WO2016153038A1

WO2016153038A1 - Cyclic olefin resin composition film

Info

Publication number: WO2016153038A1
Application number: PCT/JP2016/059611
Authority: WO
Inventors: 石森　拓; 堀井　明宏; 慶小幡; 香奈子橋本
Original assignee: デクセリアルズ株式会社
Priority date: 2015-03-26
Filing date: 2016-03-25
Publication date: 2016-09-29
Also published as: TW201708375A; JP2016183303A

Abstract

Provided is a cyclic olefin resin composition film having excellent mechanical isotropy. The cyclic olefin resin composition film according to the present invention is obtained by drawing a cyclic olefin resin composition comprising a cyclic olefin resin and an elastomer, and configuring the refractive index in the MD direction so as to be 0.001-0.0035 greater than the refractive index in the TD direction. Good mechanical isotropy can thereby be obtained.

Description

Cyclic olefin resin composition film

The present invention relates to a cyclic olefin resin composition film in which an elastomer or the like is added and dispersed in a cyclic olefin resin. This application claims priority on the basis of Japanese Patent Application No. 2015-065268 filed on Mar. 26, 2015 in Japan. This application is incorporated herein by reference. Is done.

Cyclic olefin resin is an amorphous and thermoplastic olefin resin that has a cyclic olefin skeleton in its main chain, has excellent optical properties (transparency, low birefringence), low water absorption, It has excellent performance such as dimensional stability and high moisture resistance based thereon (see, for example, Patent Documents 1 to 3). Therefore, films or sheets made of cyclic olefin resins are expected to be developed for various optical applications such as retardation films, polarizing plate protective films, light diffusion plates, and moisture proof packaging applications such as pharmaceutical packaging and food packaging. Yes.

Since a film of a cyclic olefin resin is inferior in toughness, it is known to improve toughness by adding and dispersing an elastomer or the like (see, for example, Patent Document 3).

JP-A-1-256548 JP 2001-72837 A JP 2004-156048 A

In recent years, a cyclic olefin-based resin composition film excellent in mechanical isotropy has been desired. As a result of studies by the present inventors, a film containing a cyclic olefin resin and an elastomer is inevitably mechanically anisotropic because the elastomer is oriented in the flow direction of the cyclic olefin resin during film formation. It was found that it was difficult to obtain a film having excellent mechanical isotropy.

The present invention has been proposed in view of such a conventional situation, and provides a cyclic olefin-based resin composition film excellent in mechanical isotropy.

As a result of intensive studies, the inventors of the present application stretched a cyclic olefin resin composition composed of a cyclic olefin resin and an elastomer, and made the refractive index in the MD direction a predetermined value larger than the refractive index in the TD direction. The present inventors have found that the problem can be solved and have completed the present invention.

That is, the cyclic olefin-based resin composition film according to the present invention is obtained by stretching a cyclic olefin-based resin composition composed of a cyclic olefin-based resin and an elastomer, and having a refractive index in the MD direction of 0.001 to less than a refractive index in the TD direction. It is made larger by 0.0035.

The method for producing a cyclic olefin-based resin composition film according to the present invention includes heating and melting a cyclic olefin-based resin composition containing a cyclic olefin-based resin and an elastomer, and stretching the heat-melted cyclic olefin-based resin composition. Thus, a cyclic olefin-based resin composition film having a refractive index in the MD direction that is 0.001 to 0.0035 larger than a refractive index in the TD direction is obtained.

According to the present invention, by stretching a cyclic olefin resin composition composed of a cyclic olefin resin and an elastomer, and making the refractive index in the MD direction larger than the refractive index in the TD direction by a predetermined value, it becomes mechanically isotropic. An excellent cyclic olefin resin composition film is obtained.

FIG. 1 is a cross-sectional perspective view showing an outline of a cyclic olefin-based resin composition film according to the present embodiment. FIG. 2 is a schematic diagram illustrating a configuration example of a film manufacturing apparatus. 3A and 3B are cross-sectional views illustrating an example of a transparent conductive film, and FIGS. 3C and 3D are cross-sectional views illustrating an example of a transparent conductive film provided with a moth-eye-shaped structure. FIG. 4 is a schematic cross-sectional view showing a configuration example of the touch panel. FIG. 5 is an external view illustrating an example of a television device as an electronic apparatus. 6A and 6B are external views illustrating examples of a digital camera as an electronic device. FIG. 7 is an external view illustrating an example of a notebook personal computer as an electronic device. FIG. 8 is an external view illustrating an example of a video camera as an electronic device. FIG. 9 is an external view illustrating an example of a mobile phone as an electronic device. FIG. 10 is an external view illustrating an example of a tablet computer as an electronic device.

Hereinafter, embodiments of the present invention will be described in detail in the following order with reference to the drawings.
1. 1. Cyclic olefin resin composition film 2. Production method of cyclic olefin-based resin composition film 3. Application example to electronic equipment Example

<1. Cyclic Olefin Resin Composition Film>
The cyclic olefin-based resin composition film according to the present embodiment is obtained by stretching a cyclic olefin-based resin composition composed of a cyclic olefin-based resin and an elastomer, and having a refractive index in the MD direction that is 0.001 to less than that in the TD direction. It is made larger by 0.0035. By setting it as such a structure, the cyclic olefin resin composition film excellent in mechanical isotropy is obtained.

FIG. 1 is a cross-sectional perspective view showing an outline of a cyclic olefin-based resin composition film according to the present embodiment. As shown in FIG. 1, the cyclic olefin-based resin composition film contains a cyclic olefin-based resin 11 and an elastomer 12.

