WO2017141680A1 - Film de polyester et son procédé de fabrication, film de revêtement dur et son procédé de fabrication, appareil d'affichage d'image et écran tactile - Google Patents

Film de polyester et son procédé de fabrication, film de revêtement dur et son procédé de fabrication, appareil d'affichage d'image et écran tactile Download PDF

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Publication number
WO2017141680A1
WO2017141680A1 PCT/JP2017/003241 JP2017003241W WO2017141680A1 WO 2017141680 A1 WO2017141680 A1 WO 2017141680A1 JP 2017003241 W JP2017003241 W JP 2017003241W WO 2017141680 A1 WO2017141680 A1 WO 2017141680A1
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Prior art keywords
film
polyester film
hard coat
group
layer
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PCT/JP2017/003241
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English (en)
Japanese (ja)
Inventor
真一 中居
啓吾 植木
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富士フイルム株式会社
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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=59625847&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2017141680(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by 富士フイルム株式会社 filed Critical 富士フイルム株式会社
Priority to KR1020187023552A priority Critical patent/KR102222794B1/ko
Priority to KR1020217005601A priority patent/KR102455947B1/ko
Priority to CN201780010643.6A priority patent/CN108602237A/zh
Priority to JP2018500014A priority patent/JP6594518B2/ja
Publication of WO2017141680A1 publication Critical patent/WO2017141680A1/fr

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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
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
    • B29C55/08—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique transverse to the direction of feed
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • 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
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • 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
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers

Definitions

  • the present disclosure relates to a polyester film and a manufacturing method thereof, a hard coat film and a manufacturing method thereof, an image display device, and a touch panel.
  • hard coat film is a protective film on the outermost surface of an image display device such as a touch panel.
  • Patent Document 1 states that “a laminated base material in which a functional layer is formed on one surface to form a laminated body, A light-transmitting substrate having in-plane birefringence; A refractive index adjusting layer laminated with a light transmissive substrate and having in-plane birefringence, comprising a refractive index adjusting layer that is positioned between the light transmissive substrate and the functional layer, Refractive index n 1x in the slow axis direction that is the direction with the highest refractive index in the plane of the light transmissive substrate, and refractive index n of the refractive index adjusting layer in a direction parallel to the slow axis direction of the light transmissive substrate.
  • the refractive index n 3y of the functional layer in the direction parallel to the fast axis direction of the light transmissive substrate is n 1y ⁇ n 2y ⁇ n 3y or n 1y > n 2y > n 3y
  • a laminated base material that satisfies the following relationship is disclosed.
  • Patent Document 2 states that “a coating layer is formed on both surfaces of a multilayer polyester film having a laminated structure of at least three layers, the polyester layers of both outermost layers have a higher softening point than the intermediate layer, and the surface of one coating layer A surface protective film comprising a pressure-sensitive adhesive layer, wherein the coating layer is formed from a coating solution containing 70% by weight or more of a crosslinking agent with respect to the nonvolatile component " Yes.
  • uniaxially oriented polyester film having the following characteristics: (1) The film surface has 1 or less scratches per 1 m 2 in height difference, and 20 or less scratches per 1 m 2 in height difference of 0.3 ⁇ m or more and less than 1 ⁇ m, (2) The film has 1 or less foreign matter having a major axis of 100 ⁇ m or more per 1 m 2 , (3) The film surface has a three-dimensional average surface roughness (SRa) in the range of 0.020 to 0.060 ⁇ m, and (4) the maximum orientation principal axis of the film measured with a microwave transmission type molecular orientation meter The distortion is within 7 degrees. Is disclosed.
  • Patent Document 4 states that “a uniaxially oriented coextruded laminated film composed of at least three polyester layers of A layer, B layer and C layer, and the outermost layer A and C layers have an average particle size of 0.
  • the layer B which is a substantially homogenous polyester containing 0.01 to 0.5% by weight of inert particles of 1 to 5.0 ⁇ m, is a dicarboxylic acid component, aliphatic or cycloaliphatic.
  • the ratio of the thickness of the B layer to the total film thickness comprising a diol component and a polyalkylene ether glycol component having a number average molecular weight of 300 to 4000 as a main component and a polyester containing 10 to 35% by weight of the polyalkylene ether glycol component
  • Uniaxially oriented laminated polyester film characterized in that is 65 to 95%.
  • JP2013-257550A Japanese Patent Laying-Open No. 2015-128897 JP 2005-2220 A JP 2004-351788 A International Publication No. 2015/46122
  • the shear plane normal stress is insufficient, and dents are likely to occur when a load is locally applied in the thickness direction of the film. It is considered that when a hard coat film obtained by laminating a hard coat layer on these films and punching is performed, the hard coat layer is easily cracked or peeled off.
  • An object of the present disclosure is to provide a polyester film that hardly causes a dent even when a load is locally applied in the thickness direction of the film, and a method for manufacturing the polyester film.
  • the present disclosure provides a hard coat film in which cracking and peeling of the hard coat layer are unlikely to occur when a hard coat film in which a hard coat layer is laminated on a polyester film is produced and punched, and a method for producing the same. With the goal.
  • an object of the present disclosure is to provide an image display device and a touch panel in which a reduction in visibility due to rainbow unevenness is suppressed even when a load is locally applied to the display screen.
