WO2013118641A1 - ハードコートフィルム、偏光板、画像表示装置用ガラス飛散防止フィルム、タッチパネル及び液晶表示装置 - Google Patents
ハードコートフィルム、偏光板、画像表示装置用ガラス飛散防止フィルム、タッチパネル及び液晶表示装置 Download PDFInfo
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- WO2013118641A1 WO2013118641A1 PCT/JP2013/052311 JP2013052311W WO2013118641A1 WO 2013118641 A1 WO2013118641 A1 WO 2013118641A1 JP 2013052311 W JP2013052311 W JP 2013052311W WO 2013118641 A1 WO2013118641 A1 WO 2013118641A1
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- 0 *(*c1ccccc1)*c1ccc(*c2ccccc2)cc1 Chemical compound *(*c1ccccc1)*c1ccc(*c2ccccc2)cc1 0.000 description 7
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- G02B1/105—
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/044—Forming conductive coatings; Forming coatings having anti-static properties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/056—Forming hydrophilic coatings
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
- G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
- G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/08—Cellulose derivatives
- C08J2301/10—Esters of organic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
Definitions
- the present invention relates to a hard coat film, a polarizing plate using the same, a glass scattering prevention film for an image display device, a touch panel and a liquid crystal display device. More specifically, a hard coat film that suppresses occurrence of flatness deterioration and unevenness when rolled into a roll, a polarizing plate excellent in visibility using the hard coat film, a glass scattering prevention film for an image display device, The present invention relates to a touch panel and a liquid crystal display device.
- liquid crystal display devices have attracted attention as image display elements.
- Liquid crystal display devices are widely used in monitors for personal computers and portable devices, and for television applications because of their various advantages, such as low voltage and low power consumption, enabling miniaturization and thinning.
- a film having a hard coat layer on a cellulose ester film such as a triacetate film (hereinafter referred to as a hard coat film) is used on the surface of the liquid crystal display device.
- a panel of a liquid crystal display device has a structure in which a liquid crystal cell is sandwiched between two polarizing plates.
- the polarizing plate used on the front side is a polyvinyl alcohol (hereinafter abbreviated as PVA) film in which iodine or a dichroic dye is adsorbed and dyed between a hard coat film and a cellulose ester film in a certain direction. It has a three-layer structure with a polarizing element (polarizing film) stretched and oriented in between.
- PVA polyvinyl alcohol
- these films are laminated after alkali treatment in order to improve the adhesion between the PVA and the hard coat film and between the PVA and the cellulose ester film.
- the thin hard coat film needs to have a certain degree of slipperiness in order to prevent generation of scratches and wrinkles during roll conveyance during the production. Therefore, it is considered desirable to make the surface contact angle with water relatively high.
- the polarizing plate is manufactured by a roll-to-roll method from the viewpoint of production, and manufactured in a roll state.
- the protective film of the polarizing plate into a thin film, the polarizing plate itself can be wound up and transported in a roll state, or rolled out from the roll-shaped polarizing plate when being attached to a liquid crystal panel. ⁇ Manufacturing of liquid crystal display devices using the two-panel method is also under consideration.
- the compressed air layer is easy to come out of the winding, and the problem of winding misalignment is likely to occur.
- the polarizing plate composed of a thin film was likely to buckle and deform due to the stress when wound in a roll shape, and unevenness due to flatness deterioration or distortion was likely to occur. In particular, unevenness due to deterioration of flatness and distortion was remarkable after a durability test assuming long-term transportation.
- the hard coat layer of the hard coat film and the film of the cellulose ester film are wound in a state where the films face each other. It is disclosed.
- Patent Document 1 includes one or two or more strip-shaped end hard coat layers at both ends in the width direction of the hard coat layer, and the film thickness of the end hard coat layer is set to the thickness of the hard coat layer. This is a technique for preventing winding slippage by causing blocking at the end by reducing the slipperiness of the film by making it thicker than the thickness.
- the above-described technique can achieve a certain degree of effect in preventing winding deviation in a single film, the effect is insufficient in preventing winding deviation particularly in a polarizing plate in which the hard coat film or cellulose ester film is thinned. It was. Moreover, it is difficult to control only the edge film thickness, and there is a problem in productivity.
- the present invention has been made in view of the above-described problems and situations, and its solution is to suppress slippage between films and to prevent winding misalignment when wound into a roll shape, or to be wound into a roll shape. It is intended to provide a hard coat film that suppresses buckling deformation and distortion at the time of occurrence, and suppresses flatness deterioration and occurrence of unevenness. Moreover, it is providing the polarizing plate excellent in visibility using this hard coat film, the glass scattering prevention film for image display apparatuses, a touch panel, and a liquid crystal display device.
- the present inventor is a hard coat film having a hard coat layer on a substrate film that is thinned in the process of examining the cause of the above-mentioned problem, and an alkali treatment of the hard coat layer
- ⁇ ⁇ the difference between the front and rear water contact angles
- the hard coat film of the present invention maintains an air layer between roll-shaped layers in addition to winding misalignment, and therefore has excellent blocking properties (sticking between films), and is excellent in flatness and unevenness. Provided excellent visibility when used in a glass scattering prevention film for a display device, a touch panel and a liquid crystal display device.
- a hard coat film having a hard coat layer on at least one surface of a cellulose ester film having a thickness in the range of 5 to 34 ⁇ m, before and after the alkali treatment when the hard coat layer is alkali treated under the following conditions A hard coat film having a difference in contact angle with water ( ⁇ ⁇ ) within a range of 5 to 55 °.
- Alkaline treatment conditions Alkaline solution: 2.5 mol / L potassium hydroxide solution Treatment temperature: 50 ° C Processing time: 120 seconds 2.
- Item 4 The hard coat film according to any one of items 1 to 3, wherein an arithmetic average roughness Ra (JIS B0601: 2001) of the hard coat layer is in a range of 2 to 100 nm. .
- Ra arithmetic average roughness
- hard coat film according to any one of items 1 to 4, wherein the hard coat layer contains an active energy ray-curable isocyanurate derivative.
- the in-plane retardation value Ro was in the range of 0 to 10 nm and the thickness direction 6.
- Polarized light characterized by sandwiching a polarizing element using the hard coat film according to any one of items 1 to 6 and a cellulose ester film having a thickness of 5 to 34 ⁇ m. Board.
- a glass scattering prevention film for an image display device wherein the hard coat film according to any one of items 1 to 6 is used.
- a touch panel comprising the hard coat film according to any one of items 1 to 6.
- a liquid crystal display device comprising the polarizing plate according to item 7 on at least one surface of a liquid crystal cell.
- the hard coat film that suppresses slipperiness between films and has a high effect of preventing winding displacement when wound into a roll in a thin film.
- the hard coat film is excellent in flatness and unevenness, it is possible to provide a polarizing plate, a glass scattering prevention film for an image display device, a touch panel, and a liquid crystal display device having excellent visibility by using the hard coat film. Can do.
- the hard coat layer of the hard coat film is wound into a roll shape by bringing the wettability (contact angle with water) of the hard coat film close to the wettability of the cellulose ester film used as a substrate and making them hydrophilic to each other. It is presumed that slipping when the films come into contact with each other is suppressed, and an effect of preventing winding deviation is obtained. In addition, the air layer between the roll layers is also retained, and the stress load on the film is suppressed, so buckling deformation and distortion are unlikely to occur, and it is estimated that a hard coat film excellent in flatness and unevenness can be obtained. Yes.
- An example of a touch panel display device using the hard coat film according to the present invention An example of an image display device with a touch panel
- An example of a schematic sectional view using a glass scattering prevention film for an image display device in the image display device Cross section of polarizing plate 101
- the hard coat film of the present invention is a hard coat film having a hard coat layer on at least one surface of a cellulose ester film having a thickness in the range of 5 to 34 ⁇ m, and the hard coat layer is subjected to an alkali treatment under the following conditions.
- the difference ( ⁇ ⁇ ) in water contact angle before and after the alkali treatment is in the range of 5 to 55 °.
- Alkaline treatment conditions Alkaline solution: 2.5 mol / L potassium hydroxide solution Treatment temperature: 50 ° C Processing time: 120 seconds This feature is a technical feature common to the inventions according to claims 1 to 10.
- the water contact angle ( ⁇ ) of the hard coat layer before the alkali treatment is preferably in the range of 50 to 120 °, and the water contact angle of the hard coat layer is
- the alkali treatment conditions decrease after the alkali treatment as compared to before the alkali treatment.
- the arithmetic average roughness Ra (JIS B0601: 2001) of the hard coat layer is in the range of 2 to 100 nm. It is preferable because it suppresses slipperiness and increases the effect of preventing winding deviation.
- the hard coat layer contains an active energy ray-curable isocyanurate derivative because the effect of suppressing slippage between films is enhanced.
- the in-plane retardation value Ro is in the range of 0 to 10 nm.
- the retardation value Rth in the thickness direction is preferably in the range of ⁇ 10 to 10 nm.
- a polarizing plate in which a polarizing element is sandwiched between a hard coat film according to the present invention and a cellulose ester film having a film thickness in the range of 5 to 34 ⁇ m. Can be prevented, which is preferable.
- the hard coat film of the present invention has good visibility, it can be suitably provided for a glass scattering prevention film for an image display device, a touch panel and a liquid crystal display device.
- ⁇ is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
- the difference ( ⁇ ⁇ ) in water contact angle before and after the alkali treatment of the hard coat layer is in the range of 5 to 55 °. More preferably, the difference ( ⁇ ⁇ ) in water contact angle is in the range of 15 to 50 °.
- the difference ( ⁇ ⁇ ) between the water contact angle before and after the alkali treatment was alkali-treated under the conditions shown below from the water contact angle ( ⁇ ) of the hard coat layer before the alkali treatment of the hard coat film. This is a value obtained by subtracting the water contact angle ( ⁇ a) of the subsequent hard coat layer to obtain the difference ( ⁇ ) in water contact angle before and after the alkali treatment.
- the conditions for the alkali treatment are conditions for immersing the hard coat film in a 2.5 mol / L potassium hydroxide solution at a temperature of 50 ° C. for 120 seconds.
- the contact angle with water is measured by a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.) in an atmosphere at a temperature of 23 ° C. and a relative humidity of 55%.
- the contact angle of pure water is measured 1 minute after dropping 1 ⁇ L of pure water using a product name DropMaster DM100). It is a value obtained by measuring seven times and averaging five measured values excluding the maximum value and the minimum value.
- the hard coat layer when the difference ( ⁇ ⁇ ) in water contact angle before and after alkali treatment of the hard coat layer satisfies the above range, the hard coat layer exhibits hydrophilicity, and when the hard coat layer is wound into a roll, Slip property between films is suppressed, and an effect of preventing winding deviation is obtained.
- the water contact angle ( ⁇ ) of the hard coat layer before the alkali treatment is preferably in the range of 50 to 120 °, more preferably in the range of 60 to 110 °.
- the water contact angle ( ⁇ a) of the hard coat layer after the alkali treatment is not particularly limited as long as the difference from the hard coat layer before the alkali treatment is within the range of 5 to 55 °. It can be appropriately selected within a range in which the winding deviation in the polarizing plate is suppressed. Specifically, it is preferably in the range of 40 to 110 °, and particularly preferably in the range of 40 to 80 °.
- the contact angle with water decreases after the alkali treatment, and the difference ( ⁇ ⁇ ) in the contact angle with water satisfies the above range.
- the alkali treatment of the present invention includes a step of immersing at least a hard coat film in an alkaline solution (hereinafter also referred to as a saponification step), washing with water and drying, and the conditions for the alkali treatment are the conditions described above.
- the solution may be washed with water and dried after neutralization in an acidic water process.
- the difference in contact angle with water before and after alkali treatment ( ⁇ ⁇ ) can be adjusted to satisfy the above range.
- the hard coat layer according to the present invention preferably contains an actinic radiation curable resin from the viewpoint of excellent mechanical film strength (abrasion resistance, pencil hardness). That is, it is a layer mainly composed of a resin that is cured through a crosslinking reaction upon irradiation with active rays (also called active energy rays) such as ultraviolet rays and electron beams.
- active rays also called active energy rays
- the actinic radiation curable resin a component containing a monomer having an ethylenically unsaturated double bond is preferably used, and an actinic radiation curable resin layer is formed by curing by irradiation with actinic radiation such as ultraviolet rays or electron beams.
- the Typical examples of the actinic radiation curable resin include an ultraviolet curable resin and an electron beam curable resin, but a resin curable by ultraviolet irradiation is particularly excellent in mechanical film strength (abrasion resistance, pencil hardness). It is preferable from the point.
- the ultraviolet curable resin include an ultraviolet curable acrylate resin, an ultraviolet curable urethane acrylate resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, an ultraviolet curable polyol acrylate resin, and an ultraviolet ray.
- a curable epoxy resin or the like is preferably used, and among them, an ultraviolet curable acrylate resin or an ultraviolet curable urethane acrylate resin is preferable.
- polyfunctional acrylate is preferable.
- the polyfunctional acrylate is preferably selected from the group consisting of pentaerythritol polyfunctional acrylate, dipentaerythritol polyfunctional acrylate, pentaerythritol polyfunctional methacrylate, and dipentaerythritol polyfunctional methacrylate.
- the polyfunctional acrylate is a compound having two or more acryloyloxy groups or methacryloyloxy groups in the molecule.
- polyfunctional acrylate monomer examples include ethylene glycol diacrylate, diethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, and tetramethylolmethane triacrylate.
- the active energy ray-curable isocyanurate derivative is not particularly limited as long as it is a compound having a structure in which one or more ethylenically unsaturated groups are bonded to an isocyanuric acid skeleton.
- a compound having three or more ethylenically unsaturated groups and one or more isocyanurate rings in the same molecule shown is preferable from the viewpoint of the object effect of the present invention.
- the kind of ethylenically unsaturated group is an acryloyl group, a methacryloyl group, a styryl group, and a vinyl ether group, more preferably a methacryloyl group or an acryloyl group, and particularly preferably an acryloyl group.
- L 2 is a divalent linking group, preferably a substituted or unsubstituted alkyleneoxy group or polyalkyleneoxy group having 4 or less carbon atoms in which a carbon atom is bonded to the isocyanurate ring, Particularly preferred are alkyleneoxy groups, which may be the same or different.
- R 2 represents a hydrogen atom or a methyl group, and may be the same or different.
- Other compounds include isocyanuric acid diacrylate compounds, and isocyanuric acid ethoxy-modified diacrylate represented by the following general formula (2).
- ⁇ -caprolactone-modified active energy ray-curable isocyanurate derivatives specifically, compounds represented by the following general formula (3).
- the functional groups represented by a, b and c below are attached to the positions of R 1 to R 3 in the above chemical structural formula, and at least one of R 1 to R 3 is a functional group of b.
- Examples of commercially available isocyanuric acid triacrylate compounds include A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd.
- Examples of commercially available isocyanuric acid diacrylate compounds include Aronix M-215 manufactured by Toagosei Co., Ltd.
- Examples of the mixture of the isocyanuric acid triacrylate compound and the isocyanuric acid diacrylate compound include Aronix M-315 and Aronix M-313 manufactured by Toagosei Co., Ltd.
- ⁇ -Caprolactone-modified active energy ray-curable isocyanurate derivatives include ⁇ -caprolactone-modified tris- (acryloxyethyl) isocyanurate, Shin-Nakamura Chemical Co., Ltd. A-9300-1CL, Toagosei Co., Ltd. Examples include, but are not limited to, Aronix M-327.
- Adekaoptomer N series Sunrad H-601, RC-750, RC-700, RC-600, RC-500, RC-611, RC-612 (manufactured by Sanyo Chemical Industries, Ltd.) , Aronix M-6100, M-8030, M-8060, Aronix M-215, Aronix M-315, Aronix M-313, Aronix M-327 (manufactured by Toagosei Co., Ltd.), NK-ester A-TMM-3L NK-ester AD-TMP, NK-ester ATM-35E, NK ester A-DOG, NK ester A-IBD-2E, A-9300, A-9300-1CL (Shin Nakamura Chemical Co., Ltd.), PE- 3A (Kyoeisha Chemical) etc. are mentioned.
- the ultraviolet curable urethane acrylate resin examples include, for example, a polyurethane obtained by reacting an alcohol, a polyol, and / or a hydroxyl group-containing compound such as a hydroxyl group-containing acrylate and an isocyanate or, if necessary, these reactions. It is obtained by esterifying a compound with (meth) acrylic acid. More specifically, it is an addition reaction product of polyisocyanate and an acrylate having one hydroxy group and one or more (meth) acryloyl groups in one molecule.
- polyisocyanate examples include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 4,4 ' A compound having two isocyanate groups bonded to an alicyclic hydrocarbon such as aromatic isocyanate such as diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, norbornane diisocyanate, 1,4-cyclohexane diisocyanate (hereinafter referred to as alicyclic diisocyanate and A compound having two isocyanate groups bonded to an aliphatic hydrocarbon such as trimethylene diisocyanate and hexamethylene diisocyanate (hereinafter referred to as aliphatic diisocyanate).
- aromatic isocyanate such as diphenyl
- Phenylene diisocyanate aromatic diisocyanates such as toluene diisocyanate, and aromatic aliphatic diisocyanates such as xylylene diisocyanate.
- aromatic diisocyanates can be used alone or in combination of two or more, preferably aliphatic diisocyanates and alicyclic diisocyanates. Of these, isophorone diisocyanate, norbornane diisocyanate, toluene diisocyanate and hexamethylene diisocyanate are preferred.
- Examples of the acrylate having one hydroxy group and one or more (meth) acryloyl groups in one molecule include, for example, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol penta (meth).
- Examples include polyacrylates of polyvalent hydroxy group-containing compounds such as acrylates, adducts of these polyacrylates and ⁇ -caprolactone, adducts of these polyacrylates and alkylene oxides, and epoxy acrylates. It is done.
- the acrylate having one hydroxy group and one or more (meth) acryloyl groups in one molecule can be used alone or in combination of two or more.
- acrylates having one hydroxy group and one or more (meth) acryloyl groups in one molecule acrylates having one hydroxy group and three to five (meth) acryloyl groups in one molecule are preferable.
- examples of such acrylates include pentaerythritol triacrylate and dipentaerythritol pentaacrylate.
- UV curable urethane acrylate resin examples include: Nippon Synthetic Chemical Industry Co., Ltd., Shikou UV-1700B, UV-6300B, UV-7600B, UV-7630B, UV-7630B, UV-7640B, Kyoeisha Chemical Co., Ltd. Company-made, UA-306H, UA-306T, UA-306I, UA-510H, Shin-Nakamura Chemical Co., Ltd., NK Oligo UA-1100H, NK Oligo UA-53H, NK Oligo UA-33H, NK Oligo UA-15HA Etc.
- the viscosity of the actinic radiation curable resin can be measured using a B-type viscometer under the condition of 25 ° C. after stirring and mixing the resin with a disper.
- a monofunctional acrylate may also be used.
- Monofunctional acrylates include isobornyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, isostearyl acrylate, benzyl acrylate, ethyl carbitol acrylate, phenoxyethyl acrylate, lauryl acrylate, isooctyl acrylate, tetrahydrofurfuryl acrylate, behenyl Examples thereof include acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and cyclohexyl acrylate.
