 × 1000

Above-mentioned polyester polyol preferably with the number-average molecular weight in the range of 300~3000, more preferably have 350~ 2000 number-average molecular weight.

In addition, the dispersion degree of the molecular weight of the polyester polyol of present embodiment is preferably 1.0~3.0, more preferably 1.0 ~2.0.If dispersion degree is in above range, it is easy to get the polyester polyol excellent in compatibility with cellulose esters.

In addition, the ingredient that the molecular weight that above-mentioned polyester polyol preferably comprises 50% or more is 300~1800.By making number Average molecular weight becomes above range, so as to which compatibility is significantly increased.

As long as at least one of 2 terminal groups B of end capped polyesters are monocarboxylic acid residue.That is, in 2 terminal groups B One can be hydroxyl, another can be monocarboxylic acid residue.However, it is preferred to which both 2 terminal groups B are monocarboxylic acid residue.

As terminal groups B, above-mentioned benzene monocarboxylic acid residue, aliphatic monocarboxylic acid residue can be used, it is preferable that can make With benzene monocarboxylic acid residue.That is, end capped polyesters are preferably aromatic series end polyester.

For above-mentioned end capped polyesters, can by make glycol (ingredient for being equivalent to the G of general formula (A)) and dicarboxylic acids or it Ester formative derivative (ingredient for being equivalent to the A of general formula (A)) and monocarboxylic acid or their ester formative derivative (quite In the ingredient of the B of general formula (A)) carry out esterification and obtain, for example, can refer to Japanese Unexamined Patent Publication 2011-52205 bulletins, Japanese Unexamined Patent Publication 2008-69225 bulletins, Japanese Unexamined Patent Publication 2008-88292 bulletins, Japanese Unexamined Patent Publication 2008-115221 bulletins etc. Synthesis.

The ester compounds of present embodiment are the mixture of molecular weight and molecular structure with distribution at its synthesis moment, but Contain the preferred ingredient of institute at least one kind of present embodiment preferably wherein, such as residual with phthalic acid residue and adipic acid Petchem of the base as the A of general formula (A).

The number-average molecular weight of end capped polyesters is preferably 300~1500, and more preferably 400~1000.In addition, acid value is 0.5mgKOH/g hereinafter, hydroxyl (hydroxy) value be 25mgKOH/g hereinafter, it is highly preferred that acid value be 0.3mgKOH/g hereinafter, Hydroxyl (hydroxy) value is 15mgKOH/g or less.

Hereinafter, the specific compound of polyester (ester based compound) that can be used in present embodiment is shown, but this It's not limited to that for embodiment.

[changing 1]

[changing 2]

[changing 3]

As sugar ester (saccharide ester compound), it is the ester other than cellulose esters, is by following monosaccharide, disaccharides, trisaccharide or oligomerization Compound made of the whole of the OH bases of the sugar such as sugar or an esterification, illustrates as more specific, can enumerate by general formula (1) The compound etc. of expression.

[changing 4]

General formula (1)

In formula, R₁~R₈It indicates hydrogen atom, the alkyl-carbonyl of substituted or unsubstituted carbon number 2~22 or substitution or does not take The aryl carbonyl of the carbon number 2~22 in generation.R₁~R₈Can be identical, it also can be different.

Hereinafter, the compound (compound 1-1~compound 1-23) indicated by general formula (1) is more specifically shown, but simultaneously It is not limited to these.It is explained, in the case that average substitution degree is less than 8.0 in the following table, R₁~R₈Any of indicate hydrogen Atom.

[changing 5]

[changing 6]

[changing 7]

1-22

1-23

For these plasticizer, relative to 100 mass parts of cellulose ester membrane, 0.5~30 mass parts are preferably added.

[hard conating]

In the present embodiment, the hard conating as functional layer can be formed on the surface of optical film.Hard conating is preferably for example It is made of active energy ray-curable resin.

(active energy ray-curable resin)

Active energy ray-curable resin refers to anti-by crosslinking by dynamic rays irradiation as ultraviolet light, electron beam It should wait and cured resin, in particular the resin with ethylenically unsaturated group.More specifically, it is preferable to use ultraviolet curing Type urethane acrylate system resin, ultraviolet hardening polyester acrylate system resin, ultraviolet hardening epoxy third Olefin(e) acid ester system resin, ultraviolet hardening polyalcohol acrylate system's resin or ultraviolet hardening epoxy resin etc..It is wherein excellent Select ultraviolet hardening acrylic ester resin.

As ultraviolet hardening acrylic ester resin, preferably polyfunctional acrylic ester.As the multifunctional acrylic acid Ester is preferably selected from pentaerythrite polyfunctional acrylic ester, dipentaerythritol polyfunctional acrylic ester, the multifunctional methyl of pentaerythrite Acrylate and the multifunctional methacrylate of dipentaerythritol.Wherein, so-called polyfunctional acrylic ester is that have in the molecule 2 or more acryloxies or the compound of methacryloxy.

As the monomer of polyfunctional acrylic ester, such as preferably enumerate glycol diacrylate, diethylene glycol (DEG) two Acrylate, 1,6 hexanediol diacrylate, neopentylglycol diacrylate, trimethylolpropane trimethacrylate, three hydroxyls Methyl ethane triacrylate, tetramethylol methane triacrylate, tetramethylol methane tetraacrylate, five glycerine, three propylene Acid esters, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, glycerol tri-acrylate, Dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, Dipentaerythritol Pentaacrylate, dipentaerythritol 6 third Olefin(e) acid ester, three (acryloyl-oxyethyl) isocyanuric acid esters, ethylene glycol dimethacrylate, diethylene glycol dimethyl base acrylic acid Ester, 1,6-HD dimethylacrylate, neopentylglycol dimethacrylate, trimethylol propane trimethyl acrylic acid Ester, trimethylol ethane trimethacrylate, tetramethylol methane trimethyl acrylic ester, tetramethylol methane tetramethyl third Olefin(e) acid ester, five glycerol trimethacrylates, dimethyl pentaerythritol acrylate, pentaerythritol acrylate trimethyl, season Penta tetrol tetramethyl acrylate, glycerol trimethacrylate, dipentaerythritol trimethyl acrylic ester, dipentaerythritol four Methacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexamethacrylate, active energy line curing The isocyanurate derivative etc. of type.As these polyfunctional acrylic esters, it is possible to use commercially available product can obtain pentaerythrite Three/tetraacrylate (manufacture of chemical industry Co., Ltd. of the villages Xin Zhong, A-TMM-3L etc.), pentaerythritol triacrylate (common prosperity Society's chemistry manufacture, PE-3A) etc..It is explained, these compounds are respectively used alone or are used in mixed way two or more.

As the isocyanurate derivative of active energy ray-curable resin, as long as in isocyanuric acid skeleton The compound of the structure of 1 or more ethylenically unsaturated group is combined, there is no particular restriction, preferably in same intramolecular The compound of isocyanurate ring with 3 or more ethylenically unsaturated groups and 1 or more.

As such isocyanuric acid triacrylate compound, can also use commercially available product, for example, can enumerate it is new in Village chemical industry Co. Ltd. system A-9300 etc..As the commercially available product of isocyanuric acid diacrylate compounds, such as can enumerate Go out Toagosei Co., Ltd ARONIX M-215 etc..As isocyanuric acid triacrylate compound and isocyanuric acid dipropyl The mixture of enoic acid ester compounds, such as Toagosei Co., Ltd ARONIX M-315, ARONIX M-313 can be enumerated Deng.As the isocyanurate derivative for the active energy ray-curable that 6-caprolactone is modified, can enumerate as ε-in oneself The villages the Xin Zhong chemical industry Co. Ltd. system A-9300-1CL of ester modified three-(acryloyl-oxyethyl) isocyanuric acid ester, East Asia Co. Ltd. system ARONIX M-327 etc. are synthesized, but are not limited to these.

In addition, as active energy ray-curable resin, monofunctional acrylate can be used.As simple function acrylic acid Ester can enumerate isobornyl acrylate, acrylic acid 2- hydroxyl -3- phenoxy-propyls, isostearyl acrylate, acrylic acid benzyl Ester, ethyl carbitol acrylate, phenoxyethyl acrylate, lauryl acrylate, Isooctyl acrylate monomer, acrylic acid tetrahydrochysene chaff Ester, behenyl base ester, acrylic acid 4- hydroxybutyls, acrylic acid 2- hydroxy methacrylates, acrylic acid 2- hydroxy propyl esters, propylene Sour cyclohexyl etc..It, can be from chemical industry Co., Ltd. of the villages Xin Zhong, Osaka Organic Chemical Industry strain as monofunctional acrylate The acquisitions such as formula commercial firm.These compounds can respectively be used alone or be used in mixed way two or more.Furthermore it is possible to be above-mentioned The oligomer such as 2 aggressiveness of monomer, 3 aggressiveness.

In turn, as active energy ray-curable resin, urethane acrylate can be used.As carbamate Acrylate, such as the UA- of Arakawa Chemical Industries (strain) ビ ー system セ ッ ト 575CB processed, common prosperity society chemistry can be used The commercially available products such as 306H.

For the viscosity of above-mentioned such polyfunctional acrylic ester, viscosity at preferably 25 DEG C be 3000mPas with Under, more preferable 1500mPas or less.Particularly preferably 1000mPas or less.As such low viscosity resin, Neng Goulie Enumerate glycerol tri-acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate etc..It is explained, above-mentioned viscosity It is the value measured under conditions of 25 DEG C using E types viscosimeter.

For the use level of the above-mentioned active energy ray-curable resin in hard coating composition, if composition is complete Body is set as 100 mass parts, usually 10~99 mass parts, preferably 35~99 mass parts.If active energy ray-curable tree The use level of fat is few, then is difficult to fully obtain the film-strength of hard conating.In addition, if use level is more, occur using aftermentioned The coating of well known coating method when film thickness uniformity, the failure of coating striped etc., therefore not preferably.

(cationically polymerizable compound)

Hard conating can also contain cationically polymerizable compound.Cationically polymerizable compound is by energy active ray The compound of irradiation, thermally-induced cationic polymerization and resinification.Specifically, epoxy group, cyclic ether group, cyclic acetal can be enumerated Base, annular lactone base, cyclic thioether base, spiro orthoester compound, vinyl oxo base etc..Wherein, in the present embodiment It is preferable to use the compounds with functional groups such as epoxy group, vinyl ether groups.