  • ⁇ 1> The thickness is 40 to 500 ⁇ m, and the average value of the shear plane normal stress A in the slow axis direction in the surface layer of 1 ⁇ m and the shear plane normal stress B in the direction perpendicular to the slow axis direction in the film plane is 30 to A polyester film that is 100 MPa.
  • ⁇ 2> The polyester film according to ⁇ 1>, which is for a base film of a hard coat film.
  • ⁇ 3> The polyester film according to ⁇ 1> or ⁇ 2>, which is a uniaxially oriented polyester film.
  • ⁇ 4> The polyester film according to any one of ⁇ 1> to ⁇ 3>, wherein an in-plane retardation Re at a measurement wavelength of 589 nm of the polyester film is 4000 to 50000 nm.
  • ⁇ 5> The average value of the shear plane yield stress in the slow axis direction in the surface layer of 1 ⁇ m of the polyester film and the shear plane yield stress in the direction perpendicular to the slow axis direction in the film plane is 20 to 60 MPa.
  • ⁇ 1> The polyester film as described in any one of ⁇ 4>.
  • ⁇ 6> The polyester film according to any one of ⁇ 1> to ⁇ 5>, wherein the ratio of the shear plane normal stress A to the shear plane normal stress B is 1.1 to 2.0.
  • ⁇ 7> The ratio of the in-plane retardation Re to the retardation Rth in the film thickness direction at a measurement wavelength of 589 nm of the polyester film is 0.6 to 1.2. Any one of ⁇ 1> to ⁇ 6> The polyester film as described. ⁇ 8> A base film comprising the polyester film according to any one of ⁇ 1> to ⁇ 7>, A hard coat layer laminated on at least one side of the base film; Hard coat film having ⁇ 9> The hard coat film according to ⁇ 8>, wherein the thickness of the hard coat layer is 5 ⁇ m or more.
  • Hard coat layer At least a structure derived from a) below, a structure derived from b) below, c) and d) below, When the total solid content of the hard coat layer is 100% by mass, the structure derived from the following a) is 15 to 70% by mass, the structure derived from the following b) is 25 to 80% by mass, and the following c) The hard coat film according to ⁇ 8> or ⁇ 9>, containing 0.1 to 10% by mass and 0.1 to 10% by mass of the following d).
  • a touch panel comprising the hard coat film according to any one of ⁇ 8> to ⁇ 10>, wherein the hard coat film is disposed on the outermost surface.
  • the surface temperature at the start of the transverse stretching is controlled to 80 ° C. or more and 95 ° C. or less, and the surface temperature at the end of the transverse stretching is controlled to 90 ° C. or more and 105 ° C. or less.
  • a transverse stretching step for controlling the range to be less than double A heat setting step of heat-setting the polyester film after the transverse drawing step by heating to the maximum temperature in the transverse drawing apparatus,
  • a method for producing a polyester film comprising producing a polyester film having a thickness of 40 to 500 ⁇ m.
  • the surface temperature is gradually increased at a heating rate of 60 ° C./min or less,
  • the surface temperature when the transverse draw ratio is in the range of 1 to less than 2 times is 80 to 92 ° C.
  • the surface temperature when the transverse draw ratio is in the range of 2 times or more and less than 3 times is 85 ° C. or more and 97 ° C. or less
  • ⁇ 13> The method for producing a polyester film according to ⁇ 13>, wherein the surface temperature when the transverse draw ratio is in the range of 3 times or more is controlled to 90 ° C. or higher and 102 ° C. or lower.
  • the rate of temperature increase of the surface temperature of the polyester film from the end of the transverse stretching step to the maximum temperature in the heat setting step is controlled to 1000 ° C./min or less, ⁇ 13> or ⁇ 14>, wherein the maximum surface temperature of the polyester film in the heat setting step is controlled to 130 ° C. or more and 230 ° C. or less, and the time that the surface temperature of the polyester film exceeds 130 ° C. is controlled to 180 seconds or less.
  • a method for producing a polyester film. ⁇ 16> The polyester film according to any one of ⁇ 13> to ⁇ 15>, further comprising a heat relaxation step of heating the polyester film after the heat setting step and shrinking at least the length of the polyester film in the lateral direction. Manufacturing method.
  • ⁇ 17> a step of producing a polyester film by the method for producing a polyester film according to any one of ⁇ 13> to ⁇ 16>; Laminating a hard coat layer on at least one side of the polyester film; The manufacturing method of the hard coat film which has this.
  • a polyester film that hardly causes a dent even when a load is locally applied in the thickness direction of the film, and a method for manufacturing the polyester film.
  • a hard coat film in which a hard coat layer is hardly cracked and peeled when a hard coat film in which a hard coat layer is laminated on a polyester film is manufactured and punched, and a method for manufacturing the hard coat film are provided. Is done.
  • an image display device and a touch panel in which a reduction in visibility due to rainbow unevenness is suppressed even when a load is locally applied to the display screen.
  • a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value. Further, when a unit is attached to one of the numerical values described before and after “to”, it means that the unit is the same throughout the numerical range.
  • the polyester film according to the present embodiment (hereinafter also simply referred to as “film”) has a thickness of 40 to 500 ⁇ m, a shear plane normal stress A in the slow axis direction in the surface layer of 1 ⁇ m, and a slow axis direction in the film plane.
  • the average value with the shear plane normal stress B in the orthogonal direction is 30 to 100 MPa.
  • the “slow axis direction” of the film is a direction in which the refractive index becomes maximum in the film plane, and the direction orthogonal to the slow axis direction in the film plane is also referred to as “fast axis direction”.