- Such monofunctional acrylates can be obtained from Nippon Kasei Kogyo Co., Ltd., Shin-Nakamura Chemical Co., Ltd., Osaka Organic Chemical Co., Ltd., etc.
- monofunctional acrylate 80: 20 to 98: 2 in terms of the mass ratio of polyfunctional acrylate to monofunctional acrylate.
- the hard coat layer preferably contains a photopolymerization initiator to accelerate the curing of the actinic radiation curable resin.
- Specific examples of the photopolymerization initiator include alkylphenone series, acetophenone, benzophenone, hydroxybenzophenone, Michler ketone, ⁇ -amyloxime ester, thioxanthone, and derivatives thereof. In particular, it is not limited to these.
- photopolymerization initiators Commercially available products may be used as such photopolymerization initiators, and preferred examples include Irgacure 184, Irgacure 907, and Irgacure 651 manufactured by BASF Japan.
- the hard coat layer may contain a conductive agent in order to impart antistatic properties.
- Preferred conductive agents include metal oxide particles or ⁇ -conjugated conductive polymers.
- An ionic liquid is also preferably used as the conductive compound.
- a silicone-based surfactant for the hard coat layer, from the viewpoint of controlling the difference ( ⁇ ⁇ ) in water contact angle before and after the alkali treatment within the above range, a silicone-based surfactant, a fluorine-based surfactant, an anionic surfactant, and fluorine-siloxane are used. You may contain additives, such as a graft compound, a fluorine-type compound, and an acrylic copolymer. Further, a compound having an HLB value in the range of 3 to 18 may be contained. By adjusting the type and amount of these additives, water repellency can be controlled, and ⁇ ⁇ can be easily controlled within the above range.
- the HLB value is Hydrophile-Lipophile-Balance, hydrophilic-lipophilic-balance, and is a value indicating the hydrophilicity or lipophilicity of a compound.
- HLB 7 + 11.7Log (Mw / Mo)
- Mw represents the molecular weight of the hydrophilic group
- Mo represents the molecular weight of the lipophilic group
- Mw + Mo M (molecular weight of the compound).
- Emulgen 102KG (6.3), Emulgen 103 (8.1), Emulgen 104P (9.6), Emulgen 105 (9.7), Emulgen 106 (10.5), Emulgen 108 (12. 1), Emulgen 109P (13.6), Emulgen 120 (15.3), Emulgen 123P (16.9), Emulgen 147 (16.3), Emulgen 210P (10.7), Emulgen 220 (14.2) , Emulgen 306P (9.4), Emulgen 320P (13.9), Emulgen 404 (8.8), Emulgen 408 (10.0), Emulgen 409PV (12.0), Emulgen 420 (13.6), Emulgen 430 (16.2), Emulgen 705 (10.5), Emulgen 707 (12.1), Emulgen 09 (13.3), Emulgen 1108 (13.5), Emulgen 1118S-70 (16.4), Emulgen 1135S-70 (17.9), Emulgen 2020G-HA (13.0), Emulgen 2025G (15.
- Emulgen LS-106 (12.5), Emulgen LS-110 (13.4), Emulgen LS-114 (14.0), manufactured by Nissin Chemical Industry Co., Ltd .: Surfynol 104E (4), Surfynol 104H (4), Surfinol 104A (4), Surfinol 104BC (4), Surfinol 104DPM (4), Surfinol 104PA (4), Surfinol 104PG-50 (4), Surfinol 104S (4), Surfi Knoll 420 (4), Surfynol 440 (8), Surfynol 4 5 (13), Surfynol 485 (17), Surfynol SE (6), manufactured by Shin-Etsu Chemical Co., Ltd .: X-22-4272 (7), X-22-6266 (8), KF-351 (12) ), KF-352 (7), KF-353 (10), KF-354L (16), KF-355A (12), KF-615A (10), K),
- silicone surfactant examples include polyether-modified silicone, and the KF series manufactured by Shin-Etsu Chemical Co., Ltd. can be used.
- acrylic copolymer examples include commercially available compounds such as BYK-350 and BYK-352 manufactured by BYK Japan.
- fluorosurfactant examples include MegaFuck RS series and MegaFuck F-444 MegaFuck F-556 manufactured by DIC Corporation.
- the fluorine-siloxane graft compound refers to a copolymer compound obtained by grafting polysiloxane and / or organopolysiloxane containing siloxane and / or organosiloxane alone to at least a fluorine-based resin.
- Such a fluorine-siloxane graft compound can be prepared by a method as described in Examples described later.
- examples of commercially available products include ZX-022H, ZX-007C, ZX-049, and ZX-047-D manufactured by Fuji Chemical Industry Co., Ltd.
- a fluorine-type compound Daikin Industries Ltd.
- OPTOOL DSX, OPTOOL DAC, etc. can be mentioned. These components are preferably added in the range of 0.005 parts by mass or more and 5 parts by mass or less with respect to the solid component in the hard coat composition.
- a hard-coat layer may further contain the ultraviolet absorber demonstrated by the cellulose-ester film mentioned later.
- the ultraviolet absorber when it is constituted by two or more layers, it is preferable to contain the ultraviolet absorber in the hard coat layer in contact with the cellulose ester film.
- the thickness of the hard coat layer in contact with the cellulose ester film is preferably in the range of 0.05 to 2 ⁇ m.
- Two or more layers may be formed as a simultaneous multilayer.
- the simultaneous multi-layering is to form a hard coat layer by applying two or more hard coat layers by wet on wet without passing through a drying step.
- the layers are stacked one after another with an extrusion coater or simultaneously with a slot die having a plurality of slits. Can be done.
- the hard coat layer is formed by diluting the above-described components forming the hard coat layer with a solvent that swells or partially dissolves the cellulose ester film, and is applied onto the cellulose film by the following method and dried. It is preferable to provide a hard coat layer by curing.
- ketones methyl ethyl ketone, acetone, etc.
- acetate esters methyl acetate, ethyl acetate, butyl acetate, etc.
- alcohols ethanol, methanol
- propylene glycol monomethyl ether cyclohexanone, methyl isobutyl ketone, etc.
- the coating amount of the hard coat layer is suitably in the range of 0.1 to 40 ⁇ m as wet film thickness, and preferably in the range of 0.5 to 30 ⁇ m.
- the dry film thickness is in the range of an average film thickness of 0.01 to 20 ⁇ m, preferably in the range of 0.5 to 10 ⁇ m. More preferably, it is in the range of 0.5 to 5 ⁇ m.
- a gravure coater As a method for applying the hard coat layer, known methods such as a gravure coater, a dip coater, a reverse coater, a wire bar coater, a die coater, and an ink jet method can be used.
- Hard coat layer forming method After applying the hard coat layer composition, it may be dried and cured by irradiation with active rays (also referred to as UV curing treatment), and if necessary, heat treatment may be performed after the UV curing treatment.
- the heat treatment temperature after the UV curing treatment is preferably 80 ° C. or higher, more preferably 100 ° C. or higher, and particularly preferably 120 ° C. or higher.
- Drying is preferably performed by high-temperature treatment at a temperature of 90 ° C. or higher in the rate of drying section. More preferably, the temperature in the decreasing rate drying section is 90 ° C. or higher and 125 ° C. or lower.
- the temperature of the rate-decreasing drying section is set to a high temperature treatment, convection occurs in the coating resin during the formation of the hard coat layer, and as a result, irregular surface roughness tends to appear on the hard coat layer surface, which will be described later. It is easy to control the arithmetic average roughness Ra.
- the drying process changes from a constant state to a gradually decreasing state when drying starts.
- the decreasing section is called the decreasing rate drying section.
- the constant rate drying section the amount of heat flowing in is all consumed for solvent evaporation on the coating film surface, and when the solvent on the coating film surface decreases, the evaporation surface moves from the surface to the inside and enters the decreasing rate drying section. Thereafter, the temperature of the coating film surface rises and approaches the hot air temperature, so that the temperature of the actinic radiation curable resin composition rises, the resin viscosity decreases, and the fluidity increases.
- any light source that generates ultraviolet rays can be used without limitation.
- a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used.
- Irradiation conditions vary depending on each lamp, but the irradiation amount of active rays is usually in the range of 50 to 1000 mJ / cm 2 , preferably in the range of 50 to 300 mJ / cm 2 .
- oxygen removal for example, replacement with an inert gas such as nitrogen purge
- the cured state of the surface can be controlled by adjusting the removal amount of the oxygen concentration. This makes it possible to control the presence state of the additive on the hard coat layer surface, and as a result, it is easy to control ⁇ within the above range.
- irradiating actinic radiation it is preferably performed while applying tension in the film transport direction, and more preferably while applying tension in the width direction.
- the tension to be applied is preferably 30 to 300 N / m.
- the method for applying the tension is not particularly limited, and the tension may be applied in the conveying direction on the back roller, or the tension may be applied in the width direction or biaxial direction by a tenter. Thereby, a film having further excellent flatness can be obtained.
- the arithmetic average roughness Ra (JIS B0601: 2001) of the hard coat layer is preferably in the range of 2 to 100 nm, particularly preferably in the range of 5 to 80 nm.
- the effects of the present invention can be suitably obtained even after a more severe vibration test.
- the height of the protrusion shape for obtaining the arithmetic average roughness Ra is preferably in the range of 2 nm to 4 ⁇ m.
- the width of the protrusion shape is in the range of 50 nm to 300 ⁇ m, preferably in the range of 50 nm to 100 ⁇ m.
- the 10-point average roughness Rz of the hard coat layer is 10 times or less of the centerline average roughness Ra, and the average mountain-valley distance Sm is preferably 5 to 150 ⁇ m, more preferably 20 to 100 ⁇ m, and the height of the protrusion from the deepest part of the unevenness Is preferably 0.5 ⁇ m or less, a standard deviation of an average mountain-valley distance Sm based on the center line is 20 ⁇ m or less, and a surface with an inclination angle of 0 to 5 degrees is preferably 10% or more.
- Arithmetic average roughness Ra, Sm, and Rz described above are values measured with an optical interference surface roughness meter (manufactured by ZYGO, NewView) in accordance with JIS B0601: 2001.
- the haze of the hard coat film is preferably in the range of 0.2 to 10% in view of visibility when used in an image display device.
- the haze can be measured according to JIS-K7105 and JIS K7136.
- the hard coat film of the present invention has a pencil hardness, which is an index of hardness, of HB or more, more preferably H or more. If it is more than HB, it is hard to be damaged in the polarizing plate forming step.
- the pencil hardness is determined by conditioning the prepared optical film at a temperature of 23 ° C. and a relative humidity of 55% for 2 hours or more, and then using a test pencil specified by JIS S6006 under a load of 500 g, It is the value which measured the functional layer in accordance with the pencil hardness evaluation method prescribed
- ⁇ Cellulose ester film> The cellulose ester film which is the base material of the hard coat film according to the present invention and the cellulose ester film bonded to the back side of the polarizing plate will be described.
- cellulose ester film examples include a triacetyl cellulose film, a cellulose acetate propionate film, a cellulose diacetate film, and a cellulose acetate butyrate film.
- the cellulose ester film may be used in combination with polyester resins such as polyethylene terephthalate and polyethylene naphthalate, polycarbonate resins, polyethylene resins, polypropylene resins, norbornene resins, fluororesins, and cycloolefin polymers.
- Examples of the commercially available cellulose ester film include Konica Minoltak KC8UX, KC4UX, KC8UY, KC4UY, KC6UA, KC4UA, KC4UE, and KC4UZ (manufactured by Konica Minolta Advanced Layer Co., Ltd.).
- the refractive index of the cellulose ester film is preferably 1.45 to 1.55.
- the refractive index can be measured according to JIS K7142-2008.
- the cellulose ester resin (hereinafter also referred to as cellulose ester) is preferably a lower fatty acid ester of cellulose.
- the lower fatty acid in the lower fatty acid ester of cellulose means a fatty acid having 6 or less carbon atoms.
- mixed fatty acid esters such as cellulose acetate butyrate can be used.
- the lower fatty acid esters of cellulose particularly preferably used are cellulose diacetate, cellulose triacetate, and cellulose acetate propionate. These cellulose esters can be used alone or in combination.
- cellulose diacetate an average degree of acetylation (bound acetic acid amount) in the range of 51.0 to 56.0% is preferably used.
- Commercially available products include L20, L30, L40, and L50 manufactured by Daicel Corporation, and Ca398-3, Ca398-6, Ca398-10, Ca398-30, and Ca394-60S manufactured by Eastman Chemical Japan Co., Ltd. .
- the cellulose triacetate preferably has an average degree of acetylation (bound acetic acid amount) of 54.0 to 62.5%, and more preferably cellulose triacetate having an average degree of acetylation of 58.0 to 62.5%. is there.
- cellulose triacetate A having a number average molecular weight (Mn) of 125,000 or more and less than 155000, a weight average molecular weight (Mw) of 265,000 or more and less than 310,000, and Mw / Mn in the range of 1.9 to 2.1,
- the degree of acetyl group substitution is in the range of 2.75 to 2.90
- the number average molecular weight (Mn) is from 155,000 to less than 180,000
- Mw is from 290000 to less than 360,000
- Mw / Mn is from 1.8 to 2.0. It is preferable to contain cellulose triacetate B in the range.
- Cellulose acetate propionate has an acyl group having 2 to 4 carbon atoms as a substituent, and when the substitution degree of the acetyl group is X and the substitution degree of the propionyl group is Y, the following formulas (I) and ( Those satisfying II) are preferred.
- Formula (II) 0 ⁇ X ⁇ 2.5 it is preferable that 1.9 ⁇ X ⁇ 2.5 and 0.1 ⁇ Y ⁇ 0.9.
- the method for measuring the degree of substitution of the acyl group can be measured according to ASTM-D817-96.
- the number average molecular weight (Mn) and molecular weight distribution (Mw) of cellulose ester can be measured using high performance liquid chromatography.
- the measurement conditions are as follows.
- thermoplastic acrylic resin The cellulose ester film may be used in combination with a thermoplastic acrylic resin.
- Acrylic resin includes methacrylic resin.
- the acrylic resin is not particularly limited, but is preferably composed of 50 to 99% by mass of methyl methacrylate units and 1 to 50% by mass of other monomer units copolymerizable therewith.
- Examples of other copolymerizable monomers include alkyl methacrylates having 2 to 18 alkyl carbon atoms, alkyl acrylates having 1 to 18 carbon atoms, alkyl acrylates such as acrylic acid and methacrylic acid.
- Unsaturated group-containing divalent carboxylic acids such as saturated acid, maleic acid, fumaric acid and itaconic acid, aromatic vinyl compounds such as styrene and ⁇ -methylstyrene, ⁇ , ⁇ -unsaturated nitriles such as acrylonitrile and methacrylonitrile, Examples thereof include maleic anhydride, maleimide, N-substituted maleimide, and glutaric anhydride. These may be used alone or in combination of two or more.
- methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, s-butyl acrylate, 2-ethylhexyl acrylate, and the like are preferable from the viewpoint of thermal decomposition resistance and fluidity of the copolymer.
- -Butyl acrylate is particularly preferably used.
- the weight average molecular weight (Mw) is preferably 80,000 to 500,000, more preferably 110,000 to 500,000.
- the weight average molecular weight of the acrylic resin can be measured by gel permeation chromatography.
- Commercially available acrylic resins include, for example, Delpet 60N, 80N (Asahi Kasei Chemicals Co., Ltd.), Dianal BR52, BR80, BR83, BR85, BR88 (Mitsubishi Rayon Co., Ltd.), KT75 (Electrochemical Industry Co., Ltd.) )) And the like. Two or more acrylic resins can be used in combination.
- the cellulose ester film according to the present invention has, for example, acrylic particles, silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, kaolin, talc, calcined calcium silicate, and hydrated calcium silicate in order to improve handleability. It is preferable to contain a matting agent such as inorganic fine particles such as aluminum silicate, magnesium silicate and calcium phosphate and a crosslinked polymer.
- the acrylic particles are not particularly limited, but are preferably multi-layered acrylic granular composites. Among these, silicon dioxide is preferable in that the haze of the cellulose ester film can be reduced.
- the primary average particle diameter of the fine particles is preferably 20 nm or less, more preferably in the range of 5 to 16 nm, and particularly preferably in the range of 5 to 12 nm.
- the cellulose acetate film according to the present invention preferably contains an ester or sugar ester represented by the following general formula (X) from the viewpoint of improving the dimensional stability performance under environmental changes.
- an ester or sugar ester represented by the following general formula (X) will be described.
- B is a hydroxy group or carboxylic acid residue
- G is an alkylene glycol residue having 2 to 12 carbon atoms, an aryl glycol residue having 6 to 12 carbon atoms, or an oxyalkylene glycol residue having 4 to 12 carbon atoms.
- the alkylene glycol component having 2 to 12 carbon atoms includes ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,2-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 2,2-diethyl-1,3-propanediol (3,3-dimethylolpentane), 2-n-butyl-2-ethyl-1,3-propanediol (3,3-dimethylolpentane), 2-n-butyl-2-ethyl-1,3-propanediol (3,3-dimethylolpentane), 2-n-butyl-2-ethyl-1,3-propan
- alkylene glycols having 2 to 12 carbon atoms are particularly preferable because of excellent compatibility with cellulose acetate.
- aryl glycol component having 6 to 12 carbon atoms include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol, and the like. These glycols can be used alone or as a mixture of two or more.
- Examples of the oxyalkylene glycol component having 4 to 12 carbon atoms include diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, and tripropylene glycol. These glycols may be used alone or as a mixture of two or more.
- Can be used as Examples of the alkylene dicarboxylic acid component having 4 to 12 carbon atoms include succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, and the like. Used as a mixture of seeds and more.
- arylene dicarboxylic acid component having 6 to 12 carbon atoms examples include phthalic acid, terephthalic acid, isophthalic acid, 1,5-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, and the like.
- Specific examples of the compound represented by formula (X) (compound X-1 to compound X-17) are shown below, but are not limited thereto.
- the sugar ester is an ester other than cellulose ester, and is a compound obtained by esterifying all or part of the OH group of a sugar such as the following monosaccharide, disaccharide, trisaccharide or oligosaccharide.
- sugar examples include glucose, galactose, mannose, fructose, xylose, arabinose, lactose, sucrose, nystose, 1F-fructosyl nystose, stachyose, maltitol, lactitol, lactulose, cellobiose, maltose, cellotriose, maltotriose, raffinose And kestose.
- gentiobiose, gentiotriose, gentiotetraose, xylotriose, galactosyl sucrose, and the like are also included.
- compounds having a furanose structure and / or a pyranose structure are particularly preferable.
- sucrose, kestose, nystose, 1F-fructosyl nystose, stachyose and the like are preferable, and sucrose is more preferable.
- oligosaccharides maltooligosaccharides, isomaltooligosaccharides, fructooligosaccharides, galactooligosaccharides, and xylo-oligosaccharides can also be preferably used.
- the monocarboxylic acid used for esterifying the sugar is not particularly limited, and known aliphatic monocarboxylic acid, alicyclic monocarboxylic acid, aromatic monocarboxylic acid and the like can be used.