As the cationically polymerizable compound with epoxy group or vinyl ether group, such as can to enumerate phenyl glycidyl sweet Oleyl ether, ethylene glycol diglycidyl base ether, glycerine diglycidyl ether, vinyl cyclohexene dioxide, Er Yangization Limonene Alkene (リ モ ネ Application ジ オ キ サ イ De), 3,4- epoxycyclohexyl-methyls -3 ', 4 '-epoxycyclohexane carboxylates, double-(6- methyl - 3,4- epoxycyclohexyls) adipate ester, 2- (3,4- epoxycyclohexyl) ethyl trimethoxy silane, diethylene glycol divinyl ether, Polyethylene glycol divinyl ether, 1,4 cyclohexane dimethanol divinyl ether etc..In addition, as epoxide, can also make Use polymer compound.

In the case of containing above-mentioned cationically polymerizable compound in hard coating composition, with regard in hard coating composition For the use level of cationically polymerizable compound, if composition entirety is set as 100 mass parts, usually 1~90 matter Measure part, preferably 1~50 mass parts.

(particle)

Hard conating can contain particle.As particle, inorganic particles and organic fine particles can be enumerated.As inorganic particulate, energy Enough enumerate silica, titanium oxide, aluminium oxide, tin oxide, indium oxide, ITO, zinc oxide, zirconium oxide, magnesia, calcium carbonate, Calcium carbonate, talcum, clay, firing kaolin, firing calcium silicates, afwillite, alumina silicate, magnesium silicate and calcium phosphate.As Organic filler can enumerate poly-methyl methacrylate base acrylate powder, styrene system toner, gather Polymethyl methacrylate resin powder, silicon system resin powder, polystyrene resin powder, polycarbonate resin powder, benzo Guanamine series toner, melamine system toner, polyolefin-based resins powder, polyester based resin powder, polyamide series resin powder End, polyimides system resins powder or poly- ethylene fluoride system toner etc..The average grain diameter of these particles is coated with from hard conating The stability of composition, transparency consideration, preferably 30nm~200nm.In addition, hard conating containing grain size different 2 kinds with On particle.From the aspect of desired pencil hardness easy to implement, preferably make to contain silicon dioxide microparticle in hard conating.

In addition, from the aspect of the function and effect for preferably playing present embodiment, containing useful preferably in hard conating The reactive silica particle (Xa) that organic compound with polymerism unsaturated group is surface-treated.It is right below The reactive silica particle (Xa) being surface-treated using the organic compound with polymerism unsaturated group into Row explanation.

《Reactive silica particle (Xa)》

As silicon dioxide microparticle, well known silicon dioxide microparticle can be used.In addition, its shape can also may be used to be spherical Think unsetting, however it is not limited to which common colloidal silicon dioxide can also be hollow-particle, porous granule, core/shell type particle Deng the colloidal silicon dioxide that preferably pH is 2.0~6.5.

The preferred water of decentralized medium or organic solvent of silicon dioxide microparticle.As organic solvent, methanol, different can be enumerated The alcohols such as propyl alcohol, ethylene glycol, butanol, ethylene glycol monopropyl ether；The ketones such as methyl ethyl ketone, methyl iso-butyl ketone (MIBK)；Toluene, dimethylbenzene etc. It is aromatic hydrocarbon；The amides such as dimethylformamide, dimethylacetylamide, N-Methyl pyrrolidone；Ethyl acetate, acetic acid fourth The esters such as ester, gamma-butyrolacton；The organic solvents such as the ethers such as tetrahydrofuran, Isosorbide-5-Nitrae-dioxane, in these, preferably alcohols and ketone. These organic solvents also can mixedly be used as decentralized medium individually or by two or more.As commercially available product, for example, As colloidal silicon dioxide, Nissan Chemical Industries (strain) MEK-ST-L, MEK-ST-MS processed, IPA-ST-L, IPA- can be enumerated ST-ZL etc..

Reactive silica particle (Xa) by with the organic compound with polymerism unsaturated group (hereinafter referred to as " organic compound (X) ") it above-mentioned such colloidal silicon dioxide is surface-treated is obtained.Organic compound (X) is preferred For with polymerism unsaturated group, preferably ethylenically unsaturated group, also with group shown in the following general formula (a) and point There is the compound of silanol group in sub or the compound of silanol group is generated by hydrolysis.

[changing 8]

[- U-C (=V)-NH-] be specially [- O-C (=O)-NH-], [- O-C (=S)-NH-], [- S-C (=O)-NH-], This 6 kinds of [- NH-C (=O)-NH-], [- NH-C (=S)-NH-] and [- S-C (=S)-NH-].These groups can a kind individually It is applied in combination using or by two or more.Wherein, from the viewpoint of thermal stability, preferably by [- O-C (=O)-NH-] base with In [- O-C (=S)-NH-] base or [- S-C (=O)-NH-] base at least any one be used in combination.

As ethylenically unsaturated group contained in organic compound (X), there is no particular restriction, such as can enumerate third Enoyl-, methylacryloyl, vinyl are as preference.The ethylenically unsaturated group is added using living radical kind At the structural unit of polymerization.

As the compound for generating silanol group, it is former that alkoxy, aryloxy group, acetoxyl group, amino, halogen can be enumerated Son etc. is incorporated into the compound of silicon atom, and preferably alkoxy or aryloxy group is incorporated into the compound of silicon atom, contains alkoxy The compound of silicyl or compound containing aryloxysilyls.As concrete example, such as can enumerate by following Compound shown in general formula (b).

[changing 9]

In general formula (b), R²¹、R²²Can it is identical also can be different, be the alkyl or aryl of hydrogen atom or carbon number 1~8, such as Methyl, ethyl, propyl, butyl, octyl, phenyl, xylyl etc. can be enumerated.Wherein, the integer that j is 1~3.

As by [(R²¹O)_jR²² _3-jSi-] group that indicates, such as trimethoxysilyl, three ethoxies can be enumerated Base silicyl, triphenoxysilyl groups, methyl dimethoxy oxygroup silicyl, dimethylmethoxysilylgroups groups etc..In this way Group in, preferably trimethoxysilyl or triethoxysilyl etc..

R²³For the organic group of the divalent with aliphatic or aromatic structure of carbon number 1~12, chain, branch can be contained Shape or cricoid structure.As concrete example, methylene, ethylidene, propylidene, butylidene, hexa-methylene, sub- ring can be enumerated Hexyl, phenylene, xylylene, ten dimethylenes etc..

R²⁴For the organic group of divalent, usually from molecular weight 14 to 10,000, the organic group of the divalent of preferred molecular weight 76 to 500 It is selected in group.As concrete example, the chains polyalkylenes such as hexa-methylene, eight methylene, ten dimethylenes can be enumerated；Sub- ring The organic group of the ester ring types such as hexyl, sub- norborny or the divalent of polycycle；Phenylene, naphthylene, biphenylene, poly- sub- benzene The aromatic group of the divalents such as base；Replace body with their alkyl substitution body, aryl.In addition, the organic group of these divalents can contain There is the atomic group for including the element other than carbon and hydrogen atom, can also contain polyethers key, polyester key, polyamide bond, makrolon Key.

R²⁵For the organic group of (k+1) valence, preferably from chain, branch-like or cricoid saturated hydrocarbyl, unsaturated alkyl Selection.

Z indicates there is the polymerism insatiable hunger that intermolecular cross-linking reaction is carried out in the presence of living radical kind in the molecule With the organic group of 1 valence of group.In addition, k is preferably 1~20 integer, more preferably 1~10 integer, particularly preferably 1 ~5 integer.

For organic compound (X), such as can be by making hydrolysable silanes, being selected from polyisocyanate compound, more Isothiocyanic acid ester compounds and the change simultaneously with one or more of isocyanate group and the compound of isothiocyanic acid ester group Close object, the gathering containing reactive hydrogen with the active hydrogen atom for causing addition reaction with isocyanate group or isothiocyanic acid ester group Close property unsaturated compound direct addition reaction and carry out.

Preferably, mercaptopropyi trimethoxy silane and isophorone diisocyanate are deposited in dibutyl tin laurate In lower mixing, after so that it is reacted hours or so at 60~70 DEG C, pentaerythritol triacrylate is added, and then 60~70 It is set to react hours or so at DEG C.

Then, obtained organic compound (X) is mixed with silicon dioxide microparticle, makes its hydrolysis, so that the two is combined, thus Reactive silica particle (Xa) can be manufactured.

For the binding capacity of the organic compound (X) combined with silicon dioxide microparticle, silicon dioxide microparticle is set as 100 Quality %, preferably 0.01 mass % or more, more preferably 0.1 mass % or more, particularly preferably 1 mass % or more.

If it is above range, the favorable dispersibility of the reactive silica particle (Xa) in composition.In addition, anti- The mixing ratio of the silicon dioxide microparticle in raw material when answering property silicon dioxide microparticle (Xa) manufactures is preferably 5~99 mass %, More preferably 10~98 mass %.When solid constituent total amount in composition is set as 100 mass %, hard conating coating compositions The content of reactive silica particle (Xa) in object preferably 5~80 mass %, more preferable 10~80 mass %.By with this The range of sample uses, and in hard conating coating composition reactive silica particle (Xa) steadily exists.

In addition, hard conating preferably comprises above-mentioned active energy ray-curable resin and particle, indicated with containing mass ratio, For active energy ray-curable resin：Particle=90：10~20：80.

The manufacturing method of hard conating (other additives)

In hard conating, promote for the solidification of above-mentioned active energy ray-curable resin, it is preferably further poly- containing light Close initiator.It as the use level of Photoepolymerizationinitiater initiater, is indicated with mass ratio, preferably Photoepolymerizationinitiater initiater：Active energy ray Gel-type resin=20：100~0.01：100.

As Photoepolymerizationinitiater initiater, specifically, alkyl phenyl ketone system, acetophenone, benzophenone, hydroxyl two can be enumerated Benzophenone, Michler's keton, α-amyl oxime ester, thioxanthones etc. and their derivative, but it is not particularly limited to these.These Commercially available product can be used, such as イ Le ガ キ ュ ア 184, the イ Le ガ キ ュ ア of BASF ジ ャ パ Application (strain) system can be enumerated 907, イ Le ガ キ ュ ア 651 etc. are illustrated as preferred.