  • the manufacturing method of the polyester film which concerns on this embodiment is explained in full detail behind, for example, after melt-extruding a polyester resin composition in a film form, it conveys using a roll etc., At least the conveyance direction (the length of a film) of a film
  • the conveyance direction of a film may be called MD (Machine Direction)
  • TD Transverse Direction
  • the thickness of the polyester film according to this embodiment is 40 to 500 ⁇ m. If the thickness of the polyester film is 40 ⁇ m or more, it has sufficient rigidity and is easy to use as a glass substitute material. If it is 500 ⁇ m or less, the rigidity is not too strong, and the punching and handling properties of the film are good. From this viewpoint, the thickness of the polyester film according to this embodiment is more preferably 60 to 400 ⁇ m, and further preferably 80 to 300 ⁇ m.
  • the thickness of the polyester film according to the present embodiment is sampled, for example, using a contact film thickness meter, sampling 50 points each in the slow axis direction of the film and in the direction perpendicular to the slow axis direction in the film plane, The average thickness of the measured values of the thickness at these points is determined and taken as the thickness of the polyester film.
  • the polyester film according to the present embodiment has an average value of the shear plane normal stress A in the slow axis direction in the surface layer of 1 ⁇ m and the shear plane normal stress B in the direction perpendicular to the slow axis direction in the film plane (hereinafter referred to as “surface layer”). It may be referred to as “average shear plane normal stress”)) is 30 to 100 MPa.
  • surface layer of 1 ⁇ m means a region from the surface of the polyester film to a depth of 1 ⁇ m.
  • the surface layer average shear plane normal stress in the surface layer of 1 ⁇ m is 30 MPa or more, when a hard coat layer is laminated on the polyester film to form a hard coat film, the film is hardly dented and is not easily formed, and is 100 MPa or less. When it is made into a hard-coat film, it is hard to produce a crack or peeling in a hard-coat layer.
  • the surface layer average shear plane normal stress of the polyester film according to this embodiment is preferably 40 to 90 MPa, and more preferably 50 to 80 MPa.
  • the ratio (A / B) of the shear plane normal stress A to the shear plane normal stress B is preferably 1.1 to 2.0. If the ratio A / B of shear plane normal stress of the polyester film according to the present embodiment is 1.1 or more, it is easy to produce a uniaxially oriented polyester film in which rainbow unevenness is suppressed, and if it is 2.0 or less. When a hard coat layer is laminated on a polyester film to form a hard coat film, the hard coat layer is hardly cracked or peeled off. From such a viewpoint, the ratio A / B of the shear plane normal stress of the polyester film according to the present embodiment is more preferably 1.2 to 1.9, and further preferably 1.3 to 1.8.
  • the polyester film according to this embodiment has an average value of the shear surface yield stress in the slow axis direction at the surface layer of 1 ⁇ m and the shear surface yield stress in the direction perpendicular to the slow axis direction in the film plane (hereinafter referred to as “surface layer average stress”). It may be referred to as “cross-sectional yield stress”)) is preferably 20 to 60 MPa. If the surface layer average shear surface yield stress of the polyester film according to the present embodiment is 20 MPa or more, the film has dents even when the hard coat layer is laminated on the polyester film to form a hard coat film with a strong force.
  • the surface layer average shear surface yield stress of the polyester film according to this embodiment is more preferably 25 to 55 MPa, and further preferably 30 to 50 MPa.
  • 1 and 2 are schematic diagrams for explaining a method for measuring shear plane normal stress and shear plane yield stress of a film surface layer.
  • the measuring device, measurement conditions, and shear surface normal stress and shear surface yield stress calculation methods are as follows.
  • the SAIC Surface And Interfacial Cutting Analysis System
  • SAICAS can control the cutting edge speed and monitor the vertical force Fv and horizontal force F H applied to the cutting edge 10 and the vertical displacement d of the cutting edge.
  • the rake angle ⁇ and the rake angle (cutting angle) ⁇ of the cutting edge 10 with respect to the surface of the film 12 are set to predetermined angles, respectively, and cut into the inside from the film surface by the cutting edge (FIG. 1A). ). A shear fracture occurs due to the cutting with the cutting blade 10, and the cutting force is monitored (FIG. 1B). The surface layer of the film 12 is cut to a depth of 1 ⁇ m and the stress (film strength) acting on the shear surface is evaluated (FIG. 1C).
  • the measurement conditions are as follows.
  • Cutting speed horizontal speed 100 nm / s, vertical speed 10 nm / s ⁇ Blade width: 0.1 mm ⁇ Rake angle ⁇ : 20 ° ⁇ Cutting angle ⁇ : 10 ° ⁇ Blade type: Diamond cutting edge ⁇ Direction: Measured in each of slow axis direction and fast axis direction (TD, MD) ⁇ Measured 3 points at 10 mm intervals along each direction, and average value in each direction And
  • FIG. 2 shows a sample (polyester film) 12 with a cutting angle ⁇ from (A) to (C) in FIG. Indicates the direction of the force that acts when cutting.
  • Force F N acting on the force F S perpendicular acting in parallel to the sample shear plane A-B is determined by the following equation (1) using in each horizontal force monitoring F H and the vertical force F V, the shear angle ⁇ It is done.
  • shear angle ⁇ is obtained by the following equation (3) using the rake angle ⁇ and the friction angle ⁇ .