The cyclic olefin-based resin composition film is, for example, a short film or sheet, the X-axis direction which is the width direction (TD: Transverse Direction), and the Y-axis direction which is the length direction (MD: Machine Direction), And a Z-axis direction that is a thickness direction. The thickness Z of the cyclic olefin-based resin composition film is preferably 0.1 μm to 2 mm, and more preferably 1 μm to 1 mm.

Further, as shown in FIG. 1, in the cyclic olefin resin composition film, a dispersed phase (island phase) made of elastomer 12 is dispersed in a matrix (sea phase) made of cyclic olefin resin 11. The dispersed phase is dispersed with shape anisotropy in the MD direction by, for example, extrusion molding, has a major axis in the MD direction, and a minor axis in the TD direction.

The cyclic olefin-based resin composition film preferably has a refractive index in the MD direction that is 0.001 to 0.0030 higher than a refractive index in the TD direction. By setting it as such a structure, the mechanical isotropy of a cyclic olefin resin composition film can be made more favorable.

The refractive index in the MD direction of the cyclic olefin-based resin composition film is preferably 1.48 to 1.58, and more preferably 1.51 to 1.55. The refractive index in the TD direction of the cyclic olefin-based resin composition film is preferably 1.48 to 1.58, and more preferably 1.51 to 1.55.

The cyclic olefin-based resin composition film preferably satisfies the following formula (1) or formula (2), and more preferably satisfies the following formula (1). That is, the cyclic olefin-based resin composition film preferably has a small difference between the tear strength in the MD direction and the tear strength in the TD direction. By satisfy | filling such conditions, the mechanical isotropy of a cyclic olefin resin composition film can be made favorable.

(1) The tear strength (N / mm) of the larger tear strength in the MD direction or TD direction of the cyclic olefin resin composition film × 0.8 <0.8 in the MD direction or TD direction of the cyclic olefin resin composition film The tear strength (N / mm) of the smaller tear strength.

(2) The tear strength (N / mm) of the larger tear strength among the MD direction or TD direction of the cyclic olefin resin composition film × 0.8 ≧ the MD direction or TD direction of the cyclic olefin resin composition film Of these, the tear strength (N / mm) of the smaller tear strength, and the difference is 1.0 or less.

The cyclic olefin-based resin composition film preferably has a tear strength in the MD direction, that is, a tear strength in the MD direction that is pulled in the MD direction and split in the TD direction is preferably 70 N / mm or more, and more than 100 N / mm. More preferred. The upper limit of the tear strength in the MD direction is usually preferably 120 N / mm or less.

The cyclic olefin-based resin composition film has a tear strength in the TD direction, that is, a tear strength in the TD direction that is pulled in the TD direction and teared in the MD direction is preferably 70 N / mm or more, and more preferably 80 N / mm or more. More preferably, it is more preferably 100 N / mm or more. The upper limit of the tear strength in the TD direction is usually preferably 120 N / mm or less.

In the cyclic olefin-based resin composition film, the difference between the tear strength in the MD direction and the tear strength in the TD direction is preferably 25 N / mm or less, and more preferably 20 N / mm or less.

The short axis dispersion diameter of the elastomer 12 is preferably 2.0 μm or less, and more preferably 1.0 μm or less. By satisfying the above range for the minor axis dispersion diameter, it is possible to suppress the generation of gaps between the elastomer and the cyclic olefin resin due to the elastomer phase change and to prevent the refractive index of the elastomer itself from changing under environmental preservation. And as a result, it can suppress that the haze of the whole film changes greatly.

In the present specification, the short axis dispersion diameter means the size in the TD direction of the dispersed phase composed of the elastomer 12, and can be measured as follows. First, the TD-thickness (Z-axis) cross section of the cyclic olefin-based resin composition film is cut. Then, the cross section of the film is magnified, the short axis of each dispersed phase in the predetermined range at the center of the cross section of the film is measured, and the average value is defined as the short axis dispersion diameter. Moreover, when a dispersion diameter is small, it is preferable to cut | disconnect, after giving osmium dyeing | staining with respect to a film.

In the cyclic olefin-based resin composition film, the elastomer content is preferably less than 35 wt%, more preferably 5 wt% or more and 30 wt% or less. By satisfying the above range, the retardation in the in-plane direction of the cyclic olefin-based resin composition film can be prevented from becoming too large, and the toughness can be improved.

The cyclic olefin resin composition film preferably has an in-plane retardation of 30 nm or less. Thereby, for example, it can be applied as an indirect member in a liquid crystal display creation / evaluation process, for example, as an adhesive tape for reinforcement or a protective cover for a panel.

Hereinafter, the cyclic olefin resin 11 and the elastomer 12 will be described in detail.

[Cyclic olefin resin]
The cyclic olefin-based resin is a polymer compound having a main chain composed of carbon-carbon bonds and having a cyclic hydrocarbon structure in at least part of the main chain. This cyclic hydrocarbon structure is introduced by using a compound (cyclic olefin) having at least one olefinic double bond in the cyclic hydrocarbon structure as represented by norbornene or tetracyclododecene as a monomer. Is done.

Cyclic olefin resins include cyclic olefin addition (co) polymers or hydrogenated products thereof (1), cyclic olefin and α-olefin addition copolymers or hydrogenated products (2), cyclic olefin ring-opening ( Co) polymers or hydrogenated products thereof (3).