In addition, hard conating contains ultra-violet absorber same as above-mentioned ultra-violet absorber.

In turn, from the target effect for playing present embodiment well, and the film-strength for obtaining hard conating well is (resistance to It is scratch resistance), from the aspect of pencil hardness, preferably hard conating is constituted by 2 layers or more, and in the hard conating to connect with base material film In contain ultra-violet absorber.It as the content of ultra-violet absorber, is indicated with mass ratio, preferably with ultra-violet absorber：Firmly Coating composition=0.01：100~10：100 and contain.

In the case where 2 layers or more of hard conating is arranged, the film thickness of the hard conating to connect with base material film is preferably 0.05~2 μm range.2 layers or more of stacking can be formed by double-layer simultaneously.So-called while double-layer, refer to without drying process and 2 layers or more of hard conating is being coated on base material by wet on wet by is forming hard conating.Without overdrying on the 1st hard conating Drying process and when 2 hard conating is laminated by wet on wet, extrusion coated machine can be used and carry out gradually double-layer or using tool There is the slit coventry type die head coventry of multiple slits to carry out double-layer simultaneously.

In addition, the production method as hard conating, closely sealed from the interlayer for being easy to get hard conating and cellulose ethanoate film From the aspect of, preferably following method：Using the following method will with for cellulose ethanoate film carry out swelling or part it is molten The hard conating coating composition that the solvent of solution dilutes is coated and dried on cellulose ethanoate film, cures and is arranged.

As by cellulose ethanoate membrane swelling or partly soluble solvent, the solvent of ketone and/or acetate is preferably comprised. Specifically, as ketone, methyl ethyl ketone, acetone, cyclohexanone etc. can be enumerated.In addition, as acetate, acetic acid second can be enumerated Ester, methyl acetate, butyl acetate etc..Hard conating coating composition can contain alcohol series solvent as other solvents.

The coating weight of hard conating coating composition is in terms of wet coating thickness, preferably 0.1~40 μm, more preferably 0.5~30 μm.Separately Outside, in terms of dried film thickness, average film thickness is 5~20 μm or so, preferably 7~12 μm.

Hard conating can be by using heliogravure coating machine, dip coater, reversion coating machine, bar coater, mouth mold formula Coating method well known to (extrusion) coating machine, ink-jet method etc., the hard conating coating composition to forming hard conating are coated, apply It after cloth, is dried, irradiation dynamic rays (also referred to as UV curing process), in turn, as needed, is heated after UV solidifications Processing is to form.Heat treatment temperature after curing as UV, preferably 80 DEG C or more, more preferably 100 DEG C or more are especially excellent It is selected as 120 DEG C or more.By carrying out the heat treatment after UV solidifications at this high temperature, to the mechanical strength of hard conating (erasibility, pencil hardness) becomes more good.

For drying, the temperature in lapse rate drying section is preferably made to be carried out as 80 DEG C or more of high temperature.It is highly preferred that The temperature that lapse rate dries section is 95 DEG C or more, 130 DEG C or less.Become high temperature by the temperature for making lapse rate dry section, carries out It is dried, to generate convection current in applying film resin in the formation of hard conating, therefore is easy to show in hard coating surface Fine rough surface is also easy to get aftermentioned arithmetic average roughness Ra.

Usually, for drying process, it is known that if drying starts, the state certain from rate of drying is at leisure Rate of drying is that certain section is known as constant-rate method of drying section, the section of rate of drying reduction is claimed by the state change of reduction Section is dried for lapse rate.The heat flowed into constant-rate method of drying section is all consumed by the evaporation of the solvent of film coated surface, if The solvent of film coated surface tails off, then evaporating surface is internally moved from surface, and section is dried into lapse rate.After it, film coated surface Temperature rise, close to hot blast temperature, therefore, it is considered that the temperature rise of ultraviolet-curing resin composition, resin viscosity drop Low, mobility increases.

As the light source of UV curing process, as long as generating the light source of ultraviolet light, then can unlimitedly use.Such as it can Enough use low pressure mercury lamp, medium pressure mercury lamp, high-pressure sodium lamp, ultrahigh pressure mercury lamp, carbon arc lamp, metal halide lamp, xenon lamp etc..

Irradiation condition is different because of each lamp, and the exposure of dynamic rays is usually 50~1000mJ/cm², preferably 50~ 300mJ/cm²。

In addition, when irradiating dynamic rays, preferably carried out while assigning tension on the conveying direction in film, more preferably It is carried out while also assigning tension in the direction of the width.The tension of imparting is usually 30~500N/m, preferably 30~300N/ m.The method for assigning tension is not particularly limited, tension can be assigned in the conveying direction on back flow roll, it is possible to use stenter Tension is assigned in width direction or biaxially oriented.Thus, it is possible to obtain the superior film of flatness.

It in order to assign antistatic property, can make to contain conductive agent in hard conating, as preferred conductive agent, metal can be enumerated Oxide particle or pi-conjugated system's electric conductive polymer.In addition, ionic liquid also preferably acts as conductive compound.

In addition, fluoro- silicone grafted polymers, silicone based surfactants can be contained in hard conating.

So-called fluoro- silicone grafted polymers, refer at least make in fluorine resin siloxanes and/or contain organic silica The polymer of copolymer obtained from the polysiloxanes and/or organopolysiloxane grafting of alkane monomer.It, can as commercially available product Enumerate ZX-022H, ZX-007C, ZX-049, ZX-047-D etc. of the manufacture of chemical conversion industry Co., Ltd. of Fuji.

Silicone based surfactants are the surfactants that a part for the methyl of silicone oil is replaced by hydrophilic radical. As hydrophilic radical, there are polyethers, polyglycereol, pyrrolidones, glycine betaine, sulfate, phosphate, quaternary salt etc..As organosilicon The specific commodity of surfactant, such as SH200, BY16-873, PRX413 (dimethicone can be enumerated；East レ ダ ウ U ー ニ Application グ シ リ U ー Application company manufacture), SH203, SH230, SF8416 (alkyl modified silicon oil；East レ ダ ウ Us ー ニ Application グ シ リ U ー Application company manufacture), SF8417, BY16-208, BY16-209, BY16-849, BY16-872, FZ- 2222, FZ-2207 (dimethyl polysiloxanes-straight chain of polyethylene oxide shape block copolymer；The FZ of Japanese ユ ニ カ ー (strain) system Series), KF-101, KF-102, KF-105 (epoxy modified polysiloxane；Chemical industrial company of SHIN-ETSU HANTOTAI manufacture), BYK-UV3500, BYK- UV3510, BYK-333, BYK-331, BYK-337 (polyether modified silicon oil, the manufacture of ビ ッ Network ケ ミ-ジ ャ パ Application company) etc., but It is not limited to these.

In addition, for these ingredients, relative to the solid constituent in coating fluid, preferably with the model of 0.01~5 mass % Enclose addition.

(surface shape of hard conating)

For the arithmetic average roughness Ra on the surface of the hard conating in present embodiment, from when being taken with long size film roll Preventing adhesiving effect, with from the aspect of the excellent adhesion of cellulose ethanoate film, preferably 4~20nm.With regard to arithmetic average It is to be based on JIS B0601 for roughness Ra：1994 regulation, with optical interference formula surface roughness meter (RST/PLUS, WYKO companies manufacture) value that is measured.

In addition, preferably 3~40 μm of the concave-convex equispaced Sm of hard coating surface.In addition, the arithmetic on the surface of hard conating is flat The ratio (Ra/Sm) that the hard conating of equal roughness Ra and cellulose ester membrane (film base material) is coated with the concave-convex equispaced Sm in face is preferred It is 2 × 10^-4~6 × 10^-3.About Sm, in the same manner as arithmetic average roughness Ra, JIS B0601 can be based on：1994 rule Determine, measured with optical interference formula surface roughness meter (RST/PLUS, WYKO company manufacture).

In order to make hard conating surface arithmetic average roughness Ra be above range, can use make mold pressing and The method that surface forms protrusion；The method that the different resin of SP values (solubility parameter) is mixed, forms concave-convex surface；Pass through rotation Amount decomposition, karyogenesis etc. make the method that protrusion is formed.

It is explained, it, can be from concave-convex thin mold roller to concave-convex thick mold as the mold roller formed for protrusion Properly selected in roller to apply, can use by delustring shape, cylindrical lenses shape, it is spherical it is concave-convex regularly or randomly Mold roller made of arrangement.

In addition, from the aspect of obtaining sufficient brightness, high contrast, the haze value of the hard coat film of present embodiment Preferably 1% or less.

[functional layer]

(back coating)

In the face of the opposite side of the side for being provided with hard conating of the film base material of present embodiment, crimps in order to prevent, is viscous Even, back coating can be set.

From curling is prevented, from the aspect of adhesion, can be added in back coating silica, titanium dioxide, aluminium oxide, Zirconium oxide, calcium carbonate, calcium carbonate, talcum, clay, firing kaolin, firing calcium silicates, tin oxide, indium oxide, zinc oxide, The particle of ITO, afwillite, alumina silicate, magnesium silicate and calcium phosphate etc..

Relative to binder, particle preferably 0.1~50 mass % contained in back coating.Mist when from provided with back coating The increase of degree considers that preferably 0.5% hereinafter, particularly preferably 0.1% or less.As binder, preferred cellulose ester resin. In addition, in the coating composition for being used to form back coating, the solvent of alcohols, ketone and/or acetates sugar is preferably comprised.

(anti-reflection layer)

In the present embodiment, hard conating also can be formed on film base material, be coated with antireflection on the upper layer of the hard conating Layer, uses as the antireflection film with outer smooth anti-reflective function.