- the carboxylic acid to be used may be one kind or a mixture of two or more kinds.
- Preferred aliphatic monocarboxylic acids include acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, 2-ethyl-hexanecarboxylic acid, undecylic acid, lauric acid , Saturated fatty acids such as tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, heptacosanoic acid, montanic acid, melicic acid, and laccelic acid, Examples include unsaturated fatty acids such as undecylenic acid, oleic acid, sorbic acid, linoleic acid, linolenic acid, arachidonic acid and oc
- Examples of preferred alicyclic monocarboxylic acids include cyclopentane carboxylic acid, cyclohexane carboxylic acid, cyclooctane carboxylic acid, or derivatives thereof.
- Examples of preferred aromatic monocarboxylic acids include benzoic acid, aromatic monocarboxylic acids having an alkyl group or alkoxy group introduced into the benzene ring of benzoic acid, cinnamic acid, benzylic acid, biphenylcarboxylic acid, naphthalenecarboxylic acid, tetralin
- An aromatic monocarboxylic acid having two or more benzene rings such as carboxylic acid, or a derivative thereof can be mentioned, and more specifically, xylic acid, hemelic acid, mesitylene acid, planicylic acid, ⁇ -isojurylic acid, Julylic acid, mesitic acid, ⁇ -isoduric acid, cumic acid, ⁇ -toluic acid, hydroatropic acid
- the sugar ester is preferably a compound represented by the general formula (Y). Below, the compound shown by general formula (Y) is demonstrated.
- R 1 ⁇ R 8 is a hydrogen atom, a substituted or unsubstituted alkylcarbonyl group having 2 to 22 carbon atoms, or a substituted or unsubstituted arylcarbonyl group having 2 to 22 carbon atoms
- R 1 R 8 may be the same or different.
- the compounds represented by formula (Y) are shown below in more detail (compound Y-1 to compound Y-23), but are not limited thereto. In the table below, when the average degree of substitution is less than 8.0, any one of R 1 to R 8 represents a hydrogen atom.
- the substitution degree distribution can be adjusted to the desired substitution degree by adjusting the esterification reaction time or mixing compounds with different substitution degrees.
- the ester or sugar ester represented by the general formula (X) is preferably contained in the cellulose acetate film in the range of 1 to 30% by mass, more preferably in the range of 5 to 25% by mass. It is particularly preferable that the content be in the range of ⁇ 20% by mass.
- the cellulose acetate film according to the present invention may contain a plasticizer as necessary.
- the plasticizer is not particularly limited, but is a polyvalent carboxylic ester plasticizer, glycolate plasticizer, phthalate ester plasticizer, phosphate ester plasticizer, and polyhydric alcohol ester plasticizer, acrylic.
- a plasticizer etc. are mentioned.
- an acrylic plasticizer is preferable from the point which can control a cellulose-ester film to the retardation value mentioned later.
- the polyhydric alcohol ester plasticizer is a plasticizer composed of an ester of a divalent or higher aliphatic polyhydric alcohol and a monocarboxylic acid, and preferably has an aromatic ring or a cycloalkyl ring in the molecule.
- a divalent to 20-valent aliphatic polyhydric alcohol ester is preferred.
- Preferable specific examples of the polyhydric alcohol ester plasticizer include compounds described in paragraphs [0058] to [0061] of JP-A-2006-113239.
- the glycolate plasticizer is not particularly limited, but alkylphthalylalkyl glycolates can be preferably used.
- alkyl phthalyl alkyl glycolates include methyl phthalyl methyl glycolate, ethyl phthalyl ethyl glycolate, propyl phthalyl propyl glycolate, butyl phthalyl butyl glycolate, octyl phthalyl octyl glycolate, methyl phthalyl ethyl Glycolate, ethyl phthalyl methyl glycolate, ethyl phthalyl propyl glycolate, methyl phthalyl butyl glycolate, ethyl phthalyl butyl glycolate, butyl phthalyl methyl glycolate, butyl phthalyl ethyl glycolate, propyl phthalyl butyl glycol Butyl phthalyl propyl glycolate, methyl phthalyl octyl
- phthalate ester plasticizer examples include diethyl phthalate, dimethoxyethyl phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, and dicyclohexyl terephthalate.
- phosphate ester plasticizer examples include triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, diphenyl biphenyl phosphate, trioctyl phosphate, tributyl phosphate, and the like.
- the polycarboxylic acid ester plasticizer is a compound composed of an ester of a divalent or higher, preferably a divalent to 20-valent polyvalent carboxylic acid and an alcohol.
- Specific examples include triethyl citrate, tributyl citrate, acetyl triethyl citrate (ATEC), acetyl tributyl citrate (ATBC), benzoyl tributyl citrate, acetyl triphenyl citrate, acetyl tribenzyl citrate, dibutyl tartrate, tartaric acid
- examples include, but are not limited to, diacetyldibutyl, tributyl trimellitic acid, tetrabutyl pyromellitic acid, and the like.
- the acrylic plasticizer is preferably an acrylic polymer, and the acrylic polymer is preferably a homopolymer or copolymer of acrylic acid or alkyl methacrylate.
- the acrylate monomer include methyl acrylate, ethyl acrylate, propyl acrylate (i-, n-), butyl acrylate (n-, i-, s-, t-), pentyl acrylate ( n-, i-, s-), hexyl acrylate (n-, i-), heptyl acrylate (n-, i-), octyl acrylate (n-, i-), nonyl acrylate (n-, i-), myristyl acrylate (n-, i-), acrylic acid (2-ethylhexyl), acrylic acid ( ⁇ -caprolactone), acrylic acid (2-hydroxyethyl), acrylic acid (2-hydroxypropyl), acrylic Acid (3-hydroxypropyl), acrylic
- the acrylic polymer is a homopolymer or copolymer of the above-mentioned monomers, but the acrylic acid methyl ester monomer unit preferably has 30% by mass or more, and the methacrylic acid methyl ester monomer unit has 40% by mass or more. preferable. In particular, a homopolymer of methyl acrylate or methyl methacrylate is preferred.
- the amount used is preferably 1 to 50% by mass with respect to the cellulose acetate, and preferably 5 to 35% by mass. It is more preferable that the content be within the range of 5 to 25% by mass.
- the cellulose acetate film according to the present invention may contain an ultraviolet absorber. Since the ultraviolet absorber absorbs ultraviolet rays of 400 nm or less, durability can be improved. In particular, the ultraviolet absorber preferably has a transmittance of 10% or less at a wavelength of 370 nm, more preferably 5% or less, and still more preferably 2% or less. Specific examples of the ultraviolet absorber are not particularly limited. For example, oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, triazine compounds, nickel complex salts, inorganic powders. Examples include the body.
- 5-chloro-2- (3,5-di-sec-butyl-2-hydroxylphenyl) -2H-benzotriazole, (2-2H-benzotriazol-2-yl) -6 -(Linear and side chain dodecyl) -4-methylphenol, 2-hydroxy-4-benzyloxybenzophenone, 2,4-benzyloxybenzophenone, and the like can be used.
- Commercially available products may be used.
- TINUVIN such as TINUVIN 109, TINUVIN 171, TINUVIN 234, TINUVIN 326, TINUVIN 327, and TINUVIN 328 manufactured by BASF Japan Ltd. can be preferably used.
- Preferably used ultraviolet absorbers are benzotriazole ultraviolet absorbers, benzophenone ultraviolet absorbers, and triazine ultraviolet absorbers, and particularly preferably benzotriazole ultraviolet absorbers and benzophenone ultraviolet absorbers.
- a discotic compound such as a compound having a 1,3,5 triazine ring is also preferably used as an ultraviolet absorber.
- a polymer UV absorber can be preferably used, and a polymer type UV absorber is particularly preferably used.
- TINUVIN 109 octyl-3- [3-tert-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazole-2-) manufactured by BASF Japan Ltd., which is a commercial product, is available.
- TINUVIN 400 (- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) —manufactured by BASF Japan Ltd.— Reaction product of 5-hydroxyphenyl and oxirane), TINUVIN 460 (2,4-bis [2-hydroxy-4-butoxyphenyl] -6- (2,4-dibutoxyphenyl) -1,3-5 Triazine), TINUVIN 405 (2- (2,4-dihydroxyphenyl) -4,6-bis- (2,4-dimethylphenyl) -1,3,5-triazine and (2-ethylhexyl) -glycidic acid ester Reaction products) and the like.
- the ultraviolet absorber is added by dissolving the ultraviolet absorber in an alcohol, such as methanol, ethanol, butanol or the like, an organic solvent such as methylene chloride, methyl acetate, acetone, dioxolane, or a mixed solvent thereof, and then becomes a film substrate. It may be added to the resin solution (dope) or directly during the dope composition.
- an organic solvent such as methylene chloride, methyl acetate, acetone, dioxolane, or a mixed solvent thereof.
- a dissolver or a sand mill is used in the organic solvent and cellulose acetate to disperse and then added to the dope.
- the amount of the ultraviolet absorber used is preferably in the range of 0.5 to 10% by mass, more preferably in the range of 0.6 to 4% by mass with respect to the cellulose acetate film.
- the cellulose acetate film according to the present invention may further contain an antioxidant (deterioration inhibitor).
- the antioxidant has a role of delaying or preventing the cellulose acetate film from being decomposed by a residual solvent amount of halogen in the cellulose acetate film, phosphoric acid of a phosphoric acid plasticizer, or the like.
- hindered phenol compounds are preferably used.
- 2,6-di-t-butyl-p-cresol, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl) are used.
- the cellulose ester film preferably has a defect of 5 ⁇ m or more in diameter of 1 piece / 10 cm square or less. More preferably, it is 0.5 piece / 10 cm square or less, more preferably 0.1 piece / 10 cm square or less.
- the diameter of the defect indicates the diameter when the defect is circular, and when the defect is not circular, the range of the defect is determined by observing with a microscope by the following method, and the maximum diameter (diameter of circumscribed circle) is determined.
- the range of the defect is the size of the shadow when the defect is observed with the transmitted light of the differential interference microscope when the defect is a bubble or a foreign object.
- the defect is a change in the surface shape such as transfer of a roller scratch or an abrasion, the size can be confirmed by observing the defect with reflected light of a differential interference microscope.
- the film When the number of defects is more than 1/10 cm square, for example, when a tension is applied to the film during processing in a later process, the film may be broken with the defect as a starting point and productivity may be reduced. Moreover, when the diameter of a defect becomes 5 micrometers or more, it can confirm visually by polarizing plate observation etc., and when used as an optical member, a bright spot may arise.
- the coating film may not be formed uniformly, resulting in a defect (missing coating).
- the defect is a void in the film (foaming defect) generated due to the rapid evaporation of the solvent in the drying process of the solution casting, a foreign matter in the film forming stock solution, or a foreign matter mixed in the film forming. This refers to foreign matter (foreign matter defect) in the film.
- the base film preferably has a breaking elongation in at least one direction of 10% or more, more preferably 20% or more, in the measurement based on JIS-K7127-1999.
- the upper limit of the elongation at break is not particularly limited, but is practically about 250%. In order to increase the elongation at break, it is effective to suppress defects in the film caused by foreign matter and foaming.
- the cellulose ester film preferably has a total light transmittance of 90% or more, more preferably 93% or more. Moreover, as a realistic upper limit, it is about 99%.
- the haze value is preferably 2% or less, more preferably 1.5% or less.
- the total light transmittance and haze value can be measured according to JIS K7361 and JIS K7136.
- the in-plane retardation value Ro of the cellulose ester film is preferably in the range of 0 to 5 nm, and the retardation value Rth in the thickness direction is preferably in the range of ⁇ 10 to 10 nm. Further, Rth is more preferably within a range of ⁇ 5 to 5 nm.
- Ro and Rth are values defined by the following formulas (i) and (ii).
- KOBRA-21ADH manufactured by Oji Scientific Instruments.
- Retardation can be adjusted by the kind and addition amount of a plasticizer mentioned above, the film thickness of a cellulose ester film, stretching conditions, and the like.
- a production method such as an inflation method, a T-die method, a calendar method, a cutting method, a casting method, an emulsion method, a hot press method, or the like can be used.
- Organic solvent The organic solvent useful for forming a resin solution (dope composition) when a cellulose ester film is produced by a solution casting method is limited as long as it dissolves a cellulose ester resin and other additives at the same time. Can be used without any problem.
- a chlorinated organic solvent methylene chloride
- a non-chlorinated organic solvent methyl acetate, ethyl acetate, amyl acetate, acetone, tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, cyclohexanone, ethyl formate, 2,2,2-trifluoroethanol, 2,2,3,3-hexafluoro-1-propanol, 1,3-difluoro-2-propanol, 1,1,1,3,3,3-hexafluoro- 2-methyl-2-propanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 2,2,3,3,3-pentafluoro-1-propanol, nitroethane, methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol, tert-butan
- Can, methylene chloride, methyl acetate, ethyl acetate, may be used preferably acetone.
- the solvent is preferably a dope composition in which cellulose ester resin and other additives are dissolved within a total range of 15 to 45% by mass.
- solution casting film forming method a step of preparing a dope by dissolving a resin and an additive in a solvent, a step of casting the dope on a belt-shaped or drum-shaped metal support, and drying the cast dope as a web It is carried out by a step of peeling off from the metal support, a step of stretching or maintaining the width, a step of further drying, and a step of winding up the finished cellulose ester film.
- a stainless steel belt or a drum whose surface is plated with a casting is preferably used.
- the cast width can be in the range of 1-4m.
- the surface temperature of the metal support in the casting step is set to ⁇ 50 ° C. to below the temperature at which the solvent boils and does not foam. A higher temperature is preferred because the web can be dried faster, but if it is too high, the web may foam or the flatness may deteriorate.
- a preferable support temperature is appropriately determined in the range of 0 to 100 ° C., and more preferably in the range of 5 to 30 ° C.
- the method for controlling the temperature of the metal support is not particularly limited, and there are a method of blowing warm air or cold air, and a method of contacting hot water with the back side of the metal support. It is preferable to use warm water because heat transfer is performed efficiently, so that the time until the temperature of the metal support becomes constant is short.
- the amount of residual solvent when peeling the web from the metal support is preferably in the range of 10 to 150% by mass, more preferably 20 to 40% by mass.
- the range is or a range of 60 to 130% by mass, and particularly preferably a range of 20 to 30% by mass or a range of 70 to 120% by mass.
- the amount of residual solvent is defined by the following formula.
- Residual solvent amount (% by mass) ⁇ (MN) / N ⁇ ⁇ 100 Note that M is the mass of a sample collected during or after the production of the web or film, and N is the mass after heating M at 115 ° C. for 1 hour.
- the web is peeled off from the metal support and dried, and the residual solvent amount is preferably 1% by mass or less, more preferably 0.1% by mass or less, particularly preferably. It is in the range of 0 to 0.01% by mass.
- a roller drying method (a method in which webs are alternately passed through a plurality of upper and lower rollers) and a tenter method for drying while transporting the web are employed.
- the film can be sequentially or simultaneously stretched in the longitudinal direction (MD direction) and the lateral direction (TD direction).
- the draw ratios in the biaxial directions perpendicular to each other are preferably finally in the range of 1.0 to 2.0 times in the MD direction and in the range of 1.05 to 2.0 times in the TD direction. It is preferable to carry out in the range of 1.0 to 1.5 times in the direction and 1.05 to 2.0 times in the TD direction.
- a method in which a circumferential speed difference is applied to a plurality of rollers, and the roller circumferential speed difference is used to stretch in the MD direction. Both ends of the web are fixed with clips and pins, and the interval between the clips and pins is widened in the traveling direction.
- a method of stretching in the MD direction a method of stretching in the transverse direction and stretching in the TD direction, a method of stretching the MD direction and the TD direction at the same time, and stretching in both directions.
- a tenter it may be a pin tenter or a clip tenter.
- the film transport tension in the film forming process such as a tenter depends on the temperature, but is preferably in the range of 120 to 200 N / m, and more preferably in the range of 140 to 200 N / m. A range of 140 to 160 N / m is most preferred.
- the range is from Tg-5) to (Tg + 20) ° C.
- the Tg of the cellulose ester film can be controlled by the material type constituting the film and the ratio of the constituting materials.
- the Tg when the cellulose ester film is dried is preferably 110 ° C. or higher, more preferably 120 ° C. or higher. Especially preferably, it is 150 degreeC or more.
- the glass transition temperature is preferably 190 ° C. or lower, more preferably 170 ° C. or lower.
- the Tg of the cellulose ester film can be determined by the method described in JIS K7121.
- the stretching temperature is preferably 150 ° C. or more and the stretching ratio is 1.15 times or more because the surface is appropriately roughened. Roughening the surface of the cellulose ester film is preferable because it improves slipperiness and improves surface processability.
- the cellulose ester film may be formed by a melt casting film forming method.
- a composition containing other additives such as a cellulose ester resin and a plasticizer is heated and melted to a temperature showing fluidity, and then a melt containing the fluid cellulose ester is cast. To do.
- melt extrusion method is preferable from the viewpoint of mechanical strength and surface accuracy.
- a plurality of raw materials used for melt extrusion are usually preferably kneaded and pelletized in advance.
- Pelletization may be performed by a known method. For example, dry cellulose ester, plasticizer, and other additives are fed to an extruder using a feeder, kneaded using a single or twin screw extruder, and extruded from a die into a strand. It can be done by water cooling or air cooling and cutting.
- Additives may be mixed before being supplied to the extruder, or may be supplied by individual feeders.
- a small amount of additives such as particles and antioxidants are preferably mixed in advance in order to mix uniformly.
- the extruder is preferably processed at a temperature as low as possible so that it can be pelletized so that the shearing force is suppressed and the resin does not deteriorate (molecular weight reduction, coloring, gel formation, etc.).
- a temperature as low as possible so that it can be pelletized so that the shearing force is suppressed and the resin does not deteriorate (molecular weight reduction, coloring, gel formation, etc.).
- the resin does not deteriorate (molecular weight reduction, coloring, gel formation, etc.).
- a twin screw extruder it is preferable to rotate in the same direction using a deep groove type screw. From the uniformity of kneading, the meshing type is preferable.
- Film formation is performed using the pellets obtained as described above.
- the raw material powder can be directly fed to the extruder by a feeder without being pelletized to form a film as it is.
- the pellets are melted at a temperature of about 200 to 300 ° C., filtered through a leaf disk type filter or the like to remove foreign matter, and then formed into a film from a T die.
- the cellulose ester film is formed by casting, nipping the film with a cooling roller and an elastic touch roller, and solidifying the film on the cooling roller.
- the extrusion flow rate is preferably adjusted stably by introducing a gear pump or the like.
- a stainless fiber sintered filter is preferably used as a filter used for removing foreign substances.
- the stainless steel fiber sintered filter is a united stainless steel fiber body that is intricately intertwined and compressed, and the contact points are sintered and integrated. The density of the fiber is changed depending on the thickness of the fiber and the amount of compression, and the filtration accuracy is improved. Can be adjusted.
- Additives such as plasticizers and particles may be mixed with the resin in advance, or may be kneaded in the middle of the extruder. In order to add uniformly, it is preferable to use a mixing apparatus such as a static mixer.