Specific examples of the cyclic olefin include: cyclopentene, cyclohexene, cyclooctene; one-ring cyclic olefin such as cyclopentadiene, 1,3-cyclohexadiene; bicyclo [2.2.1] hept-2-ene (common name: norbornene) ), 5-methyl-bicyclo [2.2.1] hept-2-ene, 5,5-dimethyl-bicyclo [2.2.1] hept-2-ene, 5-ethyl-bicyclo [2.2. 1] Hept-2-ene, 5-butyl-bicyclo [2.2.1] hept-2-ene, 5-ethylidene-bicyclo [2.2.1] hept-2-ene, 5-hexyl-bicyclo [ 2.2.1] hept-2-ene, 5-octyl-bicyclo [2.2.1] hept-2-ene, 5-octadecyl-bicyclo [2.2.1] hept-2-ene, 5- Metilide -Bicyclo [2.2.1] hept-2-ene, 5-vinyl-bicyclo [2.2.1] hept-2-ene, 5-propenyl-bicyclo [2.2.1] hept-2-ene Bicyclic olefins such as;

Tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene (common name: dicyclopentadiene), tricyclo [4.3.0.1 ^2,5 ] dec-3-ene; tricyclo [ 4.4.0.1 ^2,5 ] undeca-3,7-diene or tricyclo [4.4.0.1 ^2,5 ] undeca-3,8-diene or a partially hydrogenated product thereof (or cyclopentadiene) And cyclohexene)), tricyclo [4.4.0.1 ^2,5 ] undec-3-ene;
5-cyclopentyl-bicyclo [2.2.1] hept-2-ene, 5-cyclohexyl-bicyclo [2.2.1] hept-2-ene, 5-cyclohexenylbicyclo [2.2.1] hepta 3-cyclic olefins such as 2-ene and 5-phenyl-bicyclo [2.2.1] hept-2-ene;

Tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene (also simply referred to as tetracyclododecene), 8-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methylidenetetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethylidenetetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-vinyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-propenyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] tetracyclic olefins such as dodec-3-ene;

8-cyclopentyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-cyclohexyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-cyclohexenyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-phenyl-cyclopentyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene; tetracyclo [7.4.1 ^3,6 . 0 ^1,9 . 0 ^2,7 ] tetradeca-4,9,11,13-tetraene (also referred to as 1,4-methano-1,4,4a, 9a-tetrahydrofluorene), tetracyclo [8.4.1 ^4,7 . 0 ^1,10 . 0 ^3,8 ] pentadeca-5,10,12,14-tetraene (also referred to as 1,4-methano-1,4,4a, 5,10,10a-hexahydroanthracene); pentacyclo [6.6.1] ^.1,3,6 . 0 ^2,7 . 0 ^9,14 ] -4-hexadecene, pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13] -4-pentadecene, pentacyclo [7.4.0.0 ^2,7. 1 ^3,6 . 1 ^10,13] -4-pentadecene; heptacyclo [8.7.0.1 ^2,9. 1 ^4,7 . 1 ^{11, 17} . 0 ^3,8 . 0 ^12,16 ] -5-eicosene, heptacyclo [8.7.0.1 ^2,9 . 0 ^3,8 . 1 ^4,7 . 0 ^12,17 . 1 ^13,16 ] ^-14-eicosene ; and polycyclic cyclic olefins such as cyclopentadiene tetramer. These cyclic olefins can be used alone or in combination of two or more.

Specific examples of the α-olefin copolymerizable with the cyclic olefin include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3 -Ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1- Hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, etc. 2-20, preferably carbon numbers Examples thereof include 2 to 8 α-olefins. These α-olefins can be used alone or in combination of two or more. As these α-olefins, those contained in the range of 5 to 200 mol% with respect to the cyclic polyolefin can be used.

There is no particular limitation on the polymerization method of the cyclic olefin or the cyclic olefin and the α-olefin and the hydrogenation method of the obtained polymer, and it can be performed according to a known method.

In the present embodiment, an addition copolymer of ethylene and norbornene is preferably used as the cyclic olefin resin.

The structure of the cyclic olefin-based resin is not particularly limited, and may be a chain, branched, or crosslinked, but is preferably a straight chain.

The molecular weight of the cyclic olefin-based resin is 5,000 to 300,000, preferably 10,000 to 150,000, and more preferably 15,000 to 100,000 according to the GPC method. If the number average molecular weight is too low, the mechanical strength decreases, and if it is too high, the moldability deteriorates.

In addition, the cyclic olefin resin has a polar group (for example, a carboxyl group, an acid anhydride group, an epoxy group, an amide group, an ester group, a hydroxyl group, etc.) in the above-mentioned cyclic olefin resins (1) to (3). What (4) which grafted and / or copolymerized the unsaturated compound (u) which has can be included. Two or more of the above cyclic olefin resins (1) to (4) may be used in combination.

Examples of the unsaturated compound (u) include (meth) acrylic acid, maleic acid, maleic anhydride, itaconic anhydride, glycidyl (meth) acrylate, alkyl (meth) acrylate (carbon number 1 to 10) ester, maleic acid Examples include alkyl (having 1 to 10 carbon atoms) ester, (meth) acrylamide, (2-hydroxyethyl) (meth) acrylate, and the like.

Affinity with metals and polar resins can be increased by using a modified cyclic olefin resin (4) obtained by grafting and / or copolymerizing an unsaturated compound (u) having a polar group, so vapor deposition, sputtering, coating It is possible to increase the strength of various secondary processing such as adhesion, and is suitable when secondary processing is required. However, the presence of the polar group has a drawback of increasing the water absorption rate of the cyclic olefin resin. Therefore, the content of polar groups (for example, carboxyl group, acid anhydride group, epoxy group, amide group, ester group, hydroxyl group, etc.) is preferably 0 to 1 mol / kg per 1 kg of cyclic olefin resin.