  • the depth distribution of the shear surface yield stress ⁇ s or the shear surface normal stress ⁇ s can be calculated by obtaining the shear angle ⁇ from the horizontal force F H and the vertical force F V at each depth.
  • the polyester film according to this embodiment is preferably a uniaxially oriented polyester film.
  • a polyester film having the above-described thickness and shear plane normal stress is easily obtained by transversely stretching and heat-fixing an unstretched polyester film formed by melt film formation or solution film formation by a method described later.
  • the polyester film according to this embodiment preferably has an in-plane retardation Re of 4000 to 50000 nm at a measurement wavelength of 589 nm. If Re of the polyester film according to the present embodiment is 4000 nm or more, rainbow unevenness is difficult to be visually recognized. It becomes. From this point of view, Re at a measurement wavelength of 589 nm of the polyester film according to this embodiment is more preferably 5000 to 40000 nm, and further preferably 7000 to 33000 nm.
  • the ratio of the in-plane retardation Re to the retardation Rth in the film thickness direction (Re / Rth) at a measurement wavelength of 589 nm is preferably 0.6 to 1.2. . If the Re / Rth at the measurement wavelength of 589 nm of the polyester film according to this embodiment is 0.6 or more, rainbow unevenness is hardly visible, and if it is 1.2 or less, the film is difficult to become brittle. From this viewpoint, the Re / Rth of the polyester film according to this embodiment is more preferably 0.7 to 1.15, and further preferably 0.8 to 1.1.
  • the retardation Rth in the thickness direction at a measurement wavelength of 589 nm of the polyester film according to this embodiment is preferably 3000 to 80000 nm, more preferably 4000 to 60000 nm, and still more preferably 6000 to 40000 nm. If Rth is 3000 nm or more, it is easy to make a film, and if it is 80000 nm or less, when a hard coat film using the polyester film according to the present embodiment is applied to, for example, a display screen of an image display device, rainbow unevenness appears on the screen. It is less likely to occur and is preferable.
  • Rainbow irregularity can also be reduced by setting an appropriate value for the Nz value representing the relationship between Re and Rth, and the absolute value of the Nz value is 2.0 or less due to the effect of reducing the rainbow irregularity and manufacturing suitability. Is more preferable, 0.5 to 2.0 is more preferable, and 0.5 to 1.5 is still more preferable. Since rainbow unevenness is generated by incident light, it is usually observed during white display.
  • the in-plane retardation Re of the polyester film according to this embodiment is represented by the following formula (4).
  • nx is the refractive index in the in-plane slow axis direction of the polyester film
  • ny is the refractive index in the in-plane fast axis direction (direction perpendicular to the in-plane slow axis direction) of the polyester film
  • y 1 is the thickness of the polyester film.
  • the retardation Rth in the thickness direction of the polyester film according to this embodiment is represented by the following formula (5).
  • Rth ⁇ (nx + ny) / 2 ⁇ nz ⁇ ⁇ y 1
  • nz is the refractive index in the thickness direction of the polyester film.
  • the Nz value of the polyester film is represented by the following formula.
  • Nz (nx ⁇ nz) / (nx ⁇ ny)
  • Re, Rth, and Nz at a wavelength ⁇ nm can be measured as follows. Using two polarizing plates, the orientation axis direction (slow axis direction and fast axis direction) of the polyester film is obtained, and a 4 cm ⁇ 2 cm rectangle is cut out so that the orientation axis directions are orthogonal to each other, and used as a measurement sample. .
  • the biaxial refractive index (Nx, Ny) perpendicular to each other and the refractive index (Nz) in the thickness direction were determined by an Abbe refractometer (Atago Co., Ltd., NAR-4T, measurement wavelength 589 nm).
  • the absolute value of the refractive index difference (
  • the thickness y 1 (nm) of the polyester film was measured using an electric micrometer (manufactured by Fine Reef, Millitron 1245D), and the unit was converted to nm. Measured Nx, Ny, Nz, Re from the value of y 1, Rth, Nz was calculated.
  • the above Re and Rth can be adjusted by the type of polyester resin used in the film, the amount of the polyester resin and the additive, the addition of the retardation developer, the film thickness, the film stretching direction and the stretching ratio, and the like. .
  • the polyester film according to the present embodiment includes a polyester resin.
  • the mass ratio of the polyester resin in the entire film is usually 50% by mass or more, preferably 70% by mass or more, and more preferably 90% by mass or more.
  • the polyester film according to the present embodiment may be a single layer film having a polyester resin as a main component, or may be a multilayer film having at least one layer having a polyester resin as a main component.
  • the polyester film which concerns on this embodiment may be surface-treated on both surfaces or one side of the film.
  • the surface treatment may be surface modification by corona treatment, saponification treatment, heat treatment, ultraviolet irradiation, electron beam irradiation or the like, or may be thin film formation by coating or vapor deposition of polymer, metal or the like.
  • the polyester film according to the present embodiment may have an easy adhesion layer on at least one side.
  • the thickness of the easy adhesion layer contained in the polyester film according to this embodiment is preferably 30 to 300 nm, more preferably 40 to 200 nm, and still more preferably 50 to 150 nm. If the thickness of an easily bonding layer is 30 nm or more, the cushion effect by an easily bonding layer will be easy to be acquired, and it will be suppressed that a shear plane normal stress and a shear plane yield stress rise too much. Moreover, if the thickness of an easily bonding layer is 300 nm or less, the cushioning effect of an easily bonding layer is not too strong, and it is suppressed that a shear plane normal stress and a shear plane yield stress fall too much.