- the cellulose ester film temperature on the touch roller side when the cellulose ester film is nipped between the cooling roller and the elastic touch roller is preferably set to Tg or more (Tg + 110 ° C.) or less of the film.
- a known roller can be used as the roller having an elastic surface used for such purposes.
- the elastic touch roller is also called a pinching rotary body.
- a commercially available one can be used as the elastic touch roller.
- the cellulose ester film obtained as described above is stretched by the stretching operation after passing through the step of contacting the cooling roller.
- the stretching method a known roller stretching machine or tenter can be preferably used.
- the stretching temperature is usually preferably in the temperature range of Tg to (Tg + 60) ° C. of the resin constituting the film.
- the end Before winding, the end may be slit and cut to the product width, and knurled (embossed) may be applied to both ends to prevent sticking and scratching during winding.
- the knurling method can be performed by heating or pressurizing using a metal ring having an uneven pattern on the side surface. Since the cellulose ester film is deformed and cannot be used as a product, the clip holding portions at both ends of the film are usually cut out and reused.
- the film thickness of the cellulose ester film in the present invention is characterized by being in the range of 5 to 34 ⁇ m.
- the effect expression of the present invention can be obtained in a cellulose ester film having a film thickness in this range. Preferably, it is in the range of 10 to 30 ⁇ m.
- the width of the cellulose ester film is preferably in the range of 1 to 4 m. If it exceeds 4 m, conveyance becomes difficult.
- the length of the cellulose ester film is preferably in the range of 500 to 10,000 m, more preferably in the range of 1000 to 8000 m. By setting it as the range of the said length, it is excellent in the processability in application
- the arithmetic average roughness Ra of the cellulose ester film is preferably in the range of 2 to 10 nm, more preferably in the range of 2 to 5 nm.
- the arithmetic average roughness Ra can be measured according to JIS B0601: 1994.
- the contact angle with water before alkali treatment of the cellulose ester film is generally in the range of 40 to 80 °, and preferably in the range of 50 to 70 °.
- the contact angle with water after the alkali treatment is generally in the range of 10 to 60 °, preferably in the range of 20 to 60 °, although it depends on the alkali treatment conditions.
- the water contact angle is a value measured according to the method described in the method for measuring the water contact angle of the hard coat layer.
- the hard coat layer has a reduced contact angle with water due to the alkali treatment, and the contact angle with water with the cellulose ester film approaches, resulting in a laminated state of the hydrophilic layers and the expression effect of the present invention is obtained. ing.
- the cellulose ester film is immersed in an alkali solution, washed with water and dried. Further, after the alkali treatment, neutralization in an acidic water step may be performed, followed by washing with water and drying.
- the alkaline solution examples include potassium hydroxide solution and sodium hydroxide solution, and the concentration of hydroxide ions is preferably in the range of 0.1 to 5 mol / L, preferably 0.5 mol / L to 3 mol / L. More preferably, it is in the range. Furthermore, the temperature of the alkaline solution is preferably in the range of 25 to 90 ° C, more preferably in the range of 40 to 70 ° C. The alkali treatment time is in the range of 5 seconds to 5 minutes, preferably in the range of 30 seconds to 3 minutes.
- the hard coat film of the present invention can be provided with other layers such as an antireflection layer and a conductive layer.
- the hard coat film according to the present invention can be used as an antireflection film having an external light antireflection function by coating an antireflection layer on the hard coat layer.
- the antireflection layer is preferably laminated in consideration of the refractive index, the film thickness, the number of layers, the layer order, and the like so that the reflectance is reduced by optical interference.
- the antireflection layer is composed of a low refractive index layer having a lower refractive index than the protective film as the support, or a combination of a high refractive index layer and a low refractive index layer having a higher refractive index than the protective film as the support.
- it is.
- it is an antireflection layer composed of three or more refractive index layers. Three layers having different refractive indexes from the support side are divided into medium refractive index layers (high refractive index layers having a higher refractive index than the support).
- an antireflection layer having a layer structure of four or more layers in which two or more high refractive index layers and two or more low refractive index layers are alternately laminated is also preferably used.
- the layer structure the following structure is conceivable, but is not limited thereto.
- the low refractive index layer preferably contains silica-based fine particles, and the refractive index is preferably in the range of 1.30 to 1.45 when measured at 23 °
- the film thickness of the low refractive index layer is preferably in the range of 5 nm to 0.5 ⁇ m, more preferably in the range of 10 nm to 0.3 ⁇ m, and in the range of 30 nm to 0.2 ⁇ m. Most preferred.
- the composition for forming a low refractive index layer preferably contains at least one kind of particles having an outer shell layer and porous or hollow inside as silica-based fine particles.
- the particles having the outer shell layer and porous or hollow inside are preferably hollow silica-based fine particles.
- composition for forming a low refractive index layer may contain an organosilicon compound represented by the following general formula (OSi-1) or a hydrolyzate thereof, or a polycondensate thereof.
- OSi-1 organosilicon compound represented by the following general formula (OSi-1) or a hydrolyzate thereof, or a polycondensate thereof.
- R represents an alkyl group having 1 to 4 carbon atoms. Specifically, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane and the like are preferably used.
- a solvent and if necessary, a silane coupling agent, a curing agent, a surfactant and the like may be added. Further, it may contain a thermosetting and / or photocurable compound mainly containing a fluorine-containing compound containing a fluorine atom in a range of 35 to 80% by mass and containing a crosslinkable or polymerizable functional group. Specifically, a fluorine-containing polymer or a fluorine-containing sol-gel compound is used.
- fluorine-containing polymer examples include hydrolysates and dehydration condensates of perfluoroalkyl group-containing silane compounds [eg (heptadecafluoro-1,1,2,2-tetrahydrodecyl) triethoxysilane], and fluorine-containing monomers. Examples thereof include fluorine-containing copolymers having units and cross-linking reactive units as constituent units.
- the refractive index of the high refractive index layer is preferably adjusted to a range of 1.4 to 2.2 by measuring at 23 ° C. and a wavelength of 550 nm.
- the thickness of the high refractive index layer is preferably 5 nm to 1 ⁇ m, more preferably 10 nm to 0.2 ⁇ m, and most preferably 30 nm to 0.1 ⁇ m.
- the means for adjusting the refractive index can be achieved by adding metal oxide fine particles and the like.
- the metal oxide fine particles used preferably have a refractive index of 1.80 to 2.60, more preferably 1.85 to 2.50.
- the kind of metal oxide fine particles is not particularly limited, and Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P and S A metal oxide having at least one element selected from can be used.
- a conductive layer may be formed on the hard coat layer.
- a generally well-known conductive material can be used.
- metal oxides such as indium oxide, tin oxide, indium tin oxide, gold, silver, and palladium can be used. These can be formed as a thin film on the hard coat film by vacuum deposition, sputtering, ion plating, solution coating, or the like.
- organic conductive material which is the above-described ⁇ -conjugated conductive polymer.
- a conductive material that is excellent in transparency and conductivity, and that has a main component of any one of indium oxide, tin oxide, and indium tin oxide obtained at a relatively low cost can be suitably used.
- the thickness of the conductive layer varies depending on the material to be applied, it cannot be said unconditionally.
- the surface resistivity is 1000 ⁇ or less, preferably 500 ⁇ or less, and considering the economy, A range of 10 nm or more, preferably 20 nm or more and 80 nm or less, preferably 70 nm or less is suitable. In such a thin film, visible light interference fringes due to uneven thickness of the conductive layer are unlikely to occur.
- the polarizing plate can be produced by a general method.
- the hard coat film of the present invention is subjected to alkali saponification treatment, and the treated hard coat film is attached to at least one surface of a polarizing film prepared by immersing and stretching in an iodine solution using a completely saponified polyvinyl alcohol aqueous solution. It is preferable to match.
- the other surface may be the hard coat film or the cellulose ester film described above.
- the film thickness of the cellulose ester film used on the other side is preferably in the range of 5 to 34 ⁇ m from the viewpoint of adjusting smoothness and curl balance and further enhancing the effect of preventing winding deviation.
- KC8UX, KC4UX, KC4UY, KC8UY, KC6UA, KC4UA, KC4UE, KC4CZ, KC8UCR, KC4FR manufactured by Konica Minolta Advanced Layer Co., Ltd.
- Arton Film manufactured by JSR Corporation
- the polarizing film which is the main component of the polarizing plate, is an element that transmits only light having a polarization plane in a certain direction.
- a typical polarizing film known at present is a polyvinyl alcohol polarizing film, which is a polyvinyl alcohol film.
- polarizing film a polyvinyl alcohol aqueous solution is formed and dyed by uniaxial stretching or dyeing, or after uniaxial stretching after dyeing, a film subjected to durability treatment with a boron compound is preferably used.
- the thickness of the polarizing film is in the range of 5 to 30 ⁇ m, preferably in the range of 8 to 15 ⁇ m.
- one side of the hard coat film according to the present invention is bonded to form a polarizing plate. It is preferably bonded with an aqueous adhesive mainly composed of completely saponified polyvinyl alcohol or the like.
- the pressure-sensitive adhesive layer used on one side of the film to be bonded to the substrate of the liquid crystal cell is preferably optically transparent and exhibits moderate viscoelasticity and adhesive properties.
- the adhesive layer include adhesives or adhesives such as acrylic copolymers, epoxy resins, polyurethanes, silicone polymers, polyethers, butyral resins, polyamide resins, polyvinyl alcohol resins, and synthetic rubbers.
- a film such as a drying method, a chemical curing method, a thermal curing method, a thermal melting method, a photocuring method, or the like can be formed and cured using a polymer such as the above.
- the acrylic copolymer can be preferably used because it is most easy to control the physical properties of the adhesive and is excellent in transparency, weather resistance, durability and the like.
- the thickness of the air layer held between the layers when the hard coat film of the present invention, the cellulose ester film according to the present invention, or the polarizing plate using the hard coat film of the present invention is wound in a roll shape is 0.
- the range of 5 to 10 ⁇ m is preferable, and the range of 1 to 5 ⁇ m is more preferable.
- D represents the winding diameter
- d represents the winding core diameter
- L represents the winding length
- t represents the thickness of the film.
- a method for winding a hard coat film, etc. provides a roller that the film touches in front of the winding shaft, and the film touches when winding the film or winding the film on the winding shaft.
- a method in which the film is wound while the roller is gradually separated at a constant distance (gap winding), a film winding part that winds the film around the core by rotating the core, and the film width on the core For example, an oscillating winding method in which winding is performed while periodically deviating in a certain range in a direction can be used.
- the thickness of the air layer can be controlled by adjusting the winding conditions such as the tension condition during winding.
- the hard coat film of this invention is preferable at the point by which the performance excellent in visibility (clearness) is exhibited by using it for an image display apparatus.
- an image display device a reflection type, a transmission type, a transflective type liquid crystal display device, a liquid crystal display device of various driving methods such as a TN type, STN type, OCB type, VA type, IPS type, ECB type, and a touch panel display device And organic EL display devices and plasma displays.
- a TN type STN type, OCB type, VA type, IPS type, ECB type
- organic EL display devices and plasma displays a touch panel display device
- the hard coat film of the present invention is used for a liquid crystal display device or a touch panel display device, it is preferable in terms of excellent visibility.
- FIG. 1 An example in the case of using the hard coat film of the present invention for a touch panel display device is shown in FIG.
- a conductive film 12 is formed on a hard coat film 11 (hereinafter referred to as double-sided hard coat film) 11 provided with a hard coat layer on both sides according to the present invention, and this is a glass substrate 13 on which a conductive film 15 is formed, By making the conductive layers face each other with a certain interval so that the conductive layers face each other, the resistive film type touch panel 10 can be configured. Electrodes (not shown) are arranged at the ends of the double-sided hard coat film 11 and the glass substrate 13 according to the present invention. The conductive film 12 comes into contact with the conductive film 15 on the glass substrate 13 by pressing the double-sided hard coat film 11 with a finger or a pen. The pressed position is detected by electrically detecting this contact through the electrode at the end. A dot-like spacer 14 is disposed on the conductive film 15 of the glass substrate 13 as necessary. Further, as shown in FIG. 2, the image display device 20 with an inner touch panel can be configured by mounting the touch panel 10 of FIG. 1 in the liquid crystal display panel.
- the hard coat film of the present invention is, for example, an inner touch panel as shown in FIG. 2 using a touch panel member under the upper surface side polarizing plate of a liquid crystal display device (upper surface side polarizing plate / liquid crystal cell / lower surface side polarizing plate configuration). It can also be used for a capacitive touch panel.
- the conductive film 12 preferably has an electrode pattern such as a lattice shape arranged at a predetermined pitch. The electrode pattern of the conductive film is such that after the conductive film is formed, the conductive film is masked with the electrode pattern, the electrode pattern is formed by alkali etching, or laser irradiation is performed to continuously pattern the conductive film. Can be provided.
- FIG. 3 shows an example of a schematic cross-sectional view in which the glass scattering prevention film for an image display device using the hard coat film of the present invention is used in the image display device.
- the image display device 30 includes an image display panel 31, a conductive glass substrate 33 disposed on the display unit (display surface) of the image display panel 31 via an adhesive layer 32, and a conductive glass substrate 33. It is comprised roughly from the glass scattering prevention film 41 for image display apparatuses stuck.
- the conductive glass substrate 33 includes a glass substrate 34 and a conductive film 35.
- the glass scattering prevention film 41 for an image display device is adhered to the glass substrate 34 with an adhesive layer 43.
- the glass scattering prevention film 41 for an image display device comprising the hard coat film 42 of the present invention has high adhesion to an adhesive or the like and does not need to be subjected to an easy adhesion treatment. Moreover, sufficient scattering prevention property can be obtained for the glass scattering prevention film. In addition, deformation and the like hardly occur after the durability test, and the flatness (visibility) is excellent.
- the hard coat film 42 preferably has a refractive index in the range of 1.45 to 1.55 at a wavelength of 589 nm measured in accordance with JIS K7142-2008.
- the pressure-sensitive adhesive layer 43 also preferably has a refractive index of 1.40 to 1.55 at a wavelength of 589 nm measured according to JIS K7142-2008, more preferably 1.45 to 1.52.
- the refractive index of the pressure-sensitive adhesive layer 43 can be adjusted by, for example, a method of increasing the refractive index by including an aromatic ring or a method of decreasing the refractive index by including a fluorine atom.
- the refractive index of the pressure-sensitive adhesive layer 43 and the glass scattering prevention film 41 for an image display device By making the refractive index of the pressure-sensitive adhesive layer 43 and the glass scattering prevention film 41 for an image display device within the above range, the refractive index when bonded to a glass substrate or the like is small, and the interference fringes are excellent.
- the thickness of the pressure-sensitive adhesive layer is preferably in the range of 5 to 30 ⁇ m, and more preferably in the range of 10 to 25 ⁇ m.
- an adhesive which comprises an adhesive layer an acrylic adhesive, a silicone adhesive, a urethane adhesive, a rubber adhesive, a polyester adhesive, etc. are mentioned. These pressure-sensitive adhesives may be emulsion type, solvent type, or solventless type. Among these pressure-sensitive adhesives, acrylic pressure-sensitive adhesives are preferable from the viewpoints of easy adhesion control and weather resistance.
- the acrylic pressure-sensitive adhesive is preferably a cross-linked acrylic resin having a weight average molecular weight in the range of 500 to 2,000,000, preferably in the range of 7,000 to 1,700,000.
- the aforementioned weight average molecular weight is a value in terms of polystyrene measured by a gel permeation chromatography (GPC) method.
- the acrylic resin contained in the acrylic adhesive a (meth) acrylic acid ester copolymer is used.
- the (meth) acrylic acid ester-based copolymer includes a (meth) acrylic acid ester in which the alkyl group of the ester moiety has 1 to 20 carbon atoms, a monomer having a functional group having active hydrogen, and, if desired, Copolymers with other monomers used are preferred.
- Examples of the (meth) acrylic acid ester having 1 to 20 carbon atoms in the alkyl group of the ester portion include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, Examples include isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and isooctyl (meth) acrylate. These may be used alone or in combination of two or more.
- Examples of monomers having a functional group having active hydrogen include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) (Meth) acrylic acid hydroxyalkyl esters such as acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, acrylamide, methacrylamide, N-methylacrylamide, N-methylmethacrylamide, N-methylol Acrylamides such as acrylamide and N-methylolmethacrylamide, monoalkylaminoalkyl (meth) acrylates such as methylaminoethyl (meth) acrylate and monoethylaminoethyl (meth) acrylate, Le acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, ethylenically unsaturated carboxylic acids such as citraconic acid
- the (meth) acrylic acid ester copolymer used as a resin component may be any of random, block, and graft copolymers in terms of the copolymerization form.
- the crosslinking agent used for the crosslinking treatment a polyisocyanate compound or an epoxy compound is preferably used.
- a crosslinking agent may be used individually by 1 type, and may be used in combination of 2 or more type. The amount used depends on the type of the crosslinking agent, but is usually in the range of 0.01 to 20 parts by mass, preferably 0.1 to 100 parts by mass of the solid content of the (meth) acrylate copolymer. It is in the range of ⁇ 10 parts by mass.
- a tackifier, antioxidant, ultraviolet absorber, light stabilizer, softener, silane coupling agent, filler and the like can be added to the acrylic pressure-sensitive adhesive.
- a protective film and a release sheet may be attached to the adhesive layer 43.
- the base material of the release sheet include polyethylene terephthalate, polyethylene, and polypropylene film.
- a release agent such as a fluorine resin, a silicone resin, or a long-chain alkyl group-containing carbamate is attached to the surface by coating.
- the thickness of the release sheet substrate is preferably in the range of 5 to 300 ⁇ m, more preferably in the range of 10 to 200 ⁇ m.
- Example 1 (Preparation of cellulose ester film 1) -Preparation of silicon dioxide dispersion Aerosil R812 (Nippon Aerosil Co., Ltd., average diameter of primary particles: 7 nm) 10 parts by mass Ethanol 90 parts by mass The above was stirred and mixed with a dissolver for 30 minutes, and then dispersed with Manton Gorin. 88 parts by mass of methylene chloride was added to the silicon dioxide dispersion with stirring, and the mixture was stirred and mixed with a dissolver for 30 minutes to prepare a silicon dioxide dispersion dilution. The mixture was filtered with a fine particle dispersion dilution filter (Advantech Toyo Co., Ltd .: polypropylene wind cartridge filter TCW-PPS-1N).
- a fine particle dispersion dilution filter Advancedtech Toyo Co., Ltd .: polypropylene wind cartridge filter TCW-PPS-1N).
- the belt was cast evenly on a stainless steel band support using a belt casting apparatus.
- the solvent was evaporated until the residual solvent amount reached 100%, and the stainless steel band support was peeled off.
- the cellulose ester film web was evaporated at 35 ° C., slit to 1.15 m width, and dried at a drying temperature of 140 ° C. while being stretched 1.15 times in the TD direction (film width direction) with a tenter. I let you. Then, it was dried for 15 minutes while being transported in a drying device at 120 ° C.
- the cellulose ester film 1 was obtained.
- the film thickness of the cellulose ester film 1 was 25 ⁇ m, and the winding length was 5000 m.