[Elastomer]
The elastomer is preferably a styrene elastomer. The styrenic elastomer is a copolymer of styrene and a conjugated diene such as butadiene or isoprene, and / or a hydrogenated product thereof. The styrene elastomer is a block copolymer having styrene as a hard segment and conjugated diene as a soft segment. The structure of the soft segment changes the storage elastic modulus of the styrene-based elastomer, and the content of styrene that is the hard segment changes the refractive index and changes the haze of the entire film. The styrene elastomer does not require a vulcanization step and is preferably used. Further, the hydrogenated one is more preferable because it has higher thermal stability.

Examples of styrenic elastomers include styrene / butadiene / styrene block copolymers, styrene / isoprene / styrene block copolymers, styrene / ethylene / butylene / styrene block copolymers, and styrene / ethylene / propylene / styrene block copolymers. Examples thereof include styrene and butadiene block copolymers.

In addition, styrene / ethylene / butylene / styrene block copolymer, styrene / ethylene / propylene / styrene block copolymer, styrene / butadiene block copolymer (hydrogenation) in which double bond of conjugated diene component is eliminated by hydrogenation May also be used.

The structure of the styrene-based elastomer is not particularly limited, and may be chain-like, branched or cross-linked, but is preferably linear in order to reduce the storage elastic modulus.

In the present embodiment, at least one styrene selected from the group consisting of styrene / ethylene / butylene / styrene block copolymers, styrene / ethylene / propylene / styrene block copolymers, and hydrogenated styrene / butadiene block copolymers. Based elastomers are preferably used. In particular, hydrogenated styrene / butadiene block copolymers are more preferably used because of high tear strength and small haze increase after environmental preservation. The ratio of butadiene to styrene in the hydrogenated styrene / butadiene block copolymer is preferably in the range of 10 to 90 mol% so as not to impair the compatibility with the cyclic olefin resin.

Further, the styrene content of the styrene elastomer is preferably 20 to 40 mol%. By setting the styrene content to 20 to 40 mol%, the haze can be further reduced.

The molecular weight of the styrene elastomer is 5,000 to 300,000, preferably 10,000 to 150,000, and more preferably 20,000 to 100,000, as determined by the GPC method. If the number average molecular weight is too low, the mechanical strength decreases, and if it is too high, the moldability deteriorates.

The weight ratio of the cyclic olefin resin to the styrene elastomer (cyclic olefin resin: styrene elastomer) is preferably 60:40 to 95: 1, and more preferably 85:15 to 95: 5. By setting it as such a range, the toughness of the film obtained can be improved more.

[Other additives]
The cyclic olefin-based resin composition film may contain various compounding agents as necessary in addition to the cyclic olefin-based resin and the elastomer as long as the characteristics thereof are not impaired. The various compounding agents are not particularly limited as long as they are usually used in thermoplastic resin materials. For example, inorganic oxide fine particles, antioxidants, ultraviolet absorbers, light stabilizers, plasticizers, lubricants, Examples thereof include antistatic agents, flame retardants, colorants such as dyes and pigments, near infrared absorbers, compounding agents such as fluorescent whitening agents, and fillers.

<2. Method for Producing Cyclic Olefin Resin Composition Film>
In the method for producing a cyclic olefin resin composition film according to the present embodiment, a cyclic olefin resin composition containing a cyclic olefin resin and an elastomer is heated and melted, and the heated and melted cyclic olefin resin composition is obtained. A cyclic olefin-based resin composition film having a refractive index in the MD direction that is 0.001 to 0.0035 larger than that in the TD direction is obtained by extrusion.

The cyclic olefin-based resin composition contains the cyclic olefin-based resin and the elastomer described above, and the preferred range is also the same.

The heating temperature of the cyclic olefin resin composition is preferably in the range of 210 to 300 ° C.

The film is preferably stretched so that the refractive index in the MD direction of the film is 0.001 to 0.0035 larger than the refractive index in the TD direction. The stretching of the film may be uniaxial stretching or biaxial stretching. In the case of uniaxial stretching, it is preferable to perform longitudinal stretching by a roll method or lateral stretching by a tenter. In the case of biaxial stretching, it is preferably performed by longitudinal stretching by a roll method and transverse stretching by a tenter. The stretching may be performed sequentially or simultaneously with the first and second axes.

FIG. 2 is a schematic diagram showing a configuration example of a film manufacturing apparatus. The film manufacturing apparatus includes a die 21, a roll 22, and a roll 23. The die 21 is a general T-die for melt molding, and extrudes the molten resin material 24 into a film shape. The resin material 24 contains the above-mentioned cyclic olefin resin composition, for example. The

rolls

22 and 23 have a configuration in which the resin material 24 extruded from the die 21 in a film shape can be nipped with an arbitrary pressure. The roll 22 and the roll 23 are configured to be rotatable in an arbitrary direction. More specifically, the roll 22 is configured to be rotatable at an arbitrary rotational speed ratio by a rotational power transmission mechanism (not shown) with respect to the rotational speed based on the roll 23. The surface shapes of the

rolls

22 and 23 are not particularly limited, and for example, a mirror surface, a textured surface, a prism, a lenticular, or the like can be arbitrarily selected. Each of the

rolls

22 and 23 has a medium flow path therein, and has a function of controlling the surface to an arbitrary temperature by an individual temperature control device. The material of the surface of the roll 22 and the roll 23 is not specifically limited, A metal, rubber | gum, resin, an elastomer, etc. can be used.