For anti-reflection layer, it is considered preferred to refractive index, film thickness, the number of layer, layer sequence etc. and be laminated so that reflectivity Reduce due to optical interference.Anti-reflection layer preferably by the refractive index low-index layer lower than the film base material as supporting mass or The refractive index high refractive index layer higher than supporting mass is combined with low-index layer and is constituted by person.It is particularly preferred that for by 3 layers or more Index layer constitute anti-reflection layer, refractive index is different since support side 3 layers it is preferable to use with middle index layer (roll over Penetrate the layer that rate is higher than supporting mass, refractive index is lower than high refractive index layer) stacking of the sequence of/high index layer/low index layer it is anti- Reflecting layer.Or it is also preferred that use be alternately laminated the low-index layer of 2 layers or more of high refractive index layer and 2 layers or more 4 Layer or more layer constitute anti-reflection layer.

Layer as the film with anti-reflection layer is constituted, and considers following such compositions, but not limited to this.

Cellulose ethanoate film/hard conating/low-index layer

Cellulose ethanoate film/hard conating/middle index layer/low-index layer

Cellulose ethanoate film/hard conating/middle index layer/high index layer/low index layer

Cellulose ethanoate film/hard conating/high refractive index layer (conductive layer)/low-index layer

Cellulose ethanoate film/hard conating/anti-glare layer/low-index layer

(low-index layer)

Low-index layer preferably comprises silica-based particle, and refractive index is preferably in 23 DEG C, wavelength 550nm are measured 1.30~1.45 range.

The film thickness of low-index layer is preferably 5nm~0.5 μm, more preferably 10nm~0.3 μm, and most preferably 30nm~ 0.2μm。

At least one or more is particularly preferably contained as silica-based particle for low-index layer formation composition With outer shell and it is internal be Porous or cavity particle.It is Porous or cavity that should particularly preferably have outer shell and inside Particle be hollow silica system particle.

It is explained, it, can be along with being indicated by the following general formula (OSi-1) in low-index layer formation composition Organo-silicon compound or its hydrolysate or its condensation polymer.

General formula (OSi-1)：Si(OR)₄

For the organo-silicon compound indicated by above-mentioned general formula, in formula, R indicates the alkyl of carbon number 1~4.Specifically, excellent Choosing uses tetramethoxy-silicane, tetraethoxysilane, tetraisopropoxysilan etc..

In addition, solvent can be added, silane coupling agent, curing agent, surfactant etc. can be added as needed.In addition, It can contain：With the range of 35~80 mass % contain fluorine atom and functional group containing bridging property or polymerism containing fluorination Close the compound with Thermocurable and/or photo-curable based on object.In particular fluoropolymer or fluorine-containing collosol and gel Compound etc..As fluoropolymer, for example, can enumerate containing perfluoroalkyl silane compound [such as (ten seven fluoro- 1,1, 2,2- tetrahydrochysene decyls) triethoxysilane] hydrolysate, dehydration condensation, can enumerate with fluorine-containing monomer unit and friendship in addition Join fluorinated copolymer of the reactive unit as structural unit.In addition, solvent can be added, can add as needed silane coupled Agent, curing agent, surfactant etc..

(high refractive index layer)

For the refractive index of high refractive index layer, in 23 DEG C, wavelength 550nm are measured, refractive index is preferably adjusted to 1.4 ~2.2 range.In addition, preferred 5nm~1 μm of the thickness of high refractive index layer, more preferably 10nm~0.2 μm, most preferably 30nm~0.1 μm.The adjustment of refractive index can be carried out by adding metal oxide microparticle etc..The metal oxide used is micro- The refractive index of grain is preferably 1.80~2.60, and more preferably 1.85~2.50.

The type of metal oxide microparticle is not particularly limited, can use have selected from Ti, Zr, Sn, Sb, Cu, Fe, The metal oxide of at least one of Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P and S element.It is aoxidized in these metals The micro atom such as Al, In, Sn, Sb, Nb, halogens, Ta can be adulterated in object particle.Alternatively, it is also possible to being their mixing Object.In present embodiment, wherein particularly preferably using selected from zirconium oxide, antimony oxide, tin oxide, zinc oxide, indium oxide-tin (ITO), at least one kind of metal oxide microparticle in antimony-doped tin oxide (ATO) and zinc antimonates is as principal component.Particularly preferably Contain metaantimmonic acid zinc particles.

The average grain diameter of the primary particle of these metal oxide microparticles is the range of 10nm~200nm, particularly preferably 10~150nm.The average grain diameter of metal oxide microparticle can be by the electron microscope using scanning electron microscope (SEM) etc. Photo measures.It can also be used and utilize the meterings such as the particle size distribution meter of dynamic light scattering method, static light scattering method etc..If grain size mistake It is small, then become easy cohesion, dispersibility deterioration.If grain size is excessive, mist degree significantly rises without preferred.Metal oxide Particle is preferably shaped to rice-shaped, spherical shape, cubic, spindle shape, needle-shaped or indefinite shape.

For metal oxide microparticle, organic compound can be used and be surface-treated.By with organic compound pair The surface of metal oxide microparticle carries out surface modification, to which dispersion stabilization in organic solvent improves, dispersion particle diameter Control becomes easy, and can inhibit through when cohesion, sedimentation.Therefore, just preferably changed with the surface of organic compound Property amount for, be the 0.1 mass % of mass %~5, more preferably 0.5 matter of mass %~3 relative to metal oxide particle Measure %.In the example for the organic compound of surface treatment, contain polyalcohol, alkanolamine, stearic acid, silane coupling agent And titanate coupling agent.Wherein preferred silane coupling agent.Two kinds or more of surface treatment can be combined.

In addition, high refractive index layer can contain pi-conjugated system's electric conductive polymer.So-called pi-conjugated system's electric conductive polymer, as long as It is the organic polymer that main chain is made of pi-conjugated system, it will be able to use.Such as polythiophene class, multi-metal polypyrrole, polyphenyl can be enumerated Amine, polyphenylene class, polyacetylene class, polyphenylene vinylene class, polyacene class, polythiophenevinylenes class and they Copolymer.From the aspect of from the easiness, stability of polymerization, preferably polythiophene class, polyaniline compound, polyacetylene class.

For pi-conjugated system's electric conductive polymer, sufficient electric conductivity is obtained in the state of unsubstituted, viscous Tie the dissolubility in agent resin, but in order to further increase electric conductivity, dissolubility, can introduce alkyl, carboxyl, sulfo group, alkoxy, The functional groups such as hydroxyl, cyano.

In addition, high refractive index layer can contain ionic compound.As ionic compound, can enumerate by imidazoles System, pyridine system, ester ring type amine system, aliphatic amine system, Phosphonium system of Zhi Fang races cation and BF₄-、PF₆Wait inorganic ions system, CF₃SO₂-、(CF₃SO₂)₂N-、CF₃CO₂Etc. the anion composition of fluorine systems compound etc..With regard to the ratio of the polymer and binder For rate, relative to 100 mass parts of polymer, binder preferably 10~400 mass parts, particularly preferably, relative to polymer 100 mass parts, binder are 100~200 mass parts.

(anti-glare layer)

Antiglare layer can be also set on hard conating as functional layer.Anti-glare layer is by making to reflect in film surface The soft edge of picture reduces the visibility of reflection image, liquid crystal display, organic el display, plasma scope in this way Image display device etc. the layer mirrored for making not having to worry reflection image when using.For antiglare layer, and specifically, it is preferable to Particle etc., the method for being pressed against above-mentioned mold and forming protrusion on surface etc. are added in above-mentioned hard conating by layer surface to use Arithmetic average roughness Ra adjust to 0.1~1 μm of layer.

In addition, the scattered reflection rate of above-mentioned antiglare layer it is shared in integrated reflectivity ratio (scattered reflection ratio) it is excellent It is selected as 2~60%.By using particle etc. by scattered reflection rate control in above range, can improve above-mentioned such has The cellulose ethanoate film of the high degree of acetylation of penetrability and the interlayer adaptation of antiglare layer.It is highly preferred that if above-mentioned scattering The range that the ratio of reflection ratio is 20~50%, then can further make adaptation become good.

It is explained, scattered reflection ratio can be by using Konica Minolta (strain) system, spectral photometric colour measuring meter CM- 2500d measures SCI (integrated reflectivity) and SCE (scattered reflection rate) under conditions of measuring diameter phi 8mm, 2 ° of field of view And it finds out.

[conductive layer]

In the present embodiment, conductive layer can be formed in the most surface (such as on hard conating) of optical film.Conductive layer is at least Containing conducting fibre, binder, photosensitive compounds are preferably comprised, further as needed containing other ingredients.

(conducting fibre)

As the structure of conducting fibre, there is no particular restriction, can be properly selected according to purpose, preferably solid knot Any one of structure and hollow structure.

Wherein, the fiber of solid construction is known as line sometimes, is known as managing by the fiber of hollow structure sometimes.

In addition, being sometimes 5nm~1000nm by average minor axis length, the electric conductivity that average major axis length is 1 μm~100 μm Fiber is known as " nano wire ".

In addition, being sometimes 1nm~1000nm by average minor axis length, average major axis length is 0.1 μm~1000 μm, has The conducting fibre of hollow structure is known as " nanotube ".

As the material of conducting fibre, as long as conductive, then there is no particular restriction, can be according to purpose suitably Selection, the preferably at least either in metal and carbon.In these, conducting fibre is preferably metal nanometer line, metal nano At least either in pipe and carbon nanotube.

＜ metal nanometer lines ＞

As the material of metal nanometer line, there is no particular restriction, can be properly selected according to purpose.For example, it is preferable to select At least one kind of metal from the 4th period, the 5th period and the 6th period of long period rule table (IUPAC1991), is more preferably selected from At least one kind of metal in race of 2nd race~the 14th, further preferably selected from the 2nd race, the 8th race, the 9th race, the 10th race, the 11st race, At least one kind of metal in 12nd race, the 13rd race and the 14th race particularly preferably contains it as principal component.

As above-mentioned metal, for example, can enumerate copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, iron, ruthenium, osmium, manganese, Molybdenum, tungsten, niobium, tantalum, titanium, bismuth, antimony, lead or their alloy etc..In these, from the aspect of excellent electric conductivity, preferably silver with And the alloy with silver.

As the metal used in above-mentioned and silver-colored alloy, platinum, osmium, palladium, iridium etc. can be enumerated.They can a kind individually It uses, also two or more may be used.