- a hard coat layer composition 1 described below was filtered with a polypropylene filter having a pore size of 0.4 ⁇ m, and an extrusion coater was used. After applying at a constant rate drying zone temperature of 50 ° C. and a reduced rate drying zone temperature of 50 ° C., the irradiation part is irradiated with an ultraviolet lamp while purging with nitrogen so that the oxygen concentration becomes 1.0% by volume or less.
- the coating layer is cured with an illuminance of 100 mW / cm 2 and an irradiation amount of 0.2 J / cm 2 to form a hard coat layer 1 having a dry film thickness of 2.5 ⁇ m, and the thickness of the air layer becomes 4 ⁇ m. In this manner, a roll-shaped hard coat film 1 was produced.
- Radical polymerizable fluororesin (A): Cefal coat CF-803 (hydroxy group number 60, number average molecular weight 15000; manufactured by Central Glass Co., Ltd.)
- One-end radically polymerizable polysiloxane (B): Silaplane FM-0721 (number average molecular weight 5000; manufactured by Chisso Corporation)
- Radical polymerization initiator Perbutyl O (t-butylperoxy-2-ethylhexanoate; manufactured by NOF Corporation)
- Curing agent Sumidur N3200 (biuret type prepolymer of hexamethylene diisocyanate; manufactured by Sumika Bayer Urethane Co., Ltd.) (Synthesis of radical polymerizable fluororesin)
- a glass reactor equipped with a mechanical stirrer, a thermometer, a condenser and a dry nitrogen gas inlet was added to cefal coat CF-803 (1554 parts by mass), xylene
- Hard Coat Layer Composition 2 70 parts by mass of pentaerythritol tri / tetraacrylate (NK ester A-TMM-3L, manufactured by Shin-Nakamura Chemical Co., Ltd.) 30 parts by mass of trimethylolpropane triacrylate (A-TMPT, manufactured by Shin-Nakamura Chemical Co., Ltd.) Photopolymerization initiator) Irgacure 184 (manufactured by BASF Japan) 6 parts by mass (additive) Optool DAC (fluorine compound, manufactured by Daikin Industries, Ltd.) 2 parts by mass (solvent) Propylene glycol monomethyl ether 20 parts by mass Methyl acetate 30 parts by mass Methyl ethyl ketone 70 parts by mass [Preparation of hard coat film 3] A hard coat film 3 was prepared in the same manner except that the hard coat film composition 1 was changed to the hard coat layer composition 3 described below.
- Hard Coat Layer Composition 3 >> (Actinic radiation curable resin) Pentaerythritol tri / tetraacrylate (NK ester A-TMM-3L, manufactured by Shin-Nakamura Chemical Co., Ltd.) 70 parts by mass Trimethylolpropane triacrylate (A-TMPT, manufactured by Shin-Nakamura Chemical Co., Ltd.) 30 parts by mass Irgacure 184 (BASF Japan) 6 parts by mass (additive) KF-354L (Polyether-modified silicone oil, Shin-Etsu Chemical Co., Ltd.) 2 parts by mass (solvent) Propylene glycol monomethyl ether 20 parts by mass Methyl acetate 30 parts by mass Methyl ethyl ketone 70 parts by mass [Preparation of hard coat film 4] A hard coat film 4 was prepared in the same manner except that the hard coat film composition 1 was changed to the hard coat layer composition 4 described below.
- Hard Coat Layer Composition 4 (Actinic radiation curable resin) 70 parts by mass of pentaerythritol tri / tetraacrylate (NK ester A-TMM-3L, manufactured by Shin-Nakamura Chemical Co., Ltd.) 30 parts by mass of trimethylolpropane triacrylate (A-TMPT, manufactured by Shin-Nakamura Chemical Co., Ltd.) Photopolymerization initiator) Irgacure 184 (manufactured by BASF Japan) 6 parts by mass (additive) BYK-UV3510 (polyether-modified polydimethylsiloxane, manufactured by Big Chemie Japan Co., Ltd.) 2 parts by mass (solvent) Propylene glycol monomethyl ether 20 parts by mass Methyl acetate 30 parts by mass Methyl ethyl ketone 70 parts by mass [Preparation of hard coat film 5] A hard coat film 5 was prepared in the same manner except that the hard coat film composition 1 was changed
- Hard Coat Layer Composition 5 (Actinic radiation curable resin) 70 parts by mass of pentaerythritol tri / tetraacrylate (NK ester A-TMM-3L, manufactured by Shin-Nakamura Chemical Co., Ltd.) 30 parts by mass of trimethylolpropane triacrylate (A-TMPT, manufactured by Shin-Nakamura Chemical Co., Ltd.) Photopolymerization initiator) Irgacure 184 (manufactured by BASF Japan) 6 parts by mass (solvent) Propylene glycol monomethyl ether 20 parts by mass Methyl acetate 30 parts by mass Methyl ethyl ketone 70 parts by mass [Preparation of hard coat film 6] A hard coat film 6 was produced in the same manner except that the hard coat film composition 1 was changed to the hard coat layer composition 6 described below.
- Hard Coat Layer Composition 6 70 parts by mass of pentaerythritol tri / tetraacrylate (NK ester A-TMM-3L, manufactured by Shin-Nakamura Chemical Co., Ltd.) 30 parts by mass of trimethylolpropane triacrylate (A-TMPT, manufactured by Shin-Nakamura Chemical Co., Ltd.) Photopolymerization initiator) Irgacure 184 (manufactured by BASF Japan) 6 parts by mass (additive) KF-354L (Polyether-modified silicone oil, manufactured by Shin-Etsu Chemical Co., Ltd.) 2 parts by mass (UV absorber) TINUVIN 928 (manufactured by BASF Japan Ltd.) 2 parts by mass (solvent) Propylene glycol monomethyl ether 20 parts by mass Methyl acetate 30 parts by mass Methyl ethyl ketone 70 parts by mass [Preparation of hard coat film 7
- a hard coat film 13 was prepared in the same manner except that the hard coat film composition 1 was changed to the hard coat layer composition 7 described below.
- Hard Coat Layer Composition 7 >> (Actinic radiation curable resin) Pentaerythritol tri / tetraacrylate (NK ester A-TMM-3L, manufactured by Shin-Nakamura Chemical Co., Ltd.) 35 parts by mass Urethane acrylate (NK Oligo UA-1100H, manufactured by Shin-Nakamura Chemical Co., Ltd.) 65 parts by mass (light Polymerization initiator) Irgacure 184 (manufactured by BASF Japan) 6 parts by mass (additive) KF-354L (Polyether-modified silicone oil, manufactured by Shin-Etsu Chemical Co., Ltd.) 2 parts by mass (solvent) Propylene glycol monomethyl ether 20 parts by mass Methyl acetate 30 parts by mass Methyl ethyl ketone 70 parts by mass [Preparation of hard coat film 14] A hard coat film 14 was prepared in the same manner except that the hard coat film composition 1 was changed to the hard coat layer composition 8
- Hard Coat Layer Composition 8 >> (Actinic radiation curable resin) Dipentaerythritol pentaacrylate (NK ester A-9550, manufactured by Shin-Nakamura Chemical Co., Ltd.) 35 parts by mass Urethane acrylate (NK Oligo UA-1100H, manufactured by Shin-Nakamura Chemical Co., Ltd.) 65 parts by mass (photopolymerization initiator) ) Irgacure 184 (manufactured by BASF Japan) 6 parts by mass (additive) KF-354L (Polyether-modified silicone oil, manufactured by Shin-Etsu Chemical Co., Ltd.) 2 parts by mass (solvent) Propylene glycol monomethyl ether 20 parts by mass Methyl acetate 30 parts by mass Methyl ethyl ketone 70 parts by mass [Preparation of hard coat film 15] A hard coat film 15 was produced in the same manner as in the production of the hard coat film 1 produced above except that the hard coat layer composition 9 was
- Hard Coat Layer Composition 9 (Actinic radiation curable resin) Dipentaerythritol pentaacrylate (NK Ester A-9550, Shin-Nakamura Chemical Co., Ltd.) 35 parts by mass Urethane acrylate (NK Oligo UA-15HA, Shin-Nakamura Chemical Co., Ltd.) 65 parts by mass (photopolymerization initiator) ) Irgacure 184 (manufactured by BASF Japan) 6 parts by mass (additive) KF-354L (Polyether-modified silicone oil, manufactured by Shin-Etsu Chemical Co., Ltd.) 2 parts by mass (solvent) Propylene glycol monomethyl ether 20 parts by mass Methyl acetate 30 parts by mass Methyl ethyl ketone 70 parts by mass [Preparation of hard coat film 16] A hard coat film 16 was prepared in the same manner except that the hard coat film composition 1 was changed to the hard coat layer composition 10 described below.
- Hard Coat Layer Composition 10 >> (Actinic radiation curable resin) Dipentaerythritol pentaacrylate (NK ester A-9550, manufactured by Shin-Nakamura Chemical Co., Ltd.) 35 parts by mass Urethane acrylate (UA-306I, manufactured by Kyoeisha Chemical Co., Ltd.) 65 parts by mass (photopolymerization initiator) Irgacure 184 (manufactured by BASF Japan) 6 parts by mass (additive) KF-354L (Polyether-modified silicone oil, manufactured by Shin-Etsu Chemical Co., Ltd.) 2 parts by mass (solvent) Propylene glycol monomethyl ether 20 parts by mass Methyl acetate 30 parts by mass Methyl ethyl ketone 70 parts by mass [Preparation of hard coat film 17] A hard coat film 17 was prepared in the same manner except that the hard coat film composition 1 was changed to the hard coat layer composition 11 described below.
- Hard Coat Layer Composition 11 (Actinic radiation curable resin) Dipentaerythritol pentaacrylate (NK ester A-9550, manufactured by Shin-Nakamura Chemical Co., Ltd.) 35 parts by mass Urethane acrylate (UA-306T, manufactured by Kyoeisha Chemical Co., Ltd.) 65 parts by mass (photopolymerization initiator) Irgacure 184 (manufactured by BASF Japan) 6 parts by mass (additive) KF-354L (Polyether-modified silicone oil, manufactured by Shin-Etsu Chemical Co., Ltd.) 2 parts by mass (solvent) Propylene glycol monomethyl ether 20 parts by mass Methyl acetate 30 parts by mass Methyl ethyl ketone 70 parts by mass [Preparation of hard coat film 18] A hard coat film 18 was prepared in the same manner except that the hard coat film composition 1 was changed to the hard coat layer composition 12 described below.
- Hard Coat Layer Composition 12 >> (Actinic radiation curable resin) Dipentaerythritol pentaacrylate (NK ester A-9550, manufactured by Shin-Nakamura Chemical Co., Ltd.) 35 parts by mass Urethane acrylate (NK Oligo UA-1100H, manufactured by Shin-Nakamura Chemical Co., Ltd.) 65 parts by mass (photopolymerization initiator) ) Irgacure 184 (manufactured by BASF Japan) 6 parts by mass (additive) KF-351A (Polyether-modified silicone oil, manufactured by Shin-Etsu Chemical Co., Ltd.) 2 parts by mass (solvent) Propylene glycol monomethyl ether 20 parts by mass Methyl acetate 30 parts by mass Methyl ethyl ketone 70 parts by mass [Preparation of hard coat film 19] A hard coat film 19 was prepared in the same manner except that the hard coat film composition 1 was changed to the hard coat layer composition 13 described below.
- Hard Coat Layer Composition 13 >> (Actinic radiation curable resin) Dipentaerythritol pentaacrylate (NK ester A-9550, manufactured by Shin-Nakamura Chemical Co., Ltd.) 35 parts by mass Urethane acrylate (NK Oligo UA-1100H, manufactured by Shin-Nakamura Chemical Co., Ltd.) 65 parts by mass (photopolymerization initiator) ) Irgacure 184 (manufactured by BASF Japan) 3 parts by mass Irgacure 907 (manufactured by BASF Japan) 3 parts by mass (additive) KF-351A (Polyether-modified silicone oil, manufactured by Shin-Etsu Chemical Co., Ltd.) 2 parts by mass (solvent) Propylene glycol monomethyl ether 20 parts by mass Methyl acetate 30 parts by mass Methyl ethyl ketone 70 parts by mass [Preparation of Polarizing Plate 101] A polarizing plate 101 was prepared using
- the obtained PVA film had an average thickness of 25 ⁇ m, a moisture content of 4.4%, and a film width of 3 m.
- the obtained PVA film was continuously processed in the order of preliminary swelling, dyeing, uniaxial stretching by a wet method, fixing treatment, drying, and heat treatment to prepare a polarizing film. That is, the PVA film was immersed in water at a temperature of 30 ° C. for 30 seconds to be pre-swelled, and immersed in an aqueous solution having an iodine concentration of 0.4 g / liter and a potassium iodide concentration of 40 g / liter at a temperature of 35 ° C. for 3 minutes.
- the film was uniaxially stretched 6 times in a 50% aqueous solution with a boric acid concentration of 4% under a tension of 700 N / m.
- the potassium iodide concentration was 40 g / liter
- the boric acid concentration was 40 g / liter.
- it was immersed in an aqueous solution having a zinc chloride concentration of 10 g / liter and a temperature of 30 ° C. for 5 minutes for fixing.
- the PVA film was taken out, dried with hot air at a temperature of 40 ° C., and further heat-treated at a temperature of 100 ° C. for 5 minutes.
- the obtained polarizing film had an average thickness of 13 ⁇ m, a polarizing performance of a transmittance of 43.0%, a polarization degree of 99.5%, and a dichroic ratio of 40.1.
- a polarizing plate 101 was produced by bonding the polarizing film, the cellulose ester film 1 and the hard coat film 1 in accordance with the following steps 1 to 4.
- Step 1 The polarizing film described above was immersed in a storage tank of a polyvinyl alcohol adhesive solution having a solid content of 2% by mass for 1 to 2 seconds.
- Step 2 The cellulose ester film 1 and the hard coat film 1 were subjected to alkali treatment under the following conditions.
- a polarizing film (described as PV1 in FIG. 4) was immersed in the polyvinyl alcohol adhesive solution. The excess adhesive adhered to the immersed polarizing film is lightly removed, and the cellulose ester film film 1 and the hard coat film 1 are sandwiched between the polarizing films as shown in FIG. Was wound so that the thickness became 5 ⁇ m, and a roll-shaped polarizing plate 101 was produced.
- Step 3 The laminate was bonded at a speed of about 2 m / min at a pressure of 20 to 30 N / cm 2 with two rotating rollers. At this time, care was taken to prevent bubbles from entering.
- Step 4 The sample prepared in Step 3 was dried in a dryer at a temperature of 100 ° C. for 5 minutes to prepare a roll-shaped polarizing plate.
- Roll-shaped polarizing plates 102 to 119 were prepared in the same manner except that the hard coat film 1 was changed to the hard coat films 2 to 19 in the production of the polarizing plate 101. None of the roll-shaped polarizing plates had any winding deviation.
- Adhesive layer A commercially available acrylic adhesive is applied to the cellulose ester film 1 of the polarizing plate so that the thickness after drying is 25 ⁇ m, dried in an oven at 110 ° C. for 5 minutes to form an adhesive layer, and then peelable to the adhesive layer. A protective film was attached.
- Liquid crystal display device 201 Of two pairs of polarizing plates installed with a liquid crystal layer sandwiched between 21.5 inch liquid crystal display devices (IPS226V-PN, LG Electronics Japan Co., Ltd.), the polarizing plate on one side on the viewer side is peeled off, The pressure-sensitive adhesive layer and the liquid crystal cell glass were bonded so that the produced polarizing plate 101 had the hard coat layer on the viewing side.
- the liquid crystal display device 201 was manufactured by arranging the transmission axis of the polarizing plate on the viewer side and the transmission axis of the polarizing plate on the backlight side to be orthogonal to each other.
- the contact angle with water is measured by a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.) in an atmosphere at a temperature of 23 ° C. and a relative humidity of 55% after leaving the sample for 24 hours in an atmosphere at a temperature of 23 ° C. and a relative humidity of 55%.
- the contact angle of pure water was measured 1 minute after dropping 1 ⁇ L of pure water using a product name DropMaster DM100).
- the measurement was performed seven times, and the average value of the five measurement values excluding the maximum value and the minimum value of the measurement values was defined as the contact angle of the sample.
- Polarizing plate / winding deviation evaluation The above-produced roll-shaped polarizing plates 101 to 119 are placed on a gantry, and a vibration test is performed for 1 hour according to JIS Z0232 using a general-purpose vibration test apparatus J series (manufactured by IMV Corporation). The difference between the winding misalignment position after the vibration test and the non-winding misalignment position was measured with a curved scale and evaluated according to the following criteria.
- Liquid Crystal Display Device Visibility was evaluated by evaluating the unevenness and flatness of the liquid crystal display devices 201 to 219. a. Unevenness Evaluation Each of the liquid crystal display devices produced above was observed from the front with a black display, and unevenness was evaluated according to the following criteria.
- the difference ( ⁇ ⁇ ) in water contact angle before and after the alkali treatment of the hard coat layer is in the range of 5 to 55 °, and the film thickness of the cellulose ester film is 5 to 5
- the use of a hard coat film within the range of 34 ⁇ m exhibits an excellent effect on winding deviation.
- the polarizing plate comprised from the hard coat film of this invention exhibits the effect excellent in the nonuniformity after a durability test, and planarity.
- the liquid crystal display device incorporating the polarizing plate comprised from the hard coat film of this invention is excellent in visibility.
- the hardness of the hard coat films 1 to 19 before the alkali treatment was confirmed by a pencil hardness test.
- the test pencil specified by JIS-S6006 in accordance with the pencil hardness evaluation method specified by JIS-K5400, the hard coat layer surfaces of the hard coat films 1 to 19 are repeated 5 times with a pencil of each hardness using a 500 g weight.
- the pencil hardness of the hard coat film of the present invention was all H or higher.
- Example 2 Hard coat films 20 to 24 were produced in the same manner as in the production of the hard coat film 3 of Example 1, except that the decreasing rate drying zone temperature of the hard coat layer was changed as shown in Table 2. Furthermore, in the same manner as the polarizing plate 103 of Example 1, roll-shaped polarizing plates 120 to 124 were produced using the hard coat films 20 to 24, respectively. In all cases, there was no winding deviation.
- the winding deviations of the polarizing plate 103 and the polarizing plates 120 to 124 were evaluated in the same manner except that the vibration test time for the winding deviation evaluation in Example 1 was changed to 3 hours. Further, for each of the hard coat layers of the hard coat film 3 and 20 to 24, it was measured 10 times using an optical interference type surface roughness meter (manufactured by ZYGO, New View 5030), and from the average of the measurement results, Arithmetic mean roughness Ra was determined.
- the durability test was performed on the polarizing plate 103 and the polarizing plates 120 to 124 after the durability test in the same manner as in Example 1 except that the durability test was changed to 65 ° C. and a relative humidity of 80%.
- 103 and polarizing plates 120 to 124 were provided with an adhesive layer as shown in FIG. 4 and incorporated in a liquid crystal display device to evaluate the visibility. The obtained results are shown in Table 2.