An example of a method for producing a cyclic olefin-based resin composition film using a film production apparatus having such a configuration will be described. First, the input resin material (cyclic olefin resin composition) is melted at an arbitrary temperature, and the resin material 24 is extruded from the die 21 into a film. The extruded molten resin material 24 is dropped and sandwiched between

rolls

22 and 23 to be stretched. By this stretching, a cyclic olefin-based resin composition film in which the refractive index in the MD direction is 0.001 to 0.0035 larger than the refractive index in the TD direction is obtained. Next, if necessary, the cyclic olefin-based resin composition film is conveyed to the next step along the roll 23 and wound into a raw fabric by a running system (not shown).

<3. Application example to electronic equipment>
In the cyclic olefin-based resin composition film according to the present embodiment, the refractive index in the MD direction of the film is 0.001 to 0.0035 larger than the refractive index in the TD direction. , Retardation of about 100 nm occurs. Therefore, the cyclic olefin-based resin composition film can be used for various optical applications, for example, a retardation film, a polarizing plate protective film, a light diffusing plate and the like, particularly a prism sheet and a liquid crystal cell substrate. Below, the application example which used the cyclic olefin resin composition film as a phase difference film is demonstrated.

3A and 3B are cross-sectional views showing an example of a transparent conductive film. This transparent conductive film (transparent conductive element) is constituted by using the above-mentioned cyclic olefin-based resin composition film as a base film (base material). Specifically, this transparent conductive film includes a retardation film 31 as a base film (base material), and a transparent conductive layer 33 on at least one surface of the retardation film 31. FIG. 3A is an example in which the transparent conductive layer 33 is provided on one surface of the retardation film 31, and FIG. 3B is an example in which the transparent conductive layer 33 is provided on both surfaces of the retardation film 31. In addition, as shown in FIGS. 3A and 3B, a hard coat layer 32 may be further provided between the retardation film 31 and the transparent conductive layer 33.

As the material of the transparent conductive layer 33, for example, one or more selected from the group consisting of electrically conductive metal oxide materials, metal materials, carbon materials, and conductive polymers can be used. Examples of the metal oxide material include indium tin oxide (ITO) zinc oxide, indium oxide, antimony-added tin oxide, fluorine-added tin oxide, aluminum-added zinc oxide, gallium-added zinc oxide, silicon-added zinc oxide, and zinc oxide- Examples thereof include a tin oxide system, an indium oxide-tin oxide system, and a zinc oxide-indium oxide-magnesium oxide system. As the metal material, for example, metal nanofillers such as metal nanoparticles and metal nanowires can be used. Specific examples of these materials include copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, iron, ruthenium, osmium, manganese, molybdenum, tungsten, niobium, tantalum, titanium, bismuth, Examples thereof include metals such as antimony and lead, and alloys thereof. Examples of the carbon material include carbon black, carbon fiber, fullerene, graphene, carbon nanotube, carbon microcoil, and nanohorn. As the conductive polymer, for example, substituted or unsubstituted polyaniline, polypyrrole, polythiofin, and one or two (co) polymers selected from these can be used.

As a method for forming the transparent conductive layer 33, for example, a PVD method such as a sputtering method, a vacuum deposition method, or an ion plating method, a CVD method, a coating method, a printing method, or the like can be used. The transparent conductive layer 33 may be a transparent electrode having a predetermined electrode pattern. Examples of the electrode pattern include a stripe shape, but are not limited thereto.

As the material of the hard coat layer 32, it is preferable to use an ionizing radiation curable resin that is cured by light or an electron beam, or a thermosetting resin that is cured by heat, and a photosensitive resin that is cured by ultraviolet rays is most preferable. As such a photosensitive resin, for example, acrylate resins such as urethane acrylate, epoxy acrylate, polyester acrylate, polyol acrylate, polyether acrylate, and melamine acrylate can be used. For example, the urethane acrylate resin is obtained by reacting a polyester polyol with an isocyanate monomer or a prepolymer, and reacting an acrylate or methacrylate monomer having a hydroxyl group with the obtained product. The thickness of the hard coat layer 32 is preferably 1 μm to 20 μm, but is not particularly limited to this range.

In addition, as shown in FIGS. 3C and 3D, the transparent conductive film is provided with a moth-eye structure 34 as an antireflection layer on at least one surface of the above-described retardation film. Also good. FIG. 3C is an example in which a moth-eye structure 34 is provided on one surface of the retardation film 31, and FIG. 3D is an example in which a moth-eye structure is provided on both surfaces of the retardation film. The antireflection layer provided on the surface of the retardation film 11 is not limited to the moth-eye structure described above, and a conventionally known antireflection layer such as a low refractive index layer can also be used. .

FIG. 4 is a schematic cross-sectional view showing one configuration example of the touch panel. The touch panel (input device) 40 is a so-called resistive film type touch panel. The resistive film type touch panel may be either an analog resistive film type touch panel or a digital resistive film type touch panel.

The touch panel 40 includes a first transparent conductive film 41 and a second transparent conductive film 42 facing the first transparent conductive film 41. The 1st transparent conductive film 41 and the 2nd transparent conductive film 42 are bonded together via the bonding part 45 between those peripheral parts. As the bonding part 45, for example, an adhesive paste, an adhesive tape or the like is used. The touch panel 40 is bonded to the display device 44 through the bonding layer 43, for example. As a material of the bonding layer 43, for example, an acrylic, rubber, or silicon adhesive can be used, and an acrylic adhesive is preferable from the viewpoint of transparency.