  • the easy-adhesion layer contains particles, and the height at which the particles protrude from the surface of the easy-adhesion layer is equal to or greater than the film thickness of the easy-adhesion layer.
  • the height at which the particles protrude from the surface of the easy adhesion layer is an average value at 5 points in the 1 mm square easy adhesion layer.
  • the type of particles is not particularly limited, and specific examples include particles such as silica, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, calcium phosphate, magnesium phosphate, kaolin, aluminum oxide, titanium oxide, and zirconium oxide. Of these, silica, aluminum oxide, titanium oxide, and zirconium oxide are preferable. Further, the heat-resistant organic particles described in JP-B-59-5216, JP-A-59-217755 and the like may be used. Examples of other heat-resistant organic particles include thermosetting urea resins, thermosetting phenol resins, thermosetting epoxy resins, benzoguanamine resins, and the like.
  • the particle diameter is preferably such that the height at which the particles protrude from the surface of the easy adhesion layer is equal to or greater than the film thickness of the easy adhesion layer. It is preferable to use particles adjusted with the primary average particle diameter, but as a result, the particles may be aggregated so that the height at which the particles protrude from the surface of the easy-adhesion layer is equal to or greater than the film thickness of the easy-adhesion layer. . In the case of agglomerated particles, the height at which the particles protrude from the surface of the easy adhesion layer can be confirmed by measuring the secondary average particle diameter.
  • polyester resin contained in the polyester film according to the present embodiment for example, a polyester resin having a composition of [0042] of WO2012 / 157762 is preferably used.
  • polyester resins polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), polycyclohexanedimethylene terephthalate (PCT), etc. can be used. More preferably, PET is more preferable. PEN tends to have a small Re / Rth.
  • PET is more preferable.
  • PEN tends to have a small Re / Rth.
  • polyethylene terephthalate is most preferable, but polyethylene naphthalate can also be preferably used.
  • polyethylene naphthalate described in JP-A-2008-39803 can be preferably used.
  • Polyethylene terephthalate is a polyester having a structural unit derived from terephthalic acid as a dicarboxylic acid component and a structural unit derived from ethylene glycol as a diol component, and 80 mol% or more of all repeating units are preferably ethylene terephthalate.
  • the structural unit derived from other copolymerization components may be included.
  • copolymer components include isophthalic acid, p- ⁇ -oxyethoxybenzoic acid, 4,4′-dicarboxydiphenyl, 4,4′-dicarboxybenzophenone, bis (4-carboxyphenyl) ethane, adipic acid, Dicarboxylic acid components such as sebacic acid, 5-sodium sulfoisophthalic acid, 1,4-dicarboxycyclohexane, propylene glycol, butanediol, neopentyl glycol, diethylene glycol, cyclohexanediol, ethylene oxide adduct of bisphenol A, polyethylene glycol, polypropylene Examples thereof include diol components such as glycol and polytetramethylene glycol.
  • dicarboxylic acid components and diol components can be used in combination of two or more if necessary.
  • an oxycarboxylic acid such as p-oxybenzoic acid can be used in combination with the carboxylic acid component or the diol component.
  • a dicarboxylic acid component and / or a diol component containing a small amount of an amide bond, a urethane bond, an ether bond, a carbonate bond, or the like may be used.
  • the production method of polyethylene terephthalate includes terephthalic acid and ethylene glycol, so-called direct polymerization method in which other dicarboxylic acids and / or other diols are directly reacted if necessary, dimethyl ester of terephthalic acid and ethylene glycol, if necessary
  • Any production method such as a so-called transesterification method in which a dimethyl ester of another dicarboxylic acid and / or another diol is transesterified can be applied.
  • the intrinsic viscosity IV (Intrinsic Viscosity) of the polyester resin is preferably 0.5 or more and 0.9 or less, more preferably 0.52 or more and 0.8. Hereinafter, it is more preferably 0.54 or more and 0.7 or less. In order to make such IV, when synthesizing a polyester resin, in addition to the melt polymerization described later, solid phase polymerization may be used in combination.
  • the acetaldehyde content of the polyester resin is preferably 50 ppm or less. More preferably, it is 40 ppm or less, Most preferably, it is 30 ppm or less. Acetaldehyde easily causes a condensation reaction between acetaldehydes, and water is generated as a side reaction product, which may cause hydrolysis of the polyester. The lower limit of the acetaldehyde content is practically about 1 ppm.
  • Sb, Ge, Ti and / or Al-based catalyst is used, preferably Sb, Ti and / or Al-based catalyst, more preferably Al-based catalyst.
  • the polyester resin used as the raw material resin is a resin polymerized using an aluminum catalyst.
  • an Al-based catalyst it becomes easier for Re to be expressed than when other catalysts (for example, Sb or Ti) are used, and PET can be thinned.
  • the use of an Al-based catalyst means that the orientation is easier. This is presumed to be due to the following reasons.
  • the Al-based catalyst has a lower reactivity (polymerization activity) than the Sb-based catalyst or Ti-based catalyst, and thus the reaction is mild, and a by-product (diethylene glycol unit: DEG) is hardly generated. As a result, the regularity of PET increases, and it is easy to align and to express Re.