- the arithmetic average roughness Ra of the hard coat layer is controlled to 2 to 100 nm, excellent winding displacement resistance can be obtained in a more severe vibration test. Therefore, it turns out that it is preferable. Further, it can be seen that by using a polarizing plate composed of the hard coat film of the present invention in which Ra is controlled to 2 to 100 nm, an effect excellent in unevenness and flatness after a more severe durability test is exhibited. More preferably, the arithmetic average roughness Ra of the hard coat layer is in the range of 5 to 80 nm.
- Example 3 In the production of the hard coat film 3 of Example 1, hard coat films 25 and 26 were produced in the same manner except that the active ray curable resin of the hard coat layer composition was changed as described in Table 3. Further, in the same manner as the polarizing plate 103 of Example 1, polarizing plates 125 and 126 were produced using the hard coat films 25 and 26. In all cases, there was no winding deviation.
- An adhesive layer is provided on the polarizing plate 103 and the polarizing plates 125 and 126 after the endurance test in the same manner as in Example 1 except that the durability test condition assuming long-term transportation is changed to 65 ° C. and a relative humidity of 80%. The visibility was incorporated into the display device. The obtained results are shown in Table 3.
- Pentaerythritol tri / tetraacrylate is PETA
- trimethylolpropane triacrylate is TMPTA
- tris (2-acryloyloxyethyl) isocyanurate (NK ester A-9300, manufactured by Shin-Nakamura Chemical Co., Ltd.) is ICTA
- isocyanuric acid Table 3 shows ethoxy-modified diacrylate (Aronix M-215, manufactured by Toagosei Co., Ltd.).
- the hard coat film of the present invention using an active energy ray-curable isocyanurate derivative for the hard coat layer is preferable because excellent winding displacement resistance is obtained in a more severe vibration test. I understand that.
- a polarizing plate composed of the hard coat film of the present invention using an active energy ray-curable isocyanurate derivative it exhibits excellent effects in unevenness and flatness after a more severe durability test. I understand.
- Example 4 In the preparation of the dope composition 1 for the cellulose ester film 1 of Example 1, the dope composition was the same except that 8 parts by mass of the acrylic polymer synthesized below was added instead of 4 parts by mass of the additive X-12. Product 2 was prepared. Next, cellulose ester films 6 to 9 were prepared in the same manner except that the stretching conditions in the TD direction by the tenter were changed as shown in Table 4 in the production of the cellulose ester film 1. In all cases, there was no winding deviation.
- double-sided hard coat films 26 to 29 were prepared in the same manner as the hard coat film 3 except that the hard coat layer composition 3 of Example 1 was provided on both sides of the produced cellulose ester films 6 to 9. did. Furthermore, in the hard coat film 3, the hard coat layer composition 3 was provided on both surfaces, and the double-sided hard coat film 30 was produced.
- the double-sided hard coat films 26 to 30 thus prepared were subjected to alkali treatment under the same conditions as the alkali treatment in the production of the polarizing plate of Example 1, and the difference ( ⁇ ⁇ ) in water contact angle before and after the alkali treatment was measured.
- the vibration test of the double-sided hard coat films 26 to 30 was performed in the same manner as the vibration test of the polarizing plate of Example 1 to evaluate the winding deviation.
- the in-plane retardation value Ro and the thickness direction retardation value Rth of the cellulose ester films 1 and 6 to 9 were measured by the following methods.
- n x thickness, n y, seek n z were determined Ro and Rth of the cellulose ester film by the following equation.
- n x is a refractive index in a slow axis direction in the substrate film surface
- n y is the refractive index in the direction perpendicular to the slow axis in the base film surface
- the thickness of the n z is a substrate film
- the refractive index in the direction, d represents the thickness (nm) of the substrate film, respectively.
- Conductive hard coat films 1 to 5 were produced by providing a conductive film of indium tin oxide (ITO) having a surface resistivity of about 400 ⁇ on both sides of the double-sided hard coat films 26 to 30 by a sputtering method.
- ITO indium tin oxide
- an inner touch panel was produced using two each of the produced conductive hard coat films 1 to 5 (FIG. 2).
- a dot spacer was formed in advance on the conductive film (21D) of one of the two conductive hard coat films, and then the two conductive films were opposed to produce an inner touch panel.
- the obtained touch panel is assembled under the upper surface side polarizing plate (21F1) of the liquid crystal display device having the configuration of the upper surface side polarizing plate (21F1) / liquid crystal cell / lower surface side polarizing plate (21F2), and an inner touch panel is manufactured.
- the black display screen was observed by changing the front direction and the visual field direction, and the visibility (color change) was evaluated according to the following criteria. The results obtained are shown in Table 4.
- a conductive hard coat film composed of the double-sided hard coat film according to the present invention for a touch panel is preferable because excellent visibility (inhibition of color change) can be obtained.
- using a film for a touch panel is particularly preferable because excellent visibility (inhibition of color change) is obtained.
- the double-sided hard coat film of the present invention has excellent resistance to winding deviation.
- Example 5 In the production of the hard coat film 3 of Example 1, the hard coat film 31 was produced in the same manner except that the cellulose ester film 1 was changed to the cellulose ester film 6. In addition, in the production of the polarizing plate of Example 1 using the hard coat film 31, a roll-shaped polarization was similarly performed except that the cellulose ester film 1 to be bonded to the surface opposite to the hard coat film was changed to the cellulose ester film 6. A plate 127 was produced. Further, using the hard coat film 25, a roll-shaped polarizing plate 128 was produced in the same manner as in Example 1. In all cases, there was no winding deviation.
- the water contact angle before the alkali treatment of the prepared hard coat film 31 and the water contact angle after the alkali treatment after the production of the polarizing plate were measured, and the difference in the water contact angle before and after the alkali treatment ( ⁇ ⁇ ). Asked.
- Example 2 the winding deviation of the polarizing plate 103, the polarizing plate 127, and the polarizing plate 128 was evaluated. Further, in the same manner as in Example 1, an adhesive layer as shown in FIG. 4 is provided on the polarizing plate 103, the polarizing plate 127, and the polarizing plate 128 after the durability test, and the liquid crystal display device 227 and the liquid crystal are incorporated into the liquid crystal display device. A display device 228 was produced and evaluated in the same manner as in Example 1. Furthermore, the color change of the visibility evaluation was evaluated according to the following criteria. The obtained results are shown in Table 5.
- the hard coat film according to the invention is excellent because it has excellent resistance to winding misalignment and is particularly excellent in visibility when used in a liquid crystal display device.
- Example 6 (Production of substrate-less adhesive sheet)
- the pressure-sensitive adhesive-containing composition 1 was applied to the release surface of a release sheet (trade name: SP-PET 381031, thickness 38 ⁇ m, manufactured by Lintec Corporation) using a die coater so that the thickness after drying was 15 ⁇ m. It dried at 120 degreeC for 2 minute (s), the adhesive layer was formed, and the base material-less adhesive sheet which consists of a peeling sheet and the adhesive layer formed in the peeling surface was obtained.
- a release sheet trade name: SP-PET 381031, thickness 38 ⁇ m, manufactured by Lintec Corporation
- Adhesive-containing composition 1 The following composition was stirred to prepare an adhesive-containing composition 1. N-butyl acrylate 79% by mass, methyl acrylate 20% by mass, Acrylate ester copolymer obtained by copolymerizing 1% by mass of 2-hydroxyethyl acrylate (molecular weight 800,000, concentration 35% by mass) 100 parts by mass.
- Toluene and xylylene diisocyanate trifunctional adduct (trade name) : TD-75, concentration 75% by mass, manufactured by Soken Chemical Co., Ltd.) 0.1 part by mass
- the roll-shaped hard coat films 1 to 19 produced in Example 1 were wrapped in an aluminum moisture-proof sheet and stored for 25 days in a thermostatic bath at a temperature of 50 ° C. and a relative humidity of 80% assuming long-term transportation, and a durability test was performed. . After the durability test, the adhesive layer of the substrate-less pressure-sensitive adhesive sheet was bonded to both surfaces of the hard coat films 1 to 19 to obtain glass scattering prevention films 1 to 19 for image display devices.
- the adhesive layer of the base material-less pressure-sensitive adhesive sheet of each hard coat layer is attached to a liquid crystal display device with a touch panel (Image display devices 1 to 19 were prepared by bonding to a model name: LCD-USB10XB-T (manufactured by I / O Data Equipment Co., Ltd.), and visibility was evaluated according to the following criteria.
- a laminate composed of a glass plate and an anti-scattering film was placed on a table having a height of 10 mm with the anti-scattering film facing upward.
- the glass scattering prevention film for an image display device composed of the hard coat film of the present invention has excellent visibility when used in an image display device, and also has excellent glass scattering prevention properties. I understand that.
- the hard coat film of the present invention suppresses slipperiness between films, provides an effect of preventing winding deviation, suppresses buckling deformation and distortion of the film when wound in a roll shape, and improves flatness and unevenness. It is an excellent hard coat film.
- the hard coat film is suitable for a glass scattering prevention film for an image display device having good visibility, a touch panel, a polarizing plate and a liquid crystal display device.