The touch panel 40 further includes a polarizer 48 bonded to the surface on the touch side of the first transparent conductive film 41 via a bonding layer 50 or the like. As the 1st transparent conductive film 41 and / or the 2nd transparent conductive film 42, the above-mentioned transparent conductive film can be used. However, the retardation film as the base film (base material) is set to λ / 4. By adopting the polarizer 48 and the retardation film 31 in this way, the reflectance can be reduced and the visibility can be improved.

The touch panel 40 is preferably provided with a moth-eye structure 34 on the opposing surfaces of the first transparent conductive film 41 and the second transparent conductive film 42, that is, on the surface of the transparent conductive layer 33. Thereby, the optical characteristics (for example, a reflection characteristic, a transmission characteristic, etc.) of the 1st transparent conductive film 41 and the 2nd transparent conductive film 42 can be improved.

The touch panel 40 preferably further includes a single-layer or multi-layer antireflection layer on the surface of the first transparent conductive film 41 on the touch side. Thereby, a reflectance can be reduced and visibility can be improved.

It is preferable that the touch panel 40 further includes a hard coat layer on the surface on the touch side of the first transparent conductive film 41 from the viewpoint of improving the scratch resistance. The surface of the hard coat layer is preferably imparted with antifouling properties.

It is preferable that the touch panel 40 further includes a front panel (surface member) 49 bonded to the surface on the touch side of the first transparent conductive film 41 via the bonding layer 51. Moreover, it is preferable that the touch panel 40 further includes a glass substrate 46 bonded to the surface of the second transparent conductive film 42 bonded to the display device 44 via a bonding layer 47.

The touch panel 40 preferably further includes a plurality of structures on the surface to be bonded to the display device 44 of the second transparent conductive film 42 or the like. The adhesion between the touch panel 40 and the bonding layer 43 can be improved by the anchor effect of the plurality of structures. As this structure, a moth-eye structure is preferable. Thereby, interface reflection can be suppressed.

As the display device 44, for example, a liquid crystal display, a CRT (Cathode Ray Tube) display, a plasma display (Plasma Display Panel: PDP), an electroluminescence (Electro Luminescence: EL) display, a surface conduction electron-emitting device display (Surface-conduction) Various display devices such as Electron-emitter Display (SED) can be used.

Next, an electronic apparatus including the input device 40 described above will be described. FIG. 5 is an external view illustrating an example of a television device as an electronic apparatus. The television device 100 includes a display unit 101, and the display unit 101 includes a touch panel 40.

6A and 6B are external views illustrating examples of a digital camera as an electronic device. 6A is an external view of the digital camera viewed from the front side, and FIG. 6B is an external view of the digital camera viewed from the back side. The digital camera 110 includes a light emitting unit 111 for flash, a display unit 112, a menu switch 113, a shutter button 114, and the like, and the display unit 112 includes the touch panel 40 described above.

FIG. 7 is an external view showing an example of a notebook personal computer as an electronic device. The notebook personal computer 120 includes a main body 121 including a keyboard 122 for inputting characters, a display unit 123 for displaying images, and the like, and the display unit 123 includes the touch panel 40 described above.

FIG. 8 is an external view showing an example of a video camera as an electronic device. The video camera 130 includes a main body 131, a subject shooting lens 132 on the side facing forward, a start / stop switch 133 during shooting, a display unit 134, and the like, and the display unit 134 includes the touch panel 40 described above.

FIG. 9 is an external view showing an example of a mobile phone as an electronic device. The mobile phone 140 is a so-called smartphone, and the display unit 141 includes the touch panel 40 described above.

FIG. 10 is an external view showing an example of a tablet computer as an electronic device. The tablet computer 150 includes the touch panel 40 described above on the display unit 151.

Even in each of the electronic devices as described above, since the cyclic olefin resin composition film having excellent mechanical isotropy is used for the display portion, high-quality display with high durability becomes possible.

<3. Example>
Examples of the present invention will be described below. In this example, an elastomer was added to the cyclic olefin-based resin composition, and a cyclic olefin-based resin composition film having a refractive index in the MD direction larger than the refractive index in the TD direction by a predetermined value was produced. About the produced cyclic olefin system resin composition film, tear strength of MD direction and TD direction was measured, and mechanical isotropy was evaluated. The present invention is not limited to these examples.

[Refractive index Δn (refractive index in MD direction−refractive index in TD direction)]
The refractive index in the MD direction and the refractive index in the TD direction were measured using a retardation measuring device (manufactured by Otsuka Electronics Co., Ltd.), and the difference between the refractive index in the MD direction and the refractive index in the TD direction (refractive index Δ n) was determined.

[Tear strength (right-angle tear)]
The tear strength was measured according to JISK7128 for a film having a thickness of 80 μm. A No. 3 type test piece was used as a test piece, and measurement was performed at a test speed of 200 mm / min using a tensile tester (AG-X, manufactured by Shimadzu Corporation). The average value of the tear strength in the MD direction pulled in the MD direction and the average value of the tear strength in the TD direction pulled in the TD direction were calculated.