As the shape of metal nanometer line, there is no particular restriction, can be properly selected according to purpose.Such as can be in circle Column, rectangular-shape, section become the arbitrary shapes such as the column of polygon.The use for needing high transparency on the way, preferably The cross sectional shape that the angle of cylindric, section polygon is rounded.The cross sectional shape of metal nanometer line can be by applying on base material Cloth metal nanometer line aqueous dispersions are observed section with transmission electron microscope (TEM) and are investigated.

The average minor axis length (sometimes referred to as " average short axis diameter ", " average diameter ") of metal nanometer line be preferably 1nm~ 50nm.If above-mentioned average minor axis length is deteriorated less than 1nm, sometimes oxidative resistance, durability is deteriorated, if it exceeds 50nm, has When generation cause in the scattering of metal nanometer line, the sufficient transparency cannot be obtained.It is explained, above-mentioned average minor axis length is more Preferably 10nm~40nm, further preferably 15nm~35nm.

For the average minor axis length of metal nanometer line, transmission electron microscope (TEM is used；Japan Electronics strain formula Commercial firm's manufacture, JEM-2000FX), 300 metal nanometer lines are observed, the average minor axis of metal nanometer line has been found out by its average value Length.It is explained, for the minor axis length when short axle of metal nanometer line is not circle, longest length is set as short axle Length.

The average major axis length of metal nanometer line is preferably (sometimes referred to as " average length ") 1 μm~40 μm.If above-mentioned Average major axis length is difficult to form close network sometimes less than 1 μm, cannot obtain sufficient electric conductivity, if it exceeds 40 μm, then Metal nanometer line is long and tangles during fabrication, generates condensation product in the fabrication process sometimes.It is explained, above-mentioned average major axis Length is more preferably 3 μm~35 μm, further preferably 5 μm~30 μm.

For the average major axis length of metal nanometer line, such as use transmission electron microscope (TEM；Japan Electronics Co., Ltd.'s manufacture, JEM-2000FX), 300 metal nanometer lines are observed, being averaged for metal nanometer line has been found out by its average value Long axis length.It is explained, in the case of metal nanometer line bending, considers the circle using it as arc, it will be by its radius and song The value that rate calculates is set as long axis length.

As the manufacturing method of metal nanometer line, such as Japanese Unexamined Patent Publication 2009-215594 bulletins, Japan can be used special Open 2009-242880 bulletins, Japanese Unexamined Patent Publication 2009-299162 bulletins, Japanese Unexamined Patent Publication 2010-84173 bulletins, Japan spy Open the method described in 2010-86714 bulletins.To the manufacturing method of metal nanometer line, there is no particular restriction, can be used any Method manufactures, but is preferably as described below by will heat one on one side in halogen compounds and the lysed solvent of dispersing additive While metal ion is restored and is manufactured.

As above-mentioned solvent, preferred hydrophilic solvent, such as water outlet, alcohols, ethers, ketone can be enumerated etc., these can be a kind It is used alone, also two or more may be used.As above-mentioned alcohols, for example, can enumerate methanol, ethyl alcohol, propyl alcohol, isopropanol, Butanol, ethylene glycol etc..As above-mentioned ethers, such as dioxane, tetrahydrofuran can be enumerated etc..As above-mentioned ketone, such as can Enumerate acetone etc..

Heating temperature when above-mentioned heating is preferably 250 DEG C hereinafter, more preferably 20 DEG C~200 DEG C.Heating temperature more drops Low, core formation probability more declines, if heating temperature, less than 20 DEG C, metal nanometer line is excessively elongated and becomes easy entanglement, Sometimes dispersion stabilization is deteriorated.On the other hand, if heating temperature is more than 250 DEG C, the angle in the section of metal nanometer line becomes Sharply, the decrease in transmission in coated film evaluation sometimes.It is explained, heating temperature is more preferably 30 DEG C~180 DEG C, further Preferably 40 DEG C~170 DEG C.

It is explained, can change temperature in the forming process of metal nanometer line as needed.Pass through the temperature in midway Change, so as to improve the karyomorphism of metal nanometer line at control, generate core again inhibition, growth selection promotion caused by The effect that monodispersity improves.

In above-mentioned heating, preferably adds reducing agent and carry out.As reducing agent, there is no particular restriction, can be from usual institute It is properly selected in the reducing agent used.Such as can enumerate boron hydride metal salt, hydrogenation aluminium salt, alkanolamine, aliphatic amine, Hetero ring type amine, aromatic amine, aralkylamine, alcohol, organic acid, recuding sugars, glycitols, sodium sulfite, hydrazine compound, paste Essence, quinhydrones, hydroxylamine, ethylene glycol, glutathione etc..In these, particularly preferred recuding sugars, the sugar alcohol as its derivative Class, ethylene glycol.

As above-mentioned boron hydride metal salt, such as sodium borohydride, potassium borohydride can be enumerated etc..

As above-mentioned hydrogenation aluminium salt, such as lithium aluminium hydride reduction, aluminum hydride potassium, aluminum hydride caesium, aluminum hydride beryllium, hydrogenation can be enumerated Magnalium, calcium aluminum hydride etc..

As above-mentioned alkanolamine, such as DEAE diethylaminoethanol, ethanol amine, Propanolamine, triethanolamine, two can be enumerated Methyl aminopropyl alcohol etc..

As above-mentioned aliphatic amine, such as propylamine, butylamine, propane diamine, ethylenediamine, five amine of triethylene can be enumerated etc..

As above-mentioned hetero ring type amine, such as piperidines, pyrrolidines, N- crassitudes, morpholine can be enumerated etc..

As above-mentioned aromatic amine, such as aniline, methylphenylamine, toluidines, anisidine, phenetidine can be enumerated Deng.

As above-mentioned aralkylamine, such as benzylamine, dimethylphenylene diamine, N- methylbenzylamines can be enumerated etc..

As above-mentioned alcohol, such as methanol, ethyl alcohol, 2- propyl alcohol can be enumerated etc..

As above-mentioned organic acid, such as citric acid, malic acid, tartaric acid, citric acid, succinic acid, anti-bad can be enumerated Hematic acid or their salt etc..

As above-mentioned recuding sugars, such as glucose, galactolipin, mannose, fructose, sucrose, maltose, cotton can be enumerated Sub- sugar, stachyose etc..

As above-mentioned glycitols, such as sorbierite can be enumerated etc..

According to above-mentioned reducing agent, as function, also dispersing additive, solvent is used as to play a role sometimes, it can be similarly It is preferable to use.

When above-mentioned metal nanometer line manufactures, dispersing additive and halogen compounds or metal halide particle are preferably added Come carry out.Before the opportunity of the addition of dispersing additive and halogen compounds can be the addition of reducing agent, after can also be addition, After before the addition that can be metal ion or metal halide particle can also be addition, the better metal of monodispersity in order to obtain The addition of halogen compounds preferably it is more than the stage to be divided into 2 by nano wire.

As above-mentioned dispersing additive, there is no particular restriction, can be properly selected according to purpose.Such as it can enumerate and contain There are the compound of amino, the compound containing mercapto, the compound containing thioether group, amino acid or derivatives thereof, peptide chemical combination Object, polysaccharide, synthesis macromolecule, the gel etc. from them.In these, particularly preferred gelatin, polyvinyl alcohol, Methyl cellulose Element, hydroxy propyl cellulose, polyalkyleneamines, the part Arrcostab of polyacrylic acid, polyvinylpyrrolidone, polyvinyl pyrrole Pyrrolidone copolymer.

About the structure that can be used as above-mentioned dispersing additive and use, such as being capable of reference《The topical reference book of pigment》(her rattan sign department Youth compile, Co., Ltd. towards storehouse academy issue, 2000) record.

In addition, according to the type of the dispersing additive used, it is also possible that the change in shape of the metal nanometer line arrived.

As above-mentioned halogen compounds, as long as the compound containing bromine, chlorine, iodine, then there is no particular restriction, being capable of basis Purpose properly selects.Such as the alkali gold such as preferred sodium bromide, sodium chloride, sodium iodide, potassium iodide, potassium bromide, potassium chloride, potassium iodide Belong to halide, it is following can be with the compound of dispersing additive.According to above-mentioned halogen compounds, also has and add as dispersion Add the compound that agent functions, can equally be preferably used.

As the substitute of above-mentioned halogen compounds, silver halide grains can be used, it also can be by halogen compounds and silver halide Particle is used together.

Above-mentioned dispersant can be used in combination with halogen compounds with same substance.As by above-mentioned dispersant and halogen compounds The compound being used in combination, for example, can enumerate the HTAB (cetyl-trimethylammonium bromide) containing amino and bromide ion, HTAC (cetyl-trimethyl ammonium chloride) containing amino and chloride ion, contain amino and bromide ion or chlorination Dodecyl trimethyl ammonium bromide, dodecyl trimethyl ammonium chloride, stearyl trimethyl ammonium bromide, the stearyl three of object ion Ammonio methacrylate, thiotrimethylammonium bromide, decyl trimethyl ammonium chloride, dimethyl distearyl ammonium bromide, dimethyl two are hard Aliphatic radical ammonium chloride, dilauryl ammonium bromide, dilauryl ammonium chloride, two palmityl ammonium bromide of dimethyl, two Two palm ammonium chloride of methyl etc..

After foring metal nanometer line, can by the gimmicks such as ultrafiltration, dialysis, gel filtration, decantation, centrifugation come into Row desalting processing.

＜ metal nano-tubes ＞

As the material of metal nano-tube, there is no particular restriction, can be any metal, such as can use above-mentioned gold Belong to the material etc. of nano wire.

It can be single layer as the shape of metal nano-tube, can also be multilayer, in the side of electric conductivity and excellent thermal conductivity Face, preferably single layer.

The thickness (difference of outer diameter and internal diameter) of metal nano-tube is preferably 3nm~80nm.If above-mentioned thickness less than 3nm, Sometimes oxidative resistance deteriorates, and durability is deteriorated, if it exceeds 80nm, occurs scattering caused by metal nano-tube sometimes.It is said Bright, above-mentioned thickness is more preferably 3nm~30nm.

The average major axis length of metal nano-tube is preferably 1 μm~40 μm, more preferably 3 μm~35 μm, further preferably It is 5 μm~30 μm.

As the manufacturing method of above-mentioned metal nano-tube, there is no particular restriction, can be properly selected according to purpose.Such as The method etc. described in No. 2005/0056118 specification etc. can be disclosed using U. S. application.