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Abstract
Description
アルカリ溶液:2.5mol/L水酸化カリウム溶液
処理温度:50℃
処理時間:120秒
2.前記ハードコート層のアルカリ処理前の対水接触角(θ)が、50~120°の範囲内であることを特徴とする第1項に記載のハードコートフィルム。
アルカリ溶液:2.5mol/L水酸化カリウム溶液
処理温度:50℃
処理時間:120秒
この特徴は、請求項1から請求項10までの請求項に係る発明に共通する技術的特徴である。
最初に本発明に係るアルカリ処理前後の対水接触角の差(θΔ)について説明する。
(ハードコート層)
本発明に係るハードコート層は、活性線硬化樹脂を含有することが機械的膜強度(耐擦傷性、鉛筆硬度)に優れる点から好ましい。すなわち、紫外線や電子線のような活性線(活性エネルギー線ともいう。)照射により、架橋反応を経て硬化する樹脂を主たる成分とする層である。活性線硬化樹脂としては、エチレン性不飽和二重結合を有するモノマーを含む成分が好ましく用いられ、紫外線や電子線のような活性線を照射することによって硬化させて活性線硬化樹脂層が形成される。活性線硬化樹脂としては、紫外線硬化性樹脂や電子線硬化性樹脂等が代表的なものとして挙げられるが、紫外線照射によって硬化する樹脂が特に機械的膜強度(耐擦傷性、鉛筆硬度)に優れる点から好ましい。紫外線硬化性樹脂としては、例えば、紫外線硬化型アクリレート系樹脂、紫外線硬化型ウレタンアクリレート系樹脂、紫外線硬化型ポリエステルアクリレート系樹脂、紫外線硬化型エポキシアクリレート系樹脂、紫外線硬化型ポリオールアクリレート系樹脂、又は紫外線硬化型エポキシ樹脂等が好ましく用いられ、中でも紫外線硬化型アクリレート系樹脂又は紫外線硬化型ウレタンアクリレート系樹脂が好ましい。
b:-(CH2)n-O-(COC5H10)m-COCH=CH2(n=1~10、好ましくはn=2~6、m=2~8)
c:-(CH2)n-O-R(Rは(メタ)アクリロイル基、n=1~10、好ましくはn=2~6)
一般式(3)で示される具体的化合物を以下に示すが、これらに限られない。
また、ハードコート層には活性線硬化樹脂の硬化促進のため、光重合開始剤を含有することが好ましい。光重合開始剤量としては、質量比で、光重合開始剤:活性線硬化樹脂=20:100~0.01:100の範囲で含有することが好ましい。光重合開始剤としては、具体的には、具体的には、アルキルフェノン系、アセトフェノン、ベンゾフェノン、ヒドロキシベンゾフェノン、ミヒラーケトン、α-アミロキシムエステル、チオキサントン等及び、これらの誘導体を挙げることができるが、特にこれらに限定されるものではない。
ハードコート層には、帯電防止性を付与するために導電剤が含まれていても良い。好ましい導電剤としては、金属酸化物粒子又はπ共役系導電性ポリマーが挙げられる。また、イオン液体も導電性化合物として好ましく用いられる。
ハードコート層には、アルカリ処理前後の対水接触角の差(θΔ)を前記範囲に制御する観点から、シリコーン系界面活性剤、フッ素系界面活性剤、アニオン界面活性剤、及びフッ素-シロキサングラフト化合物、フッ素系化合物、アクリル共重合物などの添加剤を含有させても良い。また、HLB値が3~18の範囲内の化合物を含有しても良い。これら添加剤の種類や添加量を調整することで、撥水性を制御でき、θΔを前記範囲に制御しやすい。
式中、Mwは親水基の分子量、Moは親油基の分子量を表し、Mw+Mo=M(化合物の分子量)である。HLB値が3~18の範囲内の化合物の具体的化合物を下記に挙げるが、本発明はこれに限定されるものでない。( )内はHLB値を示す。
ハードコート層は、後述するセルロースエステルフィルムで説明する紫外線吸収剤をさらに含有しても良い。紫外線吸収剤を含有する場合のフィルムの構成としては、二層以上で構成される場合には、かつセルロースエステルフィルムと接するハードコート層に紫外線吸収剤を含有することが好ましい。
ハードコート層は、上記したハードコート層を形成する成分を、セルロースエステルフィルムを膨潤又は一部溶解をする溶剤で希釈してハードコート層組成物として、以下の方法でセルロースフィルム上に塗布、乾燥、硬化してハードコート層を設けることが好ましい。
ハードコート層組成物塗布後、乾燥し、活性線を照射して硬化(UV硬化処理ともいう。)し、更に必要に応じて、UV硬化処理後に加熱処理しても良い。UV硬化処理後の加熱処理温度としては80℃以上が好ましく、更に好ましくは100℃以上であり、特に好ましくは120℃以上である。このような高温でUV硬化処理後の加熱処理を行うことで、膜強度に優れたハードコート層を得ることができる。
ハードコート層の算術平均粗さRa(JIS B0601:2001)は、2~100nmの範囲内が好ましく、特に好ましくは5~80nmの範囲内である。前記範囲の算術平均粗さRaとすることで、より過酷な振動試験後も本発明の効果発現が好適に得られやすい。
ハードコートフィルムのヘイズは、画像表示装置に用いた場合の視認性から0.2~10%の範囲内であることが好ましい。ヘイズは、JIS-K7105及びJIS K7136に準じて測定できる。
本発明のハードコートフィルムは、硬度の指標である鉛筆硬度がHB以上、より好ましくはH以上である。HB以上であれば、偏光板化工程で、傷が付きにくい。鉛筆硬度は、作製した光学性フィルムを温度23℃、相対湿度55%の条件で2時間以上調湿した後、加重500g条件でJIS S6006が規定する試験用鉛筆を用いて、ハードコート層及び又は機能性層をJIS K5400が規定する鉛筆硬度評価方法に従い測定した値である。
本発明に係るハードコートフィルムの基材であるセルロースエステルフィルム、及び偏光板の裏面側に貼合されるセルロースエステルフィルムについて説明する。
セルロースエステル樹脂(以下、セルロースエステルともいう)は、セルロースの低級脂肪酸エステルであることが好ましい。セルロースの低級脂肪酸エステルにおける低級脂肪酸とは炭素原子数が6以下の脂肪酸を意味し、例えば、セルロースアセテート、セルロースジアセテート、セルローストリアセテート、セルロースプロピオネート、セルロースブチレート等や、セルロースアセテートプロピオネート、セルロースアセテートブチレート等の混合脂肪酸エステルを用いることができる。
式(II) 0≦X≦2.5
中でも1.9≦X≦2.5、0.1≦Y≦0.9であることが好ましい。
カラム:Shodex K806、K805、K803G
(昭和電工(株)製を3本接続して使用した)
カラム温度:25℃
試料濃度:0.1質量%
検出器:RI Model 504(GLサイエンス社製)
ポンプ:L6000(日立製作所(株)製)
流量:1.0ml/min
校正曲線:標準ポリスチレンSTK standard ポリスチレン(東ソー(株)製)Mw=1000000~500迄の13サンプルによる校正曲線を使用した。13サンプルは、ほぼ等間隔に用いることが好ましい。
セルロースエステルフィルムは、熱可塑性アクリル樹脂を併用しても良い。併用する場合には、熱可塑性アクリル樹脂とセルロースエステル樹脂の含有質量比が、熱可塑性アクリル樹脂:セルロースエステル樹脂=95:5~50:50の範囲が好ましい。
本発明に係るセルロースエステルフィルムには、取扱性を向上させるため、例えばアクリル粒子、二酸化ケイ素、二酸化チタン、酸化アルミニウム、酸化ジルコニウム、炭酸カルシウム、カオリン、タルク、焼成ケイ酸カルシウム、水和ケイ酸カルシウム、ケイ酸アルミニウム、ケイ酸マグネシウム、リン酸カルシウム等の無機微粒子や架橋高分子などのマット剤を含有させることが好ましい。またアクリル粒子は、特に限定されるものではないが、多層構造アクリル系粒状複合体であることが好ましい。これらの中でも二酸化ケイ素がセルロースエステルフィルムのヘイズを小さくできる点で好ましい。微粒子の一次平均粒子径としては、20nm以下が好ましく、更に好ましくは、5~16nmの範囲内であり、特に好ましくは、5~12nmの範囲内である。
(式中、Bはヒドロキシ基又はカルボン酸残基、Gは炭素数2~12のアルキレングリコール残基又は炭素数6~12のアリールグリコール残基又は炭素数が4~12のオキシアルキレングリコール残基、Aは炭素数4~12のアルキレンジカルボン酸残基又は炭素数6~12のアリールジカルボン酸残基を表す。nは1以上の整数を表す。)
一般式(X)において、炭素数2~12のアルキレングリコール成分としては、エチレングリコール、1,2-プロピレングリコール、1,3-プロピレングリコール、1,2-ブタンジオール、1,3-ブタンジオール、1,2-プロパンジオール、2-メチル-1,3-プロパンジオール、1,4-ブタンジオール、1,5-ペンタンジオール、2,2-ジメチル-1,3-プロパンジオール(ネオペンチルグリコール)、2,2-ジエチル-1,3-プロパンジオール(3,3-ジメチロールペンタン)、2-n-ブチル-2-エチル-1,3プロパンジオール(3,3-ジメチロールヘプタン)、3-メチル-1,5-ペンタンジオール1,6-ヘキサンジオール、2,2,4-トリメチル-1,3-ペンタンジオール、2-エチル-1,3-ヘキサンジオール、2-メチル-1,8-オクタンジオール、1,9-ノナンジオール、1,10-デカンジオール、1,12-オクタデカンジオール等があり、これらのグリコールは、一種又は二種以上の混合物として使用される。特に炭素数2~12のアルキレングリコールがセルロースアセテートとの相溶性に優れているため、特に好ましい。炭素数6~12のアリールグリコール成分としては、例えば、ハイドロキノン、レゾルシン、ビスフェノールA、ビスフェノールF、ビスフェノール等があり、これらのグリコールは、一種又は二種以上の混合物として使用できる。
以下に一般式(Y)で示される化合物をより具体的(化合物Y-1~化合物Y-23)に示すが、これらに限定はされない。なお、下表において平均置換度が8.0未満の場合、R1~R8のうちのいずれかは水素原子を表す。
〔可塑剤〕
本発明に係るセルロースアセテートフィルムは、必要に応じて可塑剤を含有しても良い。
本発明に係るセルロースアセテートフィルムは、紫外線吸収剤を含有していてもよい。紫外線吸収剤は400nm以下の紫外線を吸収することため、耐久性を向上させるができる。紫外線吸収剤は、特に波長370nmでの透過率が10%以下であることが好ましく、より好ましくは5%以下、更に好ましくは2%以下である。紫外線吸収剤の具体例としては特に限定されないが、例えば、オキシベンゾフェノン系化合物、ベンゾトリアゾール系化合物、サリチル酸エステル系化合物、ベンゾフェノン系化合物、シアノアクリレート系化合物、トリアジン系化合物、ニッケル錯塩系化合物、無機粉体等が挙げられる。
本発明に係るセルロースアセテートフィルムは、さらに酸化防止剤(劣化防止剤)を含有していてもよい。酸化防止剤は、セルロースアセテートフィルム中の残留溶媒量のハロゲンやリン酸系可塑剤のリン酸等によりセルロースアセテートフィルムが分解するのを遅らせたり、防いだりする役割を有する。酸化防止剤としては、ヒンダードフェノール系の化合物が好ましく用いられ、例えば2,6-ジ-t-ブチル-p-クレゾール、ペンタエリスリチル-テトラキス〔3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート〕、トリエチレングリコール-ビス〔3-(3-t-ブチル-5-メチル-4-ヒドロキシフェニル)プロピオネート〕、1,6-ヘキサンジオール-ビス〔3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート〕、2,4-ビス-(n-オクチルチオ)-6-(4-ヒドロキシ-3,5-ジ-t-ブチルアニリノ)-1,3,5-トリアジン、2,2-チオ-ジエチレンビス〔3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート〕、オクタデシル-3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート、N,N′-ヘキサメチレンビス(3,5-ジ-t-ブチル-4-ヒドロキシ-ヒドロシンナマミド)、1,3,5-トリメチル-2,4,6-トリス(3,5-ジ-t-ブチル-4-ヒドロキシベンジル)ベンゼン、トリス-(3,5-ジ-t-ブチル-4-ヒドロキシベンジル)-イソシアヌレート等を挙げることができる。これら化合物の添加量は、セルロースアセテートフィルムに対して、質量割合で1~10000ppmの範囲内が好ましく、10~1000ppmの範囲内が更に好ましい。
セルロースエステルフィルムは、直径5μm以上の欠点が1個/10cm四方以下であることが好ましい。更に好ましくは0.5個/10cm四方以下、より好ましくは0.1個/10cm四方以下である。ここで欠点の直径とは、欠点が円形の場合はその直径を示し、円形でない場合は欠点の範囲を下記方法により顕微鏡で観察して決定し、その最大径(外接円の直径)とする。
セルロースエステルフィルムは、その全光線透過率が90%以上であることが好ましく、より好ましくは93%以上である。また、現実的な上限としては、99%程度である。ヘイズ値は2%以下が好ましく、より好ましくは1.5%以下である。全光線透過率、ヘイズ値はJIS K7361及びJIS K7136に準じて測定することができる。
式(ii) Rth={(nx+ny)/2-nz}×d
(式中、nxはセルロースエステルフィルム面内の遅相軸方向の屈折率、nyはセルロースエステルフィルム面内で遅相軸に直交する方向の屈折率、nzはセルロースエステルフィルムの厚さ方向の屈折率、dはセルロースエステルフィルムの厚さ(nm)をそれぞれ表す。)
上記リターデーションは、例えばKOBRA-21ADH(王子計測機器(株)製)を用いて、23℃、相対湿度55%の環境下で、波長が590nmで求めることができる。上記リターデーション値に制御したセルロースエステルフィルムを用いることで、タッチパネルや液晶表示装置などの画像表示装置に用いた際の視認性に優れる点から好ましい。リターデーションは、前述した可塑剤の種類や添加量及びセルロースエステルフィルムの膜厚や延伸条件等で調整できる。
次に、セルロースエステルフィルムの製膜方法の例を説明するが、これに限定されるものではない。セルロースエステルフィルムの製膜方法としては、インフレーション法、T-ダイ法、カレンダー法、切削法、流延法、エマルジョン法、ホットプレス法等の製造法が使用できる。
セルロースエステルフィルムを溶液流延製膜法で製造する場合の樹脂溶液(ドープ組成物)を形成するのに有用な有機溶媒は、セルロースエステル樹脂、その他の添加剤を同時に溶解するものであれば制限なく用いることができる。例えば、塩素系有機溶媒としては、塩化メチレン、非塩素系有機溶媒としては、酢酸メチル、酢酸エチル、酢酸アミル、アセトン、テトラヒドロフラン、1,3-ジオキソラン、1,4-ジオキサン、シクロヘキサノン、ギ酸エチル、2,2,2-トリフルオロエタノール、2,2,3,3-ヘキサフルオロ-1-プロパノール、1,3-ジフルオロ-2-プロパノール、1,1,1,3,3,3-ヘキサフルオロ-2-メチル-2-プロパノール、1,1,1,3,3,3-ヘキサフルオロ-2-プロパノール、2,2,3,3,3-ペンタフルオロ-1-プロパノール、ニトロエタン、メタノール、エタノール、n-プロパノール、iso-プロパノール、n-ブタノール、sec-ブタノール、tert-ブタノール等を挙げることができ、塩化メチレン、酢酸メチル、酢酸エチル、アセトンを好ましく使用し得る。前記溶媒はセルロースエステル樹脂、その他添加剤を計15~45質量%の範囲内で溶解させたドープ組成物であることが好ましい。
溶液流延製膜法では、樹脂及び添加剤を溶剤に溶解させてドープを調製する工程、ドープをベルト状若しくはドラム状の金属支持体上に流延する工程、流延したドープをウェブとして乾燥する工程、金属支持体から剥離する工程、延伸又は幅保持する工程、更に乾燥する工程、仕上がったセルロースエステルフィルムを巻き取る工程により行われる。
なお、Mはウェブ又はフィルムを製造中又は製造後の任意の時点で採取した試料の質量で、NはMを115℃で1時間の加熱後の質量である。
セルロースエステルフィルムは、溶融流延製膜法によって製膜しても良い。溶融流延製膜法は、セルロースエステル樹脂、可塑剤等のその他の添加剤を含む組成物を、流動性を示す温度まで加熱溶融し、その後、流動性のセルロースエステルを含む溶融物を流延することをいう。
本発明におけるセルロースエステルフィルムの膜厚は、5~34μmの範囲内であることを特徴とする。該範囲の膜厚を有するセルロースエステルフィルムにおいて本発明の効果発現が得られる。好ましく、10~30μmの範囲内である。セルロースエステルフィルムの幅は、1~4mの範囲内のものが好ましく用いられる。4mを超えると搬送が困難となる。
本発明のハードコートフィルムには、反射防止層や導電性層等、その他の層を設けることができる。
本発明に係るハードコートフィルムは、ハードコート層上に反射防止層を塗設して、外光反射防止機能を有する反射防止フィルムとして用いることができる。
セルロースエステルフィルム/ハードコート層/低屈折率層
セルロースエステルフィルム/ハードコート層/高屈折率層/低屈折率層
セルロースエステルフィルム/ハードコート層/中屈折率層/高屈折率層/低屈折率層
ハードコート層/セルロースエステルフィルム/ハードコート層/低屈折率層
ハードコート層/セルロースエステルフィルム/ハードコート層/高屈折率層/低屈折率層
ハードコート層/セルロースエステルフィルム/ハードコート層/中屈折率層/高屈折率層/低屈折率層
低屈折率層/ハードコート層/セルロースエステルフィルム/ハードコート層/低屈折率層
(低屈折率層)
低屈折率層は、シリカ系微粒子を含有することが好ましく、その屈折率は、23℃、波長550nm測定で、1.30~1.45の範囲であることが好ましい。
一般式で表される有機ケイ素化合物は、式中、Rは炭素数1~4のアルキル基を表す。具体的には、テトラメトキシシラン、テトラエトキシシラン、テトライソプロポキシシラン等が好ましく用いられる。
高屈折率層の屈折率は、23℃、波長550nm測定で、屈折率を1.4~2.2の範囲に調整することが好ましい。また、高屈折率層の厚さは5nm~1μmが好ましく、10nm~0.2μmであることが更に好ましく、30nm~0.1μmであることが最も好ましい。屈折率を調整する手段は、金属酸化物微粒子等を添加することで達成できる。 また用いる金属酸化物微粒子の屈折率は1.80~2.60であるものが好ましく、1.85~2.50であるものが更に好ましい。
ハードコートフィルムには、ハードコート層上に導電性層を形成しても良い。設けられる導電性層としては、一般的に広く知られた導電性材料を用いることができる。例えば、酸化インジウム、酸化錫、酸化インジウム錫、金、銀、パラジウム等の金属酸化物を用いることができる。これらは、真空蒸着法、スパッタリング法、イオンプレーティング法、溶液塗布法等により、ハードコートフィルム上に薄膜として形成することができる。また、前記したπ共役系導電性ポリマーである有機導電性材料を用いて、導電性層を形成することも可能である。
本発明のハードコートフィルムを用いた偏光板について述べる。偏光板は一般的な方法で作製することができる。
液晶セルの基板と貼り合わせるためにフィルム片面に用いられる粘着剤層は、光学的に透明であることはもとより、適度な粘弾性や粘着特性を示すものが好ましい。
本発明のハードコートフィルムや本発明に係るセルロースエステルフィルムや本発明のハードコートフィルムを用いた偏光板が、ロール状に巻かれた際の層間に保持される空気層の厚さは、0.5~10μmの範囲が好ましく、より好ましくは1~5μmの範囲である。空気層の厚さ(t’)は、t’=[{π(D2-d2)/4L}-t]の式から求められる値である。
本発明のハードコートフィルムは、画像表示装置に使用することで、視認性(クリア性)に優れた性能が発揮される点で好ましい。画像表示装置としては、反射型、透過型、半透過型液晶表示装置、又はTN型、STN型、OCB型、VA型、IPS型、ECB型等の各種駆動方式の液晶表示装置、タッチパネル表示装置、有機EL表示装置やプラズマディスプレイ等が挙げられる。これら画像表示装置の中でも液晶表示装置やタッチパネル表示装置に本発明のハードコートフィルムを用いた場合、高い視認性に優れる点で好ましい。
タッチパネル表示装置に本発明のハードコートフィルムを用いた場合の一例を図1に示す。
次に、本発明のハードコートフィルムを用いた画像表示装置用ガラス飛散防止フィルムについて説明する。本発明のハードコートフィルムを用いた画像表示装置用ガラス飛散防止フィルムを画像表示装置に使用した概略断面図の一例を図3に示す。
(セルロースエステルフィルム1の作製)
・二酸化ケイ素分散液の調製
アエロジルR812
(日本アエロジル(株)製、一次粒子の平均径7nm) 10質量部
エタノール 90質量部
以上をディゾルバーで30分間撹拌混合した後、マントンゴーリンで分散を行った。二酸化ケイ素分散液に88質量部のメチレンクロライドを撹拌しながら投入し、ディゾルバーで30分間撹拌混合し、二酸化ケイ素分散希釈液を作製した。微粒子分散希釈液濾過器(アドバンテック東洋(株):ポリプロピレンワインドカートリッジフィルターTCW-PPS-1N)で濾過した。
(セルロースエステル樹脂)
セルローストリアセテートA(リンター綿から合成されたセルローストリアセテート、アセチル基置換度2.88、Mn=140000) 90質量部
(添加剤)
一般式(X)で表されるエステル(例示化合物X-1) 5質量部
一般式(X)で表されるエステル(例示化合物X-12) 4質量部
(紫外線吸収剤)
TINUVIN 928(BASFジャパン(株)製) 3質量部
(微粒子)
二酸化ケイ素分散希釈液 4質量部
(溶媒)
メチレンクロライド 432質量部
エタノール 38質量部
以上を密閉容器に投入し、加熱し、撹拌しながら、完全に溶解し、安積濾紙(株)製の安積濾紙No.24を使用して濾過し、ドープ(ドープ組成物1)を調製した。
セルロースエステルフィルム1の作製において、膜厚を表1に記載したように変化させた以外は、同様にしてセルロースエステルフィルム2~5を作製した。
上記作製したセルロースエステルフィルム1のA面(流延ベルトに接していない面)上に、下記のハードコート層組成物1を孔径0.4μmのポリプロピレン製フィルターで濾過したものを、押し出しコーターを用いて塗布し、恒率乾燥区間温度50℃、減率乾燥区間温度50℃で乾燥の後、酸素濃度が1.0体積%以下の雰囲気になるように窒素パージしながら、紫外線ランプを用い照射部の照度が100mW/cm2で、照射量を0.2J/cm2として塗布層を硬化させ、ドライ膜厚2.5μmのハードコート層1を形成して、空気層の厚さが4μmとなるように巻取り、ロール状のハードコートフィルム1を作製した。
〈フッ素-シロキサングラフト化合物の調製〉
フッ素-シロキサングラフト化合物の調製に用いた素材の市販品名を示す。
片末端ラジカル重合性ポリシロキサン(B):サイラプレーンFM-0721(数平均分子量5000;チッソ(株)製)
ラジカル重合開始剤:パーブチルO(t-ブチルパーオキシ-2-エチルヘキサノエート;日本油脂(株)製)
硬化剤:スミジュールN3200(ヘキサメチレンジイソシアネートのビウレット型プレポリマー;住化バイエルウレタン(株)製)
(ラジカル重合性フッ素樹脂の合成)
機械式撹拌装置、温度計、コンデンサー及び乾燥窒素ガス導入口を備えたガラス製反応器に、セフラルコートCF-803(1554質量部)、キシレン(233質量部)、及び2-イソシアナトエチルメタクリレート(6.3質量部)を入れ、乾燥窒素雰囲気下で80℃に加熱した。80℃で2時間反応し、サンプリング物の赤外吸収スペクトルによりイソシアネートの吸収が消失したことを確認した後、反応混合物を取り出し、ウレタン結合を介して50質量%のラジカル重合性フッ素樹脂を得た。