[Mechanical isotropy]
When the condition of the following formula (1) was satisfied, the evaluation of mechanical isotropy of the cyclic olefin-based resin composition film was evaluated as ◯.
(1) The tear strength (N / mm) of the larger tear strength in the MD direction or TD direction of the cyclic olefin resin composition film × 0.8 <0.8 in the MD direction or TD direction of the cyclic olefin resin composition film The tear strength (N / mm) of the smaller tear strength

When the condition of the following (2) was satisfied, the mechanical isotropy of the cyclic olefin resin composition film was evaluated as Δ.
(2) The tear strength (N / mm) of the larger tear strength among the MD direction or TD direction of the cyclic olefin resin composition film × 0.8 ≧ the MD direction or TD direction of the cyclic olefin resin composition film The tear strength (N / mm) of the smaller tear strength, and the difference is 1.0 or less

When the condition (3) below was satisfied, the mechanical isotropy of the cyclic olefin resin composition film was evaluated as x.
(3) The tear strength (N / mm) of the larger tear strength among the MD direction or TD direction of the cyclic olefin resin composition film × 0.8 ≧ the MD direction or TD direction of the cyclic olefin resin composition film Of these, the tear strength (N / mm) of the smaller tear strength, and the difference exceeds 1.0

[Cyclic olefin resin]
As the cyclic olefin resin, TOPAS6013-S04 (manufactured by Polyplastics Co., Ltd., chemical name: addition copolymer of ethylene and norbornene) was used.

[Elastomer]
The following two types were used as the elastomer.
S. O. E. L606 (manufactured by Asahi Kasei Chemicals Corporation): hydrogenated styrene / butadiene block copolymer Tuftec H1517 (manufactured by Asahi Kasei Chemicals Corporation): styrene / ethylene / butylene / styrene block copolymer

[Example 1]
90 parts by mass of TOPAS 6013-S04 as the cyclic olefin resin, and S.I. O. E. 10 parts by mass of L606 was blended. This is kneaded at a predetermined temperature in the temperature range of 210 ° C. to 300 ° C. using a twin screw extruder (specifications: diameter 25 mm, length: 26 D, T die width: 160 mm) with a T die attached to the tip, and then circular The olefin resin composition was extruded at a speed of 250 g / min to form a film having a thickness of 80 μm. Thereafter, the extruded film was stretched so that the refractive index in the MD direction was 0.001 larger than the refractive index in the TD direction. As shown in Table 1, the tear strength in the MD direction of the film was 100 N / mm, and the tear strength in the TD direction was 120 N / mm. Evaluation of mechanical isotropy was (circle).

[Example 2]
A film was obtained in the same manner as in Example 1 except that the film was stretched so that the refractive index in the MD direction was 0.003 larger than the refractive index in the TD direction. As shown in Table 1, the tear strength in the MD direction of the film was 115 N / mm, and the tear strength in the TD direction was 105 N / mm. Evaluation of mechanical isotropy was (circle).

[Example 3]
A film was obtained in the same manner as in Example 1 except that Tuftec H1517 was used as the styrene-based elastomer and the film was stretched so that the refractive index in the MD direction was 0.001 larger than the refractive index in the TD direction. . As shown in Table 1, the tear strength in the MD direction of the film was 77 N / mm, and the tear strength in the TD direction was 95 N / mm. Evaluation of mechanical isotropy was (circle).

[Example 4]
A film was obtained in the same manner as in Example 1 except that Tuftec H1517 was used as the styrene-based elastomer and the film was stretched so that the refractive index in the MD direction was 0.002 larger than the refractive index in the TD direction. . As shown in Table 1, the tear strength in the MD direction of the film was 86 N / mm, and the tear strength in the TD direction was 86 N / mm. Evaluation of mechanical isotropy was (circle).

[Example 5]
A film was obtained in the same manner as in Example 1 except that Tuftec H1517 was used as the styrene-based elastomer and the film was stretched so that the refractive index in the MD direction was 0.003 larger than the refractive index in the TD direction. . As shown in Table 1, the tear strength in the MD direction of the film was 91 N / mm, and the tear strength in the TD direction was 81 N / mm. Evaluation of mechanical isotropy was (circle).

[Example 6]
A film was obtained in the same manner as in Example 1 except that Tuftec H1517 was used as the styrene-based elastomer and the film was stretched so that the refractive index in the MD direction was 0.0035 larger than the refractive index in the TD direction. . As shown in Table 1, the tear strength in the MD direction of the film was 96 N / mm, and the tear strength in the TD direction was 76 N / mm. Evaluation of mechanical isotropy was Δ.

[Comparative Example 1]
90 parts by mass of TOPAS 6013-S04 as the cyclic olefin resin, and S.I. O. E. 10 parts by mass of L606 was blended. This is kneaded at a predetermined temperature in the temperature range of 210 ° C. to 300 ° C. using a twin screw extruder (specifications: diameter 25 mm, length: 26 D, T die width: 160 mm) with a T die attached to the tip, and then circular The olefin resin composition was extruded at a speed of 250 g / min to form a film having a thickness of 80 μm. The film obtained in Comparative Example 1 is unstretched. As shown in Table 1, the refractive index in the MD direction of the film was 0.00005 larger than the refractive index in the TD direction. The tear strength in the MD direction of the film was 53 N / mm, and the tear strength in the TD direction was 165 N / mm. Evaluation of mechanical isotropy was x.

[Comparative Example 2]
A film was obtained in the same manner as in Comparative Example 1 except that Tuftec H1517 was used as the styrene elastomer. That is, the film obtained in Comparative Example 2 is also unstretched. As shown in Table 1, the refractive index in the MD direction was 0.00005 larger than the refractive index in the TD direction. The tear strength in the MD direction of the film was 47 N / mm, and the tear strength in the TD direction was 125 N / mm. Evaluation of mechanical isotropy was x.