＜ carbon nanotubes ＞

Carbon nanotube (CNT) is the object for the coaxial tubular that graphite-like carbon atom face (graphene film) becomes single-layer or multi-layer Matter.The carbon nanotube of single layer is known as single-walled nanotube (SWNT), and the carbon nanotube of multilayer is known as many walls nanotube (MWNT), especially Ground, 2 layers of carbon nanotube are also referred to as double-walled nanotubes (DWNT).In the conducting fibre used in the present embodiment, carbon is received Mitron can be single layer, or multilayer, but in terms of electric conductivity and excellent thermal conductivity, preferably single layer.

As the manufacturing method of carbon nanotube, there is no particular restriction, can be properly selected according to purpose.Such as it can make With contact hydrogen reduction, arc discharge method, laser evaporization method, thermal cvd, plasma CVD method, the vapor phase growth of carbon dioxide Method, the HiPco methods (high- grown in the gas phase by high temperature and pressure makes carbon monoxide react with iron catalyst one Pressure carbon monoxide process) etc. well known to means.

In addition, for the obtained carbon nanotube of these methods, from the carbon nanotube that can obtain high purity From the aspect of, it is preferably by the method for cleaning, centrifugation, filtering, oxidation, chromatography etc. that by-product, catalyst metals etc. are residual Object is stayed to remove.

The aspect ratio of above-mentioned conducting fibre is preferably 10 or more.So-called above-mentioned aspect ratio generally means that threadiness The ratio between the long side of substance and short side (the ratio between average major axis length/average minor axis length).

As the assay method of aspect ratio, there is no particular restriction, can be properly selected according to purpose, such as can enumerate The method etc. being measured by electron microscope etc..

With the aspect ratio of determination of electron microscopy conducting fibre, with regard to conducting fibre aspect ratio whether For 10 or more, as long as can confirm in 1 visual field of electron microscope.In addition, being led by respectively measuring The long axis length and minor axis length of conductive fiber, can estimate the aspect ratio of conducting fibre entirety.

It is explained, in the case where conducting fibre is tubulose, as the diameter for calculating aspect ratio, uses the pipe Outer diameter.

As long as the aspect ratio of conducting fibre is 10 or more, then there is no particular restriction, can be properly selected according to purpose, Preferably 50~1000000.If above-mentioned aspect ratio less than 10, can not carry out being formed using the network of conducting fibre, have When do not obtain electric conductivity fully, if it exceeds 1000000, then in the formation of conducting fibre, in disposition thereafter, Conducting fibre is tangled, is agglomerated before film forming, therefore there is no stable liquid sometimes.It is explained, above-mentioned aspect ratio is more excellent It is selected as 100~1000000.

The ratio (ratio) for the conducting fibre that aspect ratios in whole conductive compositions, above-mentioned are 10 or more uses volume Than indicating, preferably 50% or more.If above-mentioned ratio less than 50%, contributes to the conductive material of electric conductivity to reduce, have When electric conductivity reduce, simultaneously because fine and close network cannot be formed, therefore generate voltage and concentrate, durability reduces sometimes.In addition, The contribution not big to electric conductivity of the particle of shape other than conducting fibre, and with absorption, therefore not preferably, especially In the case of metal, in the case where the phasmon of spherical shape etc. absorbs strong, transparency deteriorates sometimes.It is explained, above-mentioned ratio Rate more preferable 60% or more, particularly preferred 75% or more.

Wherein, for above-mentioned ratio, such as in the case where conducting fibre is nano silver wire, by nano silver wire moisture Dispersion liquid filters, and nano silver wire is detached with the particle other than it, is measured using ICP apparatus for analyzing luminosity and is remained on filter paper respectively Silver amount and penetrated filter paper silver amount, thus, it is possible to find out the ratio of conducting fibre.Remain on filter paper with tem observation Conducting fibre, observe 300 conducting fibres minor axis length, investigate its distribution, thereby confirm that it is that minor axis length is The conducting fibre that 200nm or less and long axis length are 1 μm or more.It is explained, for filter paper, it is preferable to use in metering State the particle other than the conducting fibre of size the longest axis, for its longest axis 2 times or more and make the length of conducting fibre The particle of the shortest length length below of axis by filter paper.

Wherein, for the average minor axis length of above-mentioned conducting fibre and average major axis length, such as can be by making With transmission electron microscope (TEM), optical microphotograph sem observation TEM pictures, optical microphotograph mirror image and find out.In present embodiment In, the average minor axis length and average major axis length of conducting fibre are to observe 300 by transmission electron microscope (TEM) Conducting fibre is found out by its average value.

＜ binders ＞

As above-mentioned binder, can from as organic high molecular polymer, in molecule (preferably with acrylic acid series copolymer Molecule as main chain) in at least one promote alkali-soluble group (such as carboxyl, phosphate, sulfonic group etc.) alkali It is properly selected in soluble resin.

In these, the preferred solvable, binder that develops using weak base aqueous solution in organic solvent, in addition, special Preferably do not have the function of becoming the soluble binder of alkali when acid dissociation group, acid dissociation group have been dissociated due to acid. It is explained, acid dissociation group indicates the functional group that can be dissociated in the presence of acid.

In the manufacture of above-mentioned binder, the method for example using well known radical polymerization can be applied.Just use Radical polymerization is stated to manufacture temperature, pressure, the type of radical initiator and its amount when alkali soluble resin, solvent It for the polymerizing conditions such as type, can easily be set by those skilled in the art, can experimentally determine condition.

As linear above-mentioned organic high molecular polymer, preferably in the side chain the polymer with carboxylic acid (with acid The photoresist of group).

As the polymer in side chain with carboxylic acid, for example, Japanese Unexamined Patent Application 59-44615, examined patent publication 54-34327 Number, examined patent publication 58-12577, examined patent publication 54-25957, Japanese Unexamined Patent Application 59-53836, Japanese Unexamined Patent Application 59-71048 Number each bulletin described in such, methacrylic acid copolymer, acrylic copolymer, itaconic acid copolymer, crotonic acid copolymerization Object, maleic acid, partial esterification maleic acid etc. and side chain have carboxylic acid acid cellulose derivative, make Acid anhydrides addition can also enumerate the height for having (methyl) acryloyl group in side chain in the product etc. of the polymer with hydroxyl Molecularly Imprinted Polymer is as the polymer preferably in side chain with carboxylic acid.

In these, particularly preferred (methyl) benzyl acrylate/(methyl) acrylic copolymer, by (methyl) acrylic acid benzyl The multiple copolymer that ester/(methyl) acrylic acid/other monomers are constituted.

In turn, can also enumerate side chain have (methyl) acryloyl group high molecular polymer, by (methyl) acrylic acid/ The multiple copolymer that (methyl) glycidyl acrylate/other monomers are constituted is as the available polymerization in side chain with carboxylic acid Object.The polymer can be used in mixed way with arbitrary amount.

In addition to the foregoing, described in Japanese Unexamined Patent Publication 7-140654 bulletins, (methyl) acrylic acid can also be enumerated 2- hydroxy propyl esters/Group-capped Polystyrene Macromer/benzyl methacrylate/methacrylic acid copolymer, acrylic acid 2- hydroxyls -3- Phenoxy-propyl/polymethyl methacrylate macromonomer/benzyl methacrylate/methacrylic acid copolymer, methyl-prop Olefin(e) acid 2- hydroxy methacrylates/Group-capped Polystyrene Macromer/methyl methacrylate/methacrylic acid copolymer, methacrylic acid 2- hydroxy methacrylates/Group-capped Polystyrene Macromer/benzyl methacrylate/methacrylic acid copolymer etc..

As the specific structural unit in above-mentioned alkali soluble resin, preferred (methyl) acrylic acid and can be with (methyl) The other monomers of acrylic acid copolymer.Such as (first can be enumerated as above-mentioned with the other monomers of (methyl) acrylic acid copolymer Base) alkyl acrylate, (methyl) benzyl acrylate, vinyl compound etc..Their alkyl and the hydrogen atom of aryl can To be substituted with a substituent.

As above-mentioned (methyl) alkyl acrylate or (methyl) benzyl acrylate, such as (methyl) propylene can be enumerated Sour methyl esters, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) amyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) 2-ethyl hexyl acrylate, (methyl) phenyl acrylate, (methyl) third Olefin(e) acid benzyl ester, (methyl) toluene toluene, (methyl) acrylic acid naphthalene ester, (methyl) cyclohexyl acrylate, (methyl) acrylic acid Bicyclic pentyl ester, (methyl) acrylic acid dicyclopentenyloxyethyl methacrylate, the bicyclic amylene oxygroup ethyl ester of (methyl) acrylic acid etc..These can a kind individually Ground uses, and also two or more may be used.

As above-mentioned vinyl compound, such as styrene, α-methylstyrene, vinyltoluene, methyl can be enumerated Glycidyl acrylate, acrylonitrile, vinyl acetate, n-vinyl pyrrolidone, tetrahydrofurfuryl methacrylate, polyphenyl second Alkene macromonomer, polymethyl methacrylate macromonomer, CH₂=CR₁R₂、CH₂=C (R₁)(COOR₃) etc..Wherein, R₁ Indicate the alkyl of hydrogen atom or carbon number 1~5, R₂Indicate the aromatic series hydrocarbon ring of carbon number 6~10, R₃Indicate carbon number 1~8 alkyl or The aralkyl of carbon number 6~12.They can a kind be used alone, also two or more may be used.

Consider from alkali solution rate, film physical property etc., the weight average molecular weight preferably 1000~500000 of above-mentioned binder, More preferable 3000~300000, further preferred 5000~200000.It is explained, above-mentioned weight average molecular weight can pass through gel Permeation chromatography is measured, is found out using standard polystyrene calibration curve.

It is all relative to above-mentioned conductive layer for the content of above-mentioned binder, the preferably 25 mass % of mass %~80, The more preferable 30 mass mass of %~75 %, the further preferred 40 mass mass of %~70 %.If in the range of above-mentioned content, Then realize taking into account for developability and the electric conductivity of metal nanometer line.