  • (1-3-1) Al-based catalyst As the Al-based catalyst, an Al-based catalyst described in [0013] to [0148] of WO2011 / 040161 ([0021] to [0123] of US2012 / 0183761) The contents described in these publications are incorporated herein by reference.
  • the method for producing a polyester resin by polymerization using an Al-based catalyst is not particularly limited, but specifically, [0091] to [0094] of WO2012 / 008488 ([0144] of US2013 / 0112271).
  • Al-based catalysts include, for example, [0052] to [0054], [0099] to [0104] of JP2012-122051A ([0045] to [0047], [0091] of WO2012 / 029725. [0096]), the contents of which are described in these publications are incorporated herein.
  • the amount of the Al-based catalyst is preferably 3 to 80 ppm, more preferably 5 to 60 ppm, and still more preferably 5 to 40 ppm as the amount of Al element with respect to the mass of the polyester resin.
  • Sb-based catalyst As the Sb-based catalyst, Sb-based catalysts described in JP-A-2012-41519, [0050], [0052] to [0054] can be used.
  • the method for polymerizing the polyester resin using the Sb-based catalyst is not particularly limited, but specifically, the polymerization can be performed according to [0086] to [0087] of WO2012 / 157762.
  • additive It is also preferable to add a known additive to the polyester film according to this embodiment.
  • a known additive include ultraviolet absorbers, particles, lubricants, antiblocking agents, heat stabilizers, antioxidants, antistatic agents, light resistance agents, impact resistance improvers, lubricants, dyes, pigments and the like.
  • the polyester film generally requires transparency, it is preferable to keep the additive amount to a minimum.
  • the polyester film according to this embodiment may contain an ultraviolet absorber in order to prevent the liquid crystal or the like of the liquid crystal display from being deteriorated by ultraviolet rays.
  • the ultraviolet absorber is a compound having ultraviolet absorbing ability, and is not particularly limited as long as it is an ultraviolet absorber that can withstand the heat applied in the production process of the polyester film.
  • Examples of the ultraviolet absorber include an organic ultraviolet absorber and an inorganic ultraviolet absorber, and an organic ultraviolet absorber is preferable from the viewpoint of transparency.
  • An ultraviolet absorber described in [0057] of WO2012 / 157762 or a cyclic iminoester-based ultraviolet absorber described later can be used.
  • cyclic iminoester-based ultraviolet absorber examples include, but are not limited to, 2-methyl-3,1-benzoxazin-4-one, 2-butyl-3,1-benzoxazin-4-one, -Phenyl-3,1-benzoxazin-4-one, 2- (1- or 2-naphthyl) -3,1-benzoxazin-4-one, 2- (4-biphenyl) -3,1-benzoxazine -4-one, 2-p-nitrophenyl-3,1-benzoxazin-4-one, 2-m-nitrophenyl-3,1-benzoxazin-4-one, 2-p-benzoylphenyl-3, 1-benzoxazin-4-one, 2-p-methoxyphenyl-3,1-benzoxazin-4-one, 2-o-methoxyphenyl-3,1-benzoxazin-4-one, 2-cyclo Xyl-3,1-benzoxazin-4-one, 2-p
  • a benzoxazinone-based compound that is difficult to be yellowed is preferably used.
  • a compound represented by the following formula (6) is more preferably used.
  • R represents a divalent aromatic hydrocarbon group
  • X 1 and X 2 are each independently selected from a hydrogen atom or the following functional group group, but are not necessarily limited thereto.
  • 2,2 '-(1,4-phenylene) bis (4H-3,1-benzoxazin-4-one) is particularly preferable.
  • the amount of the ultraviolet absorber that may be contained in the polyester film according to this embodiment is usually 10.0% by mass or less, preferably in the range of 0.3 to 3.0% by mass with respect to the whole film.
  • the ultraviolet absorber may bleed out on the surface, which may cause a decrease in surface functionality such as a decrease in adhesion.
  • the polyester film which concerns on this embodiment has a laminated structure, it is preferable that it is at least 3 layer structure, and it is preferable that the ultraviolet absorber is mix
  • the UV absorber can be prevented from bleeding out to the film surface, and as a result, the properties such as the adhesiveness of the film can be maintained.
  • the masterbatch method described in [0050] to [0051] of WO2011 / 162198 can be used.
  • additives may be used for the polyester film according to the present embodiment.
  • the additives described in [0058] of WO2012 / 157762 can be used. Is incorporated herein by reference.
  • the film is stretched in the direction perpendicular to the film conveyance path, and the surface temperature of the polyester film (hereinafter, The surface temperature at the start of the transverse stretching is 80 ° C. or more and 95 ° C. or less, and the surface temperature at the end of the transverse stretching is 90 ° C. or more and 105 ° C. or less.
  • a heat setting step of heat-setting the polyester film after the transverse drawing step by heating to the maximum temperature in the transverse drawing apparatus This is a method for producing a polyester film, which produces a polyester film having a thickness of 40 to 500 ⁇ m.
  • “unstretched polyester film” means a polyester film in which the refractive indexes of MD and TD are both 1.590 or less.
  • MD and TD may be slightly stretched in MD.
  • a polyester film having a refractive index of 1.590 or less is also included in the substantially unstretched polyester film.
  • the unstretched polyester film is preferably formed into a film by melt-extruding a polyester resin. After drying the polyester resin or the master batch of the polyester resin and additive produced by the above-described master batch method to a moisture content of 200 ppm or less, it is preferably introduced into a single or twin screw extruder and melted. At this time, in order to suppress decomposition of the polyester resin, it is also preferable to melt in a nitrogen or vacuum.