[Comparative Example 3]
A film was obtained in the same manner as in Example 1 except that Tuftec H1517 was used as the styrene-based elastomer and the film was stretched so that the refractive index in the MD direction was 0.0001 larger than the refractive index in the TD direction. . As shown in Table 1, the tear strength in the MD direction of the film was 48.5 N / mm, and the tear strength in the TD direction was 123.5 N / mm. Evaluation of mechanical isotropy was x.

[Comparative Example 4]
A film was obtained in the same manner as in Example 1 except that Tuftec H1517 was used as the styrene-based elastomer and the film was stretched so that the refractive index in the MD direction was 0.0004 larger than the refractive index in the TD direction. . As shown in Table 1, the tear strength in the MD direction of the film was 58 N / mm, and the tear strength in the TD direction was 114 N / mm. Evaluation of mechanical isotropy was x.

[Comparative Example 5]
A film was obtained in the same manner as in Example 1 except that Tuftec H1517 was used as the styrene-based elastomer and the film was stretched so that the refractive index in the MD direction was 0.0007 larger than the refractive index in the TD direction. . As shown in Table 1, the tear strength in the MD direction of the film was 68 N / mm, and the tear strength in the TD direction was 104 N / mm. Evaluation of mechanical isotropy was x.

[Comparative Example 6]
A film was obtained in the same manner as in Example 1 except that Tuftec H1517 was used as the styrene-based elastomer and the film was stretched so that the refractive index in the MD direction was 0.004 larger than the refractive index in the TD direction. . As shown in Table 1, the tear strength in the MD direction of the film was 104 N / mm, and the tear strength in the TD direction was 68 N / mm. Evaluation of mechanical isotropy was x.

As in Examples 1 to 6, the cyclic olefin resin composition film having a refractive index in the MD direction of 0.001 to 0.0035 larger than that in the TD direction is excellent in mechanical isotropy. I understood. In particular, it has been found that a cyclic olefin resin composition film having a refractive index in the MD direction of 0.001 to 0.0030 larger than that in the TD direction is superior in mechanical isotropy.

On the other hand, as in Comparative Examples 1 to 6, the cyclic olefin resin composition film that does not satisfy the condition that the refractive index in the MD direction is 0.001 to 0.0035 larger than the refractive index in the TD direction is mechanically isotropic. It turned out that it is not excellent in property. That is, as in Comparative Examples 1 to 6, it was found that mechanical anisotropy was confirmed when the refractive index Δn was less than 0.001 or when the refractive index Δn exceeded 0.0035. .

11 cyclic olefin resin, 12 elastomer, 21 die, 22, 23 roll, 24 / resin material, 31 retardation film, 32 hard coat layer, 33 transparent conductive layer, 34 moth-eye-shaped structure, 40 touch panel, 41 1st Transparent conductive film, 42 second transparent conductive film, 43 bonding layer, 44 display device, 45 bonding portion, 46 glass substrate, 47 bonding layer, 48 polarizer, 49 front panel, 50 bonding layer , 51 Bonding layer, 100 TV device, 101 display unit, 110 digital camera, 111 light emitting unit, 112 display unit, 113 menu switch, 114 shutter button, 120 notebook personal computer, 121 main body unit, 122 keyboard, 123 display unit , 130 video camera, 131 body , 132 lens, 133 a start / stop switch, 134 display unit, 140 mobile phones, 141 display unit, 150 a tablet computer, 151 display unit

Claims

A cyclic olefin-based resin composition film obtained by stretching a cyclic olefin-based resin composition composed of a cyclic olefin-based resin and an elastomer so that the refractive index in the MD direction is 0.001 to 0.0035 larger than the refractive index in the TD direction.
The cyclic olefin-based resin composition film according to claim 1, wherein the refractive index in the MD direction is 0.001 to 0.0030 larger than the refractive index in the TD direction.
The cyclic olefin resin composition film of Claim 1 or 2 which satisfy | fills the conditions of following formula (1).
(1) The tear strength (N / mm) of the larger tear strength in the MD direction or TD direction of the cyclic olefin resin composition film × 0.8 <0.8 in the MD direction or TD direction of the cyclic olefin resin composition film The tear strength (N / mm) of the smaller tear strength
The tear strength in the MD direction and TD direction is 70 N / mm or more,
The cyclic olefin resin composition film according to claim 1 or 2, wherein the difference between the tear strength in the MD direction and the tear strength in the TD direction is 20 N / mm or less.
The cyclic olefin-based resin composition film according to any one of claims 1 to 4, wherein the elastomer content is 5 wt% or more and 30 wt% or less.
The cyclic olefin resin composition film according to any one of claims 1 to 5, wherein the cyclic olefin resin is an addition copolymer of ethylene and norbornene.
The elastomer is at least one selected from the group consisting of a styrene / ethylene / butylene / styrene block copolymer, a styrene / ethylene / propylene / styrene block copolymer, and a hydrogenated styrene / butadiene block copolymer. Item 7. The cyclic olefin-based resin composition film according to any one of Items 1 to 6.
A transparent conductive element comprising the cyclic olefin-based resin composition film according to any one of claims 1 to 7 as a base material.
An input device comprising the cyclic olefin-based resin composition film according to any one of claims 1 to 7.
A display device comprising the cyclic olefin-based resin composition film according to any one of claims 1 to 7.
An electronic device comprising the cyclic olefin-based resin composition film according to any one of claims 1 to 7.
Heat-melting a cyclic olefin resin composition containing a cyclic olefin resin and an elastomer,
Cyclic olefin obtained by stretching the heat-melted cyclic olefin resin composition to obtain a cyclic olefin resin composition film in which the refractive index in the MD direction is 0.001 to 0.0035 larger than the refractive index in the TD direction Of the resin-based resin composition film.