＜ photosensitive compounds ＞

So-called above-mentioned photosensitive compounds, it is intended that conductive layer assign by expose function to form image or to Give the compound of the chance.Specifically, compound (photo-acid generator), (2) that (1) generates acid by exposure can be enumerated Photosensitive quinone di-azido compound, (3) optical free radical producing agent etc..They can a kind be used alone, also can be by two or more It is used in combination.In addition, in order to adjust sensitivity, it also can be by sensitizer etc. and land used use.

(photo-acid generator)

As photo-acid generator, the photoinitiator using light cationic polymerization, optical free radical polymerization can be properly selected Photoinitiator, pigment light depigmenting agent, phototropic agent or miniature resist etc. used in by active ray or The irradiation of radioactive ray generates the well known compound and their mixture of acid.

To photo-acid generator, there is no particular restriction, can be properly selected according to purpose.Such as diazol, Phosphonium can be enumerated Salt, sulfonium salt, salt compounded of iodine, acid imide sulphonic acid ester, oxime sulfonates, two sulfone of diazonium, two sulfones, adjacent nitro benzylsulfonate etc..In these, Particularly preferable as acid imide sulphonic acid ester, oxime sulfonates, the adjacent nitro benzylsulfonate of the compound for generating sulfonic acid.

In addition, can use the irradiation by active ray or radioactive ray is introduced in the main chain or side chain of resin by is produced The group of raw acid or the compound of compound, such as No. 3849137 specifications of U.S. Patent No., German Patent No. 3914407 Specification, Japanese Unexamined Patent Application 63-26653, Japanese Unexamined Patent Application 55-164824, Japanese Unexamined Patent Application 62-69263, Japan are special Open clear No. 63-146038, Japanese Unexamined Patent Application 63-163452, Japanese Unexamined Patent Application 62-153853, Japanese Unexamined Patent Application 63- Compound described in No. 146029 each bulletin etc..Further, it is possible to use U.S. Patent No. 3779778, European Patent The compound that acid is generated by light described in No. 126712 equal each specification.

(quinone di-azido compound)

For above-mentioned quinone di-azido compound, such as by making 1,2- quinones, two nitrine sulphonyl in the presence of desalination acid agent Chlorine class, hydroxy compounds, amino-compound etc. carry out condensation reaction and obtain.

For the use level of above-mentioned photo-acid generator and above-mentioned quinone di-azido compound, from exposure portion and unexposed portion Solution rate difference and the nargin (Xu of sensitivity hold width) from the aspect of, it is excellent relative to 100 mass parts of total amount of above-mentioned binder It is selected as the mass parts of 1 mass parts~100, the mass parts of more preferably 3 mass parts~80.It is explained, it can be by above-mentioned photo-acid generator It is used in combination with above-mentioned quinone di-azido compound.

In present embodiment, in above-mentioned photo-acid generator, the compound of sulfonic acid is preferably generated, from the sight for high sensitivity Point consideration, particularly preferably following such oxime sulfonate compounds.

[adhesive phase]

By the most surface (such as on hard conating) of the polarizing film of the viewable side in present embodiment via adhesive phase come It is bonded touch panel, can also constitute touch panel display device.As above-mentioned adhesive phase, there is no particular restriction, can make With well known adhesive.Such as can use acrylic adhesive, silicon-type adhesive, carbamate system adhesive, Elastomeric adhesive, Polyester adhesive etc. are particularly preferably relatively easy to acrylic acid using the control of bonding force, storage modulus It is adhesive.

As acrylic adhesive, (methyl) methyl acrylate of sening as an envoy to, (methyl) ethyl acrylate, (methyl) can be enumerated N-butyl acrylate, (methyl) isobutyl acrylate, (methyl) the just own ester of acrylic acid, (methyl) acrylic acid 2- ethyls butyl ester, (first Base) 1~20 alkyl of acrylic acid carbon number such as 2-EHA, (methyl) Isooctyl acrylate monomer, (methyl) decyl acrylate The one or two or more kinds of ester with and copolymerizable (methyl) acrylic acid of above-mentioned alkyl acrylate, itaconic acid, maleic acid, Malaysia The copolymer and isocyanide of the monomers such as acid anhydrides, (methyl) acrylic acid 2- hydroxy methacrylates, (methyl) acrylic acid 4- hydroxybutyls Made of the reaction of the crosslinking agents such as acid esters system crosslinking agent, epoxy crosslinking agent, aziridine system crosslinking agent, metallo-chelate system crosslinking agent Acrylic adhesive.

The thickness of adhesive phase is preferably 1 μm~13 μm.In the case where the thickness of adhesive phase is 1 μm or more, obtain Sufficient bonding force can inhibit the exudation of paste in the case that below for 13 μm in Punching Technology, when processing of cutting, and And maintain high pencil hardness.The thickness of preferred adhesive phase is 3~12 μm.

As the storage modulus of adhesive phase, the storage modulus at preferably 0 DEG C is 1.0 × 10⁶~1.0 × 10⁸Pa.Viscous The storage modulus of mixture layer is 1.0 × 10⁶In the case of Pa or more, it is suitable to obtain sufficient Punching Technology adaptability, processing of cutting Conjunction property and high pencil hardness, are being 1.0 × 10⁸In the case of Pa is below, sufficient bonding force is obtained.Preferred adhesive phase Storage modulus be 1.5 × 10⁶~1.0 × 10⁷Pa。

As the method that adhesive phase is arranged on hard conating, the following methods can be enumerated：Adhesive will additionally be contained Composition be coated on stripping film, making it dry and stacking hard coat film (film base material+hard conating) on the adhesive phase that makes.Just For the coating method of the above-mentioned composition containing adhesive, such as stick coating method can be enumerated, scraper for coating method, rolling method, scraped The conventionally known methods such as plate rubbing method, mouth die coating method, heliogravure rubbing method, curtain coating method.In addition, can also contain above-mentioned There is the composition of adhesive to be directly coated at the surface of hard coat film, make it dry, thus laminate adhesive oxidant layer.

For above-mentioned stripping film, various stripping films can be used, typically, by having the base of fissility on surface Material piece is constituted.As substrate sheets, polyester resin, polyvinyl resin, acrylic resin, polystyrene resin, poly- carbon can be enumerated The film of acid ester resin etc., film, the synthetic paper etc. for having coordinated the fillers such as filler in these films.In addition, can enumerate glassine paper, The paper base materials such as clay coated paper, vellum.

When making the surface of substrate sheets that there is fissility, Thermocurable organic siliconresin, ultraviolet light can be kept solid by coating etc. The removers such as change type organic siliconresin are attached to its surface.The coating weight of remover preferably 0.03~3.0g/m².With regard to stripping film Speech, the surface with remover is folded with adhesive phase phase ground plane.

[embodiment]

The present invention is concretely demonstrated hereinafter, enumerating embodiment, but the present invention is not limited to these embodiments.It gives With explanation, the expression of " part " or " % " is used in embodiment, as long as no special instructions, then it represents that " mass parts " or " quality % ".

The making ＞ of ＜ protective films

The making ＞ of ＜ cellulose ester membranes CE1

The preparation ＞ of ＜ particle dispersion liquids 1

Silicon dioxide microparticle (ア エ ロ ジ Le R972V Japan's ア エ ロ ジ Le (strain) manufacture)

11 mass parts

89 mass parts of ethyl alcohol

After the above substance is stirred 50 minutes with dissolvers, is disperseed with マ Application ト ン ゴ ー リ Application, be prepared for micro- Grain dispersion liquid 1.

The preparation ＞ of ＜ particulate annex solutions 1

In the dissolving tank equipped with dichloromethane on one side fully stirring, on one side slowly add particle dispersion liquid 1.Into And disperseed using ア ト ラ イ タ ー (Attritor) so that the grain size of offspring becomes defined size.Used day The Off ァ イ Application メ ッ ト NF filterings of this essence line (strain) manufacture, are prepared for particulate annex solution 1.

99 mass parts of dichloromethane

15 mass parts of particle dispersion liquid

The preparation ＞ of ＜ rubber cements

First, dichloromethane and ethyl alcohol are added in dissolved under pressure tank.Then, in the dissolved under pressure tank equipped with solvent, Cellulose ethanoate is put into while stirring.It is heated, fullys while stirring and dissolve.Use peace product filter paper (strain) The peace product filter paper No.244 of system is filtered, and main rubber cement is prepared for.

Then, in a manner of as above-mentioned ratio, by main rubber cement and each material input closed container, one is stirred on one side Side is dissolved, and rubber cement is prepared for.

＜ is film-made ＞

Then, using endless belt casting device, rubber cement is cast to not at 33 DEG C of temperature, with 1500mm even widths It becomes rusty on steel band supporting mass.The temperature of stainless steel band is controlled in 30 DEG C.Then, evaporation of the solvent is made on stainless steel band until curtain coating (cast) the residual solvent amount in film becomes 75%, then, is shelled mesh from stainless steel band with stripping tension 130N/m From.

Mesh (the cellulose esters for using stenter that will remove in the direction of the width while applying 160 DEG C hot Film) stretch 10%.It is 15% to stretch residual solvent when starting.Then, on one side using multiple rollers to complete while dry section conveys At drying.Drying temperature is 130 DEG C, and conveyance tension is set as 100N/m.After drying, by film it is longitudinal sectional be 1.5m wide, to film both ends Implement wide 10mm, the processing of high 10 μm of annular knurl, coils into web-like, obtained the cellulose ester membrane CE1 of 30 μm of dry film thickness.Fiber The a length of 5200m of volume of cellulose ester film CE1.

Use automatic birefringence meter ア Network ソ ス キ ャ Application (Axo Scan Mueller Matrix Polarimeter： Axometrics, Inc. are manufactured) phase difference value of phase difference value Ro and thickness direction in face to measure cellulose ester membrane CE1 Rth, result Ro=1nm, Rth=4nm.

The making ＞ of ＜ cellulose ester membranes CE2~CE3

Other than becoming film thickness shown in table 1 and being film-made, fibre has been made with method same as cellulose ester membrane CE1 Tie up cellulose ester film CE2~CE3.

The preparation ＞ of ＜ cellulose ester membranes CE4

It is chased after by the cellulose ester membrane (20 μm of KC2CT1, film thickness) to commercially available Konica Minolta Opto Inc. Add stretching, prepares the cellulose ester membrane CE4 of 13 μm of film thickness.