  • the detailed conditions can be carried out according to these publications, for example, with the aid of [0051] to [0052] (US 2013/0100378 publication [0085] to [0086]), which are described in these publications.
  • a gear pump in order to increase the delivery accuracy of the molten resin (melt). It is also preferable to use a filter having a pore diameter of 3 to 20 ⁇ m for removing foreign substances.
  • melt containing the polyester resin melt-kneaded from the die it may be extruded as a single layer or may be extruded as a multilayer (coextrusion).
  • a layer containing an ultraviolet absorber (UV agent) and a layer not containing it may be laminated, and more preferably, a three-layer structure in which a layer containing a UV agent is an inner layer is polarized by ultraviolet rays.
  • UV agent ultraviolet absorber
  • a layer not containing it may be laminated, and more preferably, a three-layer structure in which a layer containing a UV agent is an inner layer is polarized by ultraviolet rays.
  • the bleed-out UV agent is transferred to a roll in contact with the film in the film production process, which increases the coefficient of friction between the film and the roll and is liable to cause scratches.
  • the thickness (ratio to the total layer) of a preferable inner layer (a layer other than the outermost layer) of the obtained polyester film is preferably 50% or more and 95% or less, more preferably 60%. It is 90% or less, more preferably 70% or more and 85% or less.
  • Such lamination can be performed by using a feed block die or a multi-manifold die.
  • the refractive index in the longitudinal direction (MD) of the unstretched polyester film is preferably 1.590 or less, more preferably 1.585 or less, and 1.580 or less. Further preferred.
  • the crystallinity of the unstretched polyester film is preferably 5% or less, more preferably 3% or less, and even more preferably 1% or less.
  • the crystallinity degree of an unstretched polyester film here means the crystallinity degree of the center part of a film width direction (TD).
  • TD film width direction
  • the unstretched polyester film that has been melt-extruded may be formed by coating with a polymer layer according to the purpose before or after stretching, which will be described later.
  • the polymer layer generally include a functional layer that the polarizing plate may have, and among them, it is preferable to form an easy adhesion layer.
  • the easy-adhesion layer can be applied by the method described in [0062] to [0070] of WO2012 / 157762, for example.
  • FIG. 3 schematically shows an example of the configuration of a transverse stretching apparatus used in the transverse stretching step.
  • a preheating step until the start of stretching in the transverse stretching step it is preferable to preheat an unstretched polyester film at a temperature increase rate of 600 ° C./min or less. If the heating rate of the film until the start of stretching in the transverse stretching process is 600 ° C./min or less, the film will be stretched in a state where the molecular chain has sufficiently moved, and the shear plane normal stress and shear plane yield stress will increase excessively. Is suppressed.
  • the temperature increase rate in the preheating step is more preferably 500 ° C./min or less, and further preferably 400 ° C./min or less.
  • the heating rate in the preheating step may be 40 ° C./min or more and 600 ° C./min or less, 40 ° C./min or more and 500 ° C./min or less, or 40 ° C./min or more and 400 ° C./min or less.
  • a transverse stretching device (also referred to as “tenter-type stretching device” or “tenter”) having a plurality of clips 20 running along a pair of rails installed on both sides of the film conveyance path. .) Is used for lateral stretching while both edges of the unstretched polyester film are gripped by the clips 20 respectively. In addition, you may hold
  • transverse stretching apparatus having the clip 20 that travels along a pair of rails installed on both sides of the film conveyance path.
  • a pair of endless rails is usually used as the pair of rails.
  • a clip is synonymous with a holding member.
  • the lateral stretching is performed in a direction (TD) orthogonal to the film transport direction (MD) while transporting an unstretched polyester film along the film transport path. That is, the lateral stretching can be achieved by holding both ends of the film with clips and widening between the clips while heating.
  • ⁇ In-plane retardation Re can be greatly expressed by transverse stretching.
  • transverse stretching in order to achieve a polyester film satisfying the preferable ranges of Re and Re / Rth, it is preferable to perform at least transverse stretching. Note that longitudinal stretching may be performed before the preheating step or before the transverse stretching step.
  • the surface temperature at the start of stretching in the transverse stretching step is preferably from 80 ° C to 95 ° C, more preferably from 82 ° C to 93 ° C, and still more preferably from 84 ° C to 92 ° C. If the surface temperature at the start of stretching in the transverse stretching step is 80 ° C. or higher, the orientation and orientation crystallization do not proceed excessively in the stretching stage, and the shear plane normal stress and shear plane yield stress are prevented from excessively increasing. Further, the rise in Rth is suppressed, and the Re / Rth ratio is 0.6 or more, so that the visibility of rainbow unevenness is suppressed.
  • the surface temperature at the start of stretching in the transverse stretching process is 95 ° C or less, the growth of spherulites due to insufficient orientation is suppressed, the shear plane normal stress and the shear plane yield stress are reduced too much, and the film is prevented from becoming cloudy. In addition, Re is likely to rise sufficiently.
  • the surface temperature at the end of stretching in the transverse stretching step is preferably 90 ° C. or higher and 105 ° C. or lower, more preferably 92 ° C. or higher and 102 ° C. or lower, and 93 ° C. or higher and 100 ° C. or lower. Further preferred. If the surface temperature at the end of stretching in the transverse stretching step is 90 ° C. or higher, the orientation and orientation crystallization do not proceed excessively in the stretching step, and the shear plane normal stress and shear plane yield stress are prevented from excessively increasing. Further, the rise in Rth is suppressed, and the Re / Rth ratio is 0.6 or more, so that the visibility of rainbow unevenness is suppressed.