機械式撹拌装置、温度計、コンデンサー及び乾燥窒素ガス導入口を備えたガラス製反応器に、上記合成したラジカル重合性フッ素樹脂(26.1質量部)、キシレン(19.5質量部)、酢酸n-ブチル(16.3質量部)、メチルメタクリレート(2.4質量部)、n-ブチルメタクリレート(1.8質量部)、ラウリルメタクリレート(1.8質量部)、2-ヒドロキシエチルメタクリレート(1.8質量部)、FM-0721(5.2質量部)、及びパーブチルO(0.1質量部)を入れ、窒素雰囲気中で90℃まで加熱した後、90℃で2時間保持した。パーブチルO(0.1部)を追加し、さらに90℃で5時間保持することによって、重量平均分子量が171000である35質量%フッ素-シロキサングラフト化合物の溶液を得た。重量平均分子量はGPCにより求めた。また、フッ素-シロキサングラフト化合物の質量%は、HPLC(液体クロマトグラフィー)により求めた。
ペンタエリスリトールトリ/テトラアクリレート
(NKエステルA-TMM-3L、新中村化学工業(株)製) 70質量部
トリメチロールプロパントリアクリレート
(A-TMPT、新中村化学工業(株)製) 30質量部
(光重合開始剤)
イルガキュア184(BASFジャパン(株)製) 6質量部
(添加剤)
フッ素-シロキサングラフト化合物(35質量%) 2質量部
(溶剤)
プロピレングリコールモノメチルエーテル 20質量部
酢酸メチル 30質量部
メチルエチルケトン 70質量部
[ハードコートフィルム2の作製]
上記作製したハードコートフィルム1の作製において、下記のハードコート層組成物2に変更した以外は同様にしてハードコートフィルム2を作製した。
(活性線硬化樹脂)
ペンタエリスリトールトリ/テトラアクリレート
(NKエステルA-TMM-3L、新中村化学工業(株)製) 70質量部
トリメチロールプロパントリアクリレート
(A-TMPT、新中村化学工業(株)製) 30質量部
(光重合開始剤)
イルガキュア184(BASFジャパン(株)製) 6質量部
(添加剤)
オプツールDAC(フッ素系化合物、ダイキン工業株式会社製)2質量部
(溶剤)
プロピレングリコールモノメチルエーテル 20質量部
酢酸メチル 30質量部
メチルエチルケトン 70質量部
[ハードコートフィルム3の作製]
上記作製したハードコートフィルム1の作製において、下記のハードコート層組成物3に変更した以外は同様にしてハードコートフィルム3を作製した。
(活性線硬化樹脂)
ペンタエリスリトールトリ/テトラアクリレート
(NKエステルA-TMM-3L、新中村化学工業(株)製) 70質量部
トリメチロールプロパントリアクリレート
(A-TMPT、新中村化学工業(株)製) 30質量部
イルガキュア184(BASFジャパン(株)製) 6質量部
(添加剤)
KF-354L
(ポリエーテル変性シリコーンオイル、信越化学工業(株)) 2質量部
(溶剤)
プロピレングリコールモノメチルエーテル 20質量部
酢酸メチル 30質量部
メチルエチルケトン 70質量部
[ハードコートフィルム4の作製]
上記作製したハードコートフィルム1の作製において、下記のハードコート層組成物4に変更した以外は同様にしてハードコートフィルム4を作製した。
(活性線硬化樹脂)
ペンタエリスリトールトリ/テトラアクリレート
(NKエステルA-TMM-3L、新中村化学工業(株)製) 70質量部
トリメチロールプロパントリアクリレート
(A-TMPT、新中村化学工業(株)製) 30質量部
(光重合開始剤)
イルガキュア184(BASFジャパン(株)製) 6質量部
(添加剤)
BYK-UV3510(ポリエーテル変性ポリジメチルシロキサン、ビックケミー・ジャパン株式会社製) 2質量部
(溶剤)
プロピレングリコールモノメチルエーテル 20質量部
酢酸メチル 30質量部
メチルエチルケトン 70質量部
[ハードコートフィルム5の作製]
上記作製したハードコートフィルム1の作製において、下記のハードコート層組成物5に変更した以外は同様にしてハードコートフィルム5を作製した。
(活性線硬化樹脂)
ペンタエリスリトールトリ/テトラアクリレート
(NKエステルA-TMM-3L、新中村化学工業(株)製) 70質量部
トリメチロールプロパントリアクリレート
(A-TMPT、新中村化学工業(株)製) 30質量部
(光重合開始剤)
イルガキュア184(BASFジャパン(株)製) 6質量部
(溶剤)
プロピレングリコールモノメチルエーテル 20質量部
酢酸メチル 30質量部
メチルエチルケトン 70質量部
[ハードコートフィルム6の作製]
上記作製したハードコートフィルム1の作製において、下記のハードコート層組成物6に変更した以外は同様にしてハードコートフィルム6を作製した。
(活性線硬化樹脂)
ペンタエリスリトールトリ/テトラアクリレート
(NKエステルA-TMM-3L、新中村化学工業(株)製) 70質量部
トリメチロールプロパントリアクリレート
(A-TMPT、新中村化学工業(株)製) 30質量部
(光重合開始剤)
イルガキュア184(BASFジャパン(株)製) 6質量部
(添加剤)
KF-354L
(ポリエーテル変性シリコーンオイル、信越化学工業(株)製) 2質量部
(紫外線吸収剤)
TINUVIN 928(BASFジャパン(株)製) 2質量部
(溶剤)
プロピレングリコールモノメチルエーテル 20質量部
酢酸メチル 30質量部
メチルエチルケトン 70質量部
[ハードコートフィルム7の作製]
上記ハードコートフィルム1の作製において、窒素パージをせずに、紫外線ランプを用い照射した以外は、同様にしてロール状のハードコートフィルム7を作製した。
上記ハードコートフィルム2の作製において、窒素パージをせずに、紫外線ランプを用い照射した以外は、同様にしてロール状のハードコートフィルム8を作製した。
上記ハードコートフィルム7の作製において、セルロースエステルフィルム1を表1に記載のセルロースエステルフィルム2~5にそれぞれ変更した以外は同様にしてロール状のハードコートフィルム9~12を作製した。
上記作製したハードコートフィルム1の作製において、下記のハードコート層組成物7に変更した以外は同様にしてハードコートフィルム13を作製した。
(活性線硬化樹脂)
ペンタエリスリトールトリ/テトラアクリレート
(NKエステルA-TMM-3L、新中村化学工業(株)製) 35質量部
ウレタンアクリレート
(NKオリゴ UA-1100H、新中村化学工業(株)製) 65質量部
(光重合開始剤)
イルガキュア184(BASFジャパン(株)製) 6質量部
(添加剤)
KF-354L
(ポリエーテル変性シリコーンオイル、信越化学工業(株)製) 2質量部
(溶剤)
プロピレングリコールモノメチルエーテル 20質量部
酢酸メチル 30質量部
メチルエチルケトン 70質量部
[ハードコートフィルム14の作製]
上記作製したハードコートフィルム1の作製において、下記のハードコート層組成物8に変更した以外は同様にしてハードコートフィルム14を作製した。
(活性線硬化樹脂)
ジペンタエリスリトールペンタアクリレート
(NKエステルA-9550、新中村化学工業(株)製) 35質量部
ウレタンアクリレート
(NKオリゴ UA-1100H、新中村化学工業(株)製) 65質量部
(光重合開始剤)
イルガキュア184(BASFジャパン(株)製) 6質量部
(添加剤)
KF-354L
(ポリエーテル変性シリコーンオイル、信越化学工業(株)製) 2質量部
(溶剤)
プロピレングリコールモノメチルエーテル 20質量部
酢酸メチル 30質量部
メチルエチルケトン 70質量部
[ハードコートフィルム15の作製]
上記作製したハードコートフィルム1の作製において、下記のハードコート層組成物9に変更した以外は同様にしてハードコートフィルム15を作製した。
(活性線硬化樹脂)
ジペンタエリスリトールペンタアクリレート
(NKエステルA-9550、新中村化学工業(株)製) 35質量部
ウレタンアクリレート
(NKオリゴ UA-15HA、新中村化学工業(株)製) 65質量部
(光重合開始剤)
イルガキュア184(BASFジャパン(株)製) 6質量部
(添加剤)
KF-354L
(ポリエーテル変性シリコーンオイル、信越化学工業(株)製) 2質量部
(溶剤)
プロピレングリコールモノメチルエーテル 20質量部
酢酸メチル 30質量部
メチルエチルケトン 70質量部
[ハードコートフィルム16の作製]
上記作製したハードコートフィルム1の作製において、下記のハードコート層組成物10に変更した以外は同様にしてハードコートフィルム16を作製した。
(活性線硬化樹脂)
ジペンタエリスリトールペンタアクリレート
(NKエステルA-9550、新中村化学工業(株)製) 35質量部
ウレタンアクリレート(UA-306I、共栄社化学(株)製)
65質量部
(光重合開始剤)
イルガキュア184(BASFジャパン(株)製) 6質量部
(添加剤)
KF-354L
(ポリエーテル変性シリコーンオイル、信越化学工業(株)製) 2質量部
(溶剤)
プロピレングリコールモノメチルエーテル 20質量部
酢酸メチル 30質量部
メチルエチルケトン 70質量部
[ハードコートフィルム17の作製]
上記作製したハードコートフィルム1の作製において、下記のハードコート層組成物11に変更した以外は同様にしてハードコートフィルム17を作製した。
(活性線硬化樹脂)
ジペンタエリスリトールペンタアクリレート
(NKエステルA-9550、新中村化学工業(株)製) 35質量部
ウレタンアクリレート(UA-306T、共栄社化学(株)製)
65質量部
(光重合開始剤)
イルガキュア184(BASFジャパン(株)製) 6質量部
(添加剤)
KF-354L
(ポリエーテル変性シリコーンオイル、信越化学工業(株)製) 2質量部
(溶剤)
プロピレングリコールモノメチルエーテル 20質量部
酢酸メチル 30質量部
メチルエチルケトン 70質量部
[ハードコートフィルム18の作製]
上記作製したハードコートフィルム1の作製において、下記のハードコート層組成物12に変更した以外は同様にしてハードコートフィルム18を作製した。
(活性線硬化樹脂)
ジペンタエリスリトールペンタアクリレート
(NKエステルA-9550、新中村化学工業(株)製) 35質量部
ウレタンアクリレート
(NKオリゴ UA-1100H、新中村化学工業(株)製) 65質量部
(光重合開始剤)
イルガキュア184(BASFジャパン(株)製) 6質量部
(添加剤)
KF-351A
(ポリエーテル変性シリコーンオイル、信越化学工業(株)製) 2質量部
(溶剤)
プロピレングリコールモノメチルエーテル 20質量部
酢酸メチル 30質量部
メチルエチルケトン 70質量部
[ハードコートフィルム19の作製]
上記作製したハードコートフィルム1の作製において、下記のハードコート層組成物13に変更した以外は同様にしてハードコートフィルム19を作製した。
(活性線硬化樹脂)
ジペンタエリスリトールペンタアクリレート
(NKエステルA-9550、新中村化学工業(株)製) 35質量部
ウレタンアクリレート
(NKオリゴ UA-1100H、新中村化学工業(株)製) 65質量部
(光重合開始剤)
イルガキュア184(BASFジャパン(株)製) 3質量部
イルガキュア907(BASFジャパン(株)製) 3質量部
(添加剤)
KF-351A
(ポリエーテル変性シリコーンオイル、信越化学工業(株)製) 2質量部
(溶剤)
プロピレングリコールモノメチルエーテル 20質量部
酢酸メチル 30質量部
メチルエチルケトン 70質量部
[偏光板101の作製]
ハードコートフィルム1(図4中、HF1と記載。)とセルロースエステルフィルム1(図4中、CE1と記載。)を用いて、偏光板101を作製した。
鹸化度99.95モル%、重合度2400のポリビニルアルコール(以下、PVAと略記する)100質量部に、グリセリン10質量部、及び水170質量部を含浸させたものを溶融混練し、脱泡後、Tダイから金属ローラー上に溶融押出し、製膜した。その後、乾燥・熱処理して、PVAフィルムを得た。
下記工程1~4に従って、偏光膜とセルロースエステルフィルム1とハードコートフィルム1を貼り合わせて偏光板101を作製した。
鹸化工程 2.5mol/L-KOH 50℃ 120秒
水洗工程 水 30℃ 60秒
中和工程 10質量%HCl水溶液 30℃ 45秒
水洗工程 水 30℃ 60秒
鹸化処理後、水洗、中和、水洗の順に行い、次いで100℃で乾燥する。
偏光板101の作製において、ハードコートフィルム1をハードコートフィルム2~19に、それぞれ変更した以外は同様にしてロール状の偏光板102~119を作製した。いずれのロール状偏光板も巻きズレの発生は無かった。
(耐久試験評価)
上記作製したロール状偏光板101を、アルミ防湿シートに包み、長期輸送を想定して50℃相対湿度80%の恒温槽で25日保存した。25日間保存後、以下のようにして粘着層(図4中、NS1と記載。)を設けたのち、液晶表示装置に組み込み、液晶表示装置201を作製した。
偏光板のセルロースエステルフィルム1に市販のアクリル系粘着剤を乾燥後の厚さが25μmとなるように塗布し、110℃のオーブンで5分間乾燥して粘着層を形成後、粘着層に剥離性の保護フィルムを張り付けた。
21.5インチの液晶表示装置(IPS226V-PN、LGエレクトロニクスジャパン(株)製)に液晶層を挟んで設置されている2対の偏光板のうち、観察者側の片面の偏光板を剥がし、上記作製した偏光板101をハードコート層が視認側となるようにして、粘着剤層と液晶セルガラスとを貼合した。観察者側の偏光板の透過軸とバックライト側の偏光板の透過軸とが直交するように配置して、液晶表示装置201を作製した。
液晶表示装置201の作製において、偏光板101を偏光板102~119に、それぞれ変更した以外は同様にして、偏光板の耐久試験後、液晶表示装置に組み込み、液晶表示装置202~219を作製した。
上記作製したハードコートフィルム、偏光板及び液晶表示装置について以下の内容について評価した。
・アルカリ処理前後の対水接触角の差(θΔ)
ハードコートフィルム1~19のアルカリ処理前の各ハードコート層の対水接触角(θ)から、偏光板作製時のアルカリ処理後の各ハードコート層の対水接触角(θa)を引いて、アルカリ処理前後の対水接触角の差(θΔ)とした。
・巻きズレ評価
上記作製したロール状偏光板101~119を架台に載せて、汎用型振動試験装置Jシリーズ(IMV株式会社製)を用いて、JIS Z0232に準じて振動試験を1時間行い、振動試験後の巻きズレ箇所と巻きズレていない箇所の差を曲尺で測定し、以下の基準で評価した。
○:5mm未満
△:5mm以上、10mm以下
×:10mm超過(実用上問題あり)
3.液晶表示装置
液晶表示装置201~219についてムラと平面性を評価することで、視認性を評価した。
a.ムラ評価
上記作製した各液晶表示装置を黒表示で正面から観察し、以下の基準でムラを評価した。
○:僅かに変形起因のムラが認められる
△:細かな変形起因のムラが認められる
×:変形起因のムラが認められる。
b.平面性評価
上記作製した各液晶表示装置を、床から80cmの高さの机上に配置し、床から3mの高さの天井部に、昼色光直管蛍光灯(FLR40S・D/M-X パナソニック(株)製)40W×2本を1セットとして、1.5m間隔で10セット配置した。この場合、評価者が液晶表示パネルの表示面の正面にいるときに、評価者の頭上より後方に向けて天井部に蛍光灯がくるように配置し、平面性を以下の基準で評価した。
○:蛍光灯が若干曲がったように見えるところがある
△:蛍光灯が曲がって見える
×:蛍光灯が大きく畝って見える
以上の評価結果を表1に示した。
実施例1のハードコートフィルム3の作製において、ハードコート層の減率乾燥区間温度を表2に記載したように変更した以外は同様にして、ハードコートフィルム20~24を作製した。更に、実施例1の偏光板103と同様にして、ハードコートフィルム20~24をそれぞれ用いて、ロール状偏光板120~124を作製した。いずれも巻きズレ発生は無かった。
実施例1のハードコートフィルム3の作製において、ハードコート層組成物の活性線硬化樹脂を表3に記載したように変更した以外は同様にして、ハードコートフィルム25及び26を作製した。更に実施例1の偏光板103と同様にして、ハードコートフィルム25及び26を用いて偏光板125及び126を作製した。いずれも巻きズレ発生は無かった。
実施例1のセルロースエステルフィルム1のドープ組成物1の調製において、添加剤X-12の4質量部に変えて、以下に合成したアクリル系ポリマーを8質量部添加した以外は同様にしてドープ組成物2を調製した。次いで、セルロースエステルフィルム1の作製において、テンターによるTD方向の延伸条件を表4に記載したように変更した以外は、同様にしてセルロースエステルフィルム6~9を作製した。いずれも巻きズレ発生は無かった。
メチルアクリレート 10質量部
2-ヒドロキシエチルアクリレート 1質量部
アゾビスイソブチロニトリル(AIBN) 1質量部
トルエン 30質量部
上記組成物を四つ口フラスコ(投入口、温度計、環流冷却管、窒素導入口、撹拌機を装着)に投入し、徐々に80℃まで昇温し、撹拌しながら5時間重合を行い、重合終了後ポリマー溶液を多量のメタノールに投入して沈殿させ、更にメタノールで洗浄し、精製して乾燥し重量平均分子量5,000(GPCにて測定)のアクリル系ポリマーを得た。
Rth=((nx+ny)/2-nz)×dである。
(式中、nxは基材フィルム面内の遅相軸方向の屈折率、nyは基材フィルム面内で遅相軸に直交する方向の屈折率、nzは基材フィルムの厚さ方向の屈折率、dは基材フィルムの厚さ(nm)をそれぞれ表す。)
これら得られた結果は、表4に示した。
次に、両面ハードコートフィルム26~30について、以下の方法で導電性膜を形成し、導電性ハードコートフィルム1~5を作製した。
実施例1のハードコートフィルム3の作製において、セルロースエステルフィルム1をセルロースエステルフィルム6に変更した以外は同様にして、ハードコートフィルム31を作製した。また、ハードコートフィルム31を用いて、実施例1の偏光板作製において、ハードコートフィルムとは反対面に貼り合わせるセルロースエステルフィルム1をセルロースエステルフィルム6に変更した以外は同様にして、ロール状偏光板127を作製した。また、ハードコートフィルム25を用いて、実施例1と同様にして、ロール状偏光板128を作製した。いずれも巻きズレ発生は無かった。
・色味変化
液晶表示装置を黒表示画面で正面方向や視野方向を変えて見て、視認性を以下の基準で評価した。
(基材レス粘着シートの作製)
剥離シート(商品名:SP-PET381031、厚さ38μm、リンテック社製)の剥離面に、ダイコーターを用いて、乾燥後の厚さが15μmとなるように粘着剤含有組成物1を塗布し、120℃で2分間乾燥して、粘着剤層を形成し、剥離シートと、剥離面に形成された粘着剤層とからなる基材レス粘着シートを得た。
以下の組成物を撹拌して、粘着剤含有組成物1を調製した。
・n-ブチルアクリレート79質量%、メチルアクリレート20質量%、
2-ヒドロキシエチルアクリレート1質量%を共重合して得られたアクリル
酸エステル共重合体(分子量80万、濃度35質量%) 100質量部
・トルエン及びキシリレンジイソシアネート系3官能性アダクト体(商品名
:TD-75、濃度75質量%、綜研化学社製) 0.1質量部
[画像表示装置用ガラス飛散防止フィルム、及び画像表示装置の作製]
実施例1で作製したロール状のハードコートフィルム1~19をアルミ防湿シートに包み、長期輸送を想定して温度50℃、相対湿度80%の恒温槽で25日保存し、耐久試験を実施した。耐久試験後、ハードコートフィルム1~19の両面に基材レス粘着シートの粘着剤層を貼り合せて、画像表示装置用ガラス飛散防止フィルム1~19を得た。
・視認性評価
天井部に、昼色光直管蛍光灯(FLR40S・D/M-X パナソニック(株)製)40W×2本を1セットとして、1.5m間隔で10セット配置した室内で、画像表示装置を黒表示の状態で、様々な角度から観察し、画像表示装置に写った反射光の状態を以下の基準で評価した。
○ :画像表示装置に写った反射光の干渉縞が全く見えないレベル
× :画像表示装置に写った反射光の干渉縞が僅かに見え、実用上問題となるレベル
××:画像表示装置に写った反射光の干渉縞がはっきりと確認できるレベル。
耐久試験後のハードコートフィルム1~19の非コート面(ハードコート層が設けられている面とは反対側の面)だけに、基材レス粘着シートの粘着剤層を貼り合せた画像表示装置用ガラス飛散防止フィルム1~19を、厚さ1mmのガラス板と貼り合わせた。
11 両面ハードコートフィルム
12 導電性膜
13 ガラス基板
14 スペーサー
15 導電性膜
20 インナータッチパネル付き画像表示装置
21A ハードコート層
21B ハードコート層
21C セルロースエステルフィルム
21D 導電性膜(ITO層)
21E 液晶セル
21F1 上面側偏光板
21F2 下面側偏光板
21G 反射板
DS ドット・スペーサー
30 画像表示装置
31 画像表示パネル
32 粘着剤層
33 導電性ガラス基板
34 ガラス基板
35 導電性膜
41 画像表示装置用ガラス飛散防止フィルム
42 ハードコートフィルム
43 粘着剤層
CE1 セルロースエステルフィルム
HC1 ハードコート層
KF1 ハードコートフィルム
PV1 偏光膜
NS1 粘着層
Claims (10)
- 膜厚が5~34μmの範囲内であるセルロースエステルフィルムの少なくとも一方の面にハードコート層を有するハードコートフィルムであって、該ハードコート層が下記条件でアルカリ処理されたときのアルカリ処理前後の対水接触角の差(θΔ)が、5~55°の範囲内であることを特徴とするハードコートフィルム。
(アルカリ処理条件)
アルカリ溶液:2.5mol/L水酸化カリウム溶液
処理温度:50℃
処理時間:120秒 - 前記ハードコート層の前記アルカリ処理前の対水接触角(θ)が、50~120°の範囲内であることを特徴とする請求項1に記載のハードコートフィルム。
- 前記ハードコート層の対水接触角が、前記アルカリ処理条件で、アルカリ処理前に比べてアルカリ処理後に低下することを特徴とする請求項1又は請求項2に記載のハードコートフィルム。
- 前記ハードコート層の算術平均粗さRa(JIS B0601:2001)が、2~100nmの範囲内であることを特徴とする請求項1から請求項3までのいずれか一項に記載のハードコートフィルム。
- 前記ハードコート層が、活性エネルギー線硬化型のイソシアヌレート誘導体を含有することを特徴とする請求項1から請求項4までのいずれか一項に記載のハードコートフィルム。
- 前記セルロースエステルフィルムが、温度23℃・相対湿度55%の環境下、光波長590nmでリターデーション値を測定したとき、面内リターデーション値Roが0~10nmの範囲内であり、かつ厚さ方向のリターデーション値Rthが-10~10nmの範囲内であることを特徴とする請求項1から請求項5までのいずれか一項に記載のハードコートフィルム。
- 請求項1から請求項6までのいずれか一項に記載のハードコートフィルムと、膜厚が5~34μmの範囲内であるセルロースエステルフィルムとを用いて偏光素子を挟持したことを特徴とする偏光板。
- 請求項1から請求項6までのいずかれ一項に記載のハードコートフィルムを用いることを特徴とする画像表示装置用ガラス飛散防止フィルム。
- 請求項1から請求項6までのいずれか一項に記載のハードコートフィルムを有することを特徴とするタッチパネル。
- 請求項7に記載の偏光板を液晶セルの少なくとも一方の面に有することを特徴とする液晶表示装置。
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JP2017049310A (ja) * | 2015-08-31 | 2017-03-09 | 富士フイルム株式会社 | 調光装置 |
CN106007794A (zh) * | 2016-05-16 | 2016-10-12 | 北京航空航天大学 | 一种溶剂诱导超疏水薄膜浸润性变化的方法及用途 |
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