The film ＞ of ＜ COP films 1

＜ has the synthesis ＞ of the fluoropolymer resin of ester ring type structure

Under ethylene atmosphere, in the autoclave of capacity 1.6l with a concentration of 20mol/l of phenyl norbornene, total liquid measure at It is put into toluene and phenyl norbornene-toluene solution for the mode of 640ml.Addition is the aluminium methyl of 5.88mmol on the basis of Al Oxygen alkane (manufacture of ア Le ベ マ ー Le Co., Ltd., MAO20% toluene solutions), methylene (cyclopentadienyl group) (tetramethyl-ring penta Dialkylene) 1.5 μm of ol of zirconium dichloride, ethylene is imported, pressure is held in 0.2MPa on one side, on one side reacts at 80 DEG C it 60 minutes.

After reaction, it is directed at ethylene while natural cooling and carries out de- pressure, will be replaced in system with nitrogen.Then, it is added 3.0g's adjusts adsorption moisture amount to the silica of 10 mass % (manufacture of シ リ シ ア companies of Fuji, grade：G-3 grain sizes： 50 μm), so that it has been reacted 1 hour.The reaction solution is put into, filter paper (5C, 90mm) and セ ラ イ ト (and Wako Pure Chemical Industries are installed Company) pressure filter (ア De バ ンテック Toyo Co., Ltd., model KST-90-UH) in, will with nitrogen pressure filtration Polymer fluid recycles.Marginally the polymer fluid is added dropwise in the acetone of 5 times of amounts every time, makes its precipitation, obtains with ester ring type knot The fluoropolymer resin COP1 of structure.The weight average molecular weight of COP1 is 142000, in addition, glass transition temperature is 140 DEG C.

Using the air drier to ventilate by the polymer with ester ring type structure of above-mentioned synthesis at 70 DEG C Resin COP1 is dried 2 hours, after moisture is removed, uses the T-type of the resin melting kneading machine with the screw rod with 65mm φ Die head formula film melting extrusion molding machine (T-shaped mould head width 500mm), in 240 DEG C of molten resin temperature, 240 DEG C of T-type die head temperature Condition of molding under by the COP film extruding formings of 100 μm of film thickness.

Then, the COP film stretchings for using stenter that will remove in the direction of the width while applying 200 DEG C hot 90%.Then, on one side completing drying while dry section conveys with multiple rollers.Drying temperature is 130 DEG C, and conveyance tension is set as 100N/m.After drying, longitudinal sectional is 1.5m wide, implements wide 10mm, the processing of high 10 μm of annular knurl to film both ends, coils into web-like, obtain The COP films 1 of 8 μm of dry film thickness are arrived.The a length of 5000m of volume of COP films 1.

Using automatic birefringence meter ア Network ソ ス キ ャ Application (Axo Scan Mueller Matrix Polarimeter： ア Network ソ メ ト リ ッ Network ス companies manufacture) the phase difference value Rth of phase difference value Ro and thickness direction in the face of COP films 1 is determined, As a result it is Ro=0nm, Rth=2nm.

The film ＞ of ＜ COP films 2

In addition to use JSR (strain) make ア ー ト Application (G7810), as additive be added polyester based compound AP-15 with Outside, COP films 2 have been made in the same manner as cellulose ester membrane CE1.

Using automatic birefringence meter ア Network ソ ス キ ャ Application (Axo Scan Mueller Matrix Polarimeter： ア Network ソ メ ト リ ッ Network ス companies manufacture) the phase difference value Rth of phase difference value Ro and thickness direction in the face of COP films 2 is determined, As a result it is Ro=2nm, Rth=3nm.

The measurement ＞ of ＜ viscosity

It is measured using the determination of viscoelasticity device (DMA7100) of Hitachi Ha イ テ Network サ イ エ Application ス accurate as described above The viscosity of standby each optical film (cellulose ester membrane CE1~CE4, COP films 1~2).That is, using above-mentioned apparatus, each optical film is measured In Log (tan δ) in -40 DEG C~90 DEG C of temperature range minimum value.

The making ＞ of ＜ polarizers

Using Network ラ レ PVA films (20 μm of thickness), in iodine concentration 0.3wt% and dye bath (35 DEG C) containing KI, After being stretched, dyed again with stretching ratio 2, in the crosslinking bath (50 DEG C) equipped with boric acid, 2.5 times are stretched, makes always to stretch again Rate is stretched (7 μm of thickness) as 5 times.Then, above-mentioned PVA film is dried with 60 DEG C of drying machine, makes polarizer 1. In addition, other than making total stretching ratio be stretched as 5.7 times, 5 μ of thickness has also been made with method similar to the above The polarizer 2 of m.

The making ＞ of ＜ polarizing films

They are fitted in polarizer using bonding agent, made inclined by the combination of protective film and opposed film shown in table 1 Shake piece 1~6.

＜ evaluates ＞

(crackle)

After the polarizing film 1~6 of above-mentioned making is punched to round (profiled shape other than rectangle), with micro- sem observation Whether cracked in polarizing film.Become in addition, making the polarizing film 1~6 of above-mentioned making that temperature occur between -30 DEG C and 80 DEG C Change, after which has been repeated 200 times, sees whether to crack in polarizing film with microscope.Then, it is based on Evaluation criterion below evaluates crackle.

《Evaluation criteria》

○：In punching and when temperature change in the two, almost without crackle is found.

×：In punching and at least one of when temperature change, the generation of crackle is found.

(brightness)

The making ＞ of ＜ IPS type liquid crystal display devices

By manufacturing method shown in fig. 7, the IPS for making the common electrode of pixel electrode and strip with strip is mono- Member.Then, polarizing film 1~6 shown in table 1 is adhered to the viewable side and backlight side of IPS units with bonding agent, makes IPS The liquid crystal display device 1~6 of type.

Then, the light splitting radiance meter CS2000 made using Konica Minolta (strain), measures the IPS types of above-mentioned making Liquid crystal display device brightness, evaluated based on the following benchmarks.

《Evaluation criteria》

○：On the basis of brightness value more than value.

△：Be worth on the basis of brightness value 90% or more and less than standard value.

×：Brightness value is less than the 90% of a reference value.

Table 1 show for polarizing film 1~6 evaluation as a result, table 2 shows the evaluation for liquid crystal display device 1~6 As a result.

According to table 1 as a result, in polarizing film 1~4, the not generation of crackle is produced in polarizing film 5 and 6 in contrast Raw crackle.Think that its reason is：It is different from polarizing film 5 and 6 in polarizing film 1~4, be thickness be 20 μm or more and 65 μm It is below slim, therefore crackle is not likely to produce for punching, in addition, the value of Log (tan δ) is -1.8 or more, temperature change causes Viscosity variation it is small, therefore become to be not easy to crack because of temperature change.

In addition, according to table 2, liquid crystal display device 1~6 is completely formed the good result of brightness evaluation.Think that its reason exists In：The common electrode by IPS units with the pixel electrode and strip of strip, can realize the IPS units of high-transmission rate.

The special-shaped display device of present embodiment described above can be expressed as described below.

1. special-shaped display device is to show that picture is the special-shaped display device of the shape different from rectangle and square, It is characterized in that, it has：IPS units and each polarizing film from the above-mentioned IPS units of sandwich,

Above-mentioned IPS units have：In the display area of 1 pixel with strip place pixel electrode and with above-mentioned picture The common electrode for the strip that plain electrode is alternately arranged,

The thickness of above-mentioned each polarizing film be respectively 20 μm or more and 65 μm hereinafter,

Above-mentioned each polarizing film has：Polarizer and each optical film from the above-mentioned polarizer of sandwich,

When by indicating that the loss angle tangent of the ratio between loss modulus and storage modulus is set as tan δ, in above-mentioned each polarizing film The value of Log (tan δ) in each optical film between -40 DEG C to 100 DEG C is -1.8 or more.

2. the special-shaped display device described in above-mentioned 1, which is characterized in that each optical film of above-mentioned each polarizing film respectively contains fibre Dimension plain ester system resin.

3. the special-shaped display device described in above-mentioned 1 or 2, which is characterized in that each optical film of above-mentioned each polarizing film contains envelope The polyester at end is as plasticizer.

4. the special-shaped display device described in any one of above-mentioned 1-3, which is characterized in that above-mentioned IPS units also have：1 The basal layer of the passivating film and the above-mentioned passivating film of bearing placed with strip in the display area of a pixel,

Pixel electrodes are located on above-mentioned passivating film,

Above-mentioned common electrode is on above-mentioned basal layer and between adjacent above-mentioned passivating film.

Industrial availability

The present invention can utilize in the display device that display picture is profiled shape.

The explanation of reference numeral

1 liquid crystal display device (special-shaped display device)

1a shows picture

2 IPS units

3 polarizing films

4 polarizing films

11 polarizers

12 protective films (optical film)

13 opposed films (optical film)

21 polarizers

22 protective films (optical film)

23 opposed films (optical film)

107 organic passivation films (basal layer)

108 common electrodes

109 passivating films

110 pixel electrodes

The display areas P

Claims (4)

1. a kind of abnormity display device is to show that the abnormity display that picture is the shape different from rectangle and square fills It sets,

It has：IPS units and each polarizing film from IPS units described in sandwich,

The IPS units have：It is electric with the pixel electrode of strip placement and with the pixel in the display area of 1 pixel The common electrode for the strip that pole is alternately arranged,

The thickness of each polarizing film be respectively 20 μm or more and 65 μm hereinafter,

Each polarizing film has：Polarizer and each optical film from polarizer described in sandwich,

When by indicating that the loss angle tangent of the ratio between loss modulus and storage modulus is set as tan δ, in each light of each polarizing film It learns in film, the value of the Log (tan δ) between -40 DEG C to 100 DEG C is -1.8 or more.

2. abnormity display device according to claim 1, wherein each optical film of each polarizing film respectively contains fiber Plain ester system resin.

3. abnormity display device according to claim 1 or 2, wherein each optical film of each polarizing film contains sealing end Polyester as plasticizer.

4. abnormity display device according to any one of claim 1-3, wherein the IPS units also have：At 1 The basal layer of the passivating film and the bearing passivating film placed with strip in the display area of pixel,

The pixel electrode is located on the passivating film,

The common electrode is on the basal layer and between the adjacent passivating film.