  • the surface temperature at the end of stretching in the transverse stretching process is 105 ° C. or less, the growth of spherulites due to insufficient orientation is suppressed, the shear plane normal stress and the shear plane yield stress are excessively decreased, and the film is prevented from becoming cloudy. Therefore, Re that affects the suppression of rainbow unevenness is likely to rise sufficiently.
  • the surface temperature is gradually raised from the start of stretching in the transverse stretching step to the end of stretching.
  • “gradually rising” may be a continuous increase or a stepwise increase.
  • the difference in surface temperature between the end of stretching and the start of stretching is preferably 1 ° C. or higher, more preferably 3 ° C. or higher, and most preferably 5 ° C. or higher.
  • the transverse draw ratio in the transverse drawing step is preferably controlled in the range of 3.3 times to 4.8 times, more preferably 3.5 times to 4.5 times, and more preferably 3.7 times to 4.3 times. Even less than double is more preferable.
  • the transverse draw ratio is 3.3 times or more, the shear plane normal stress and the shear plane yield stress of the film are suppressed from being excessively decreased, and the reduction in Re effective in suppressing rainbow unevenness is suppressed.
  • the transverse draw ratio is 4.8 times or less, the shear plane normal stress and the shear plane yield stress of the film are prevented from excessively increasing and becoming brittle.
  • the surface temperature when the transverse stretching ratio is in the range of 1 to 2 is preferably 80 ° C. or more and 92 ° C. or less, more preferably 82 ° C. or more and 91 ° C. or less, and 84 ° C. or more and 91 ° C. or less. Further preferred. If the surface temperature in the transverse stretching step is in the range of 1 to 2 and the surface temperature is 80 ° C. or more, the orientation and orientation crystallization will not progress excessively in the stretching stage, and shear surface normal stress and shear surface yielding will occur. It is suppressed that the stress rises too much.
  • the rise in Rth is suppressed, and the Re / Rth ratio is 0.6 or more, so that the visibility of rainbow unevenness is suppressed.
  • the surface temperature is 92 ° C. or less when the transverse draw ratio in the transverse drawing step is in the range of 1 to 2 times, the growth of spherulites due to insufficient orientation is suppressed, and the shear plane normal stress and shear plane yield stress are reduced. Of the rainbow unevenness is suppressed without being excessively lowered and Re is not sufficiently increased.
  • the surface temperature when the transverse stretching ratio is in the range of 2 to 3 is preferably 85 ° C. or higher and 97 ° C. or lower, more preferably 86 ° C. or higher and 97 ° C. or lower, and 87 ° C. or higher and 96 ° C. or lower. Further preferred.
  • the surface temperature when the transverse stretching ratio is in the range of 2 times to less than 3 times is 85 ° C. or more, the orientation and orientation crystallization do not proceed excessively in the stretching stage, and the shear plane normal stress and shear plane An excessive increase in yield stress is suppressed.
  • the rise in Rth is suppressed, and the Re / Rth ratio is 0.6 or less, so that the visibility of rainbow unevenness is suppressed.
  • the transverse stretching step if the surface temperature when the transverse stretching ratio is in the range of 2 times to less than 3 times is 97 ° C. or less, the growth of spherulites due to insufficient orientation is suppressed, and shear plane normal stress and shear plane yielding are suppressed. It is suppressed that the stress is too low.
  • Re which is effective in suppressing rainbow unevenness, is sufficiently increased, and rainbow unevenness is suppressed from being visually recognized.
  • the surface temperature when the transverse stretching ratio is 3 or more is preferably 90 ° C. or higher and 102 ° C. or lower, more preferably 92 ° C. or higher and 101 ° C. or lower, and still more preferably 93 ° C. or higher and 100 ° C. or lower.
  • the surface temperature when the transverse stretching ratio is in the range of 3 times or more is 90 ° C. or more, the orientation and orientation crystallization do not proceed excessively in the stretching stage, and the shear plane normal stress and shear plane yield stress are It is suppressed that it goes up too much.
  • the rise of Rth is suppressed, and the Re / Rth ratio is 0.6 or more, thereby preventing the rainbow unevenness from being visually recognized.
  • the transverse stretching step if the surface temperature when the transverse stretching ratio is in the range of 3 times or more is 102 ° C. or less, the growth of spherulites due to insufficient orientation is suppressed, and the shear plane normal stress and shear plane yield stress decrease. Too much is suppressed. In addition, Re increases sufficiently, and the visibility of rainbow unevenness is suppressed.
  • the surface temperature when the transverse stretching ratio is in the range of 1 to 2 but the transverse stretching ratio is 2 or more.
  • the surface temperature in the range of less than 3 times and the surface temperature in the range of the transverse draw ratio of 3 times or more do not fall below the surface temperature in the stretch range with a small transverse draw ratio. That is, the surface temperature when the transverse draw ratio is in the range of 2 times or more and less than 3 times does not become lower than the surface temperature when the transverse draw ratio is in the range of 1 time or more and less than 2 times.
  • the surface temperature when it is in the range of 3 times or more does not fall below the surface temperature when the transverse draw ratio is in the range of 2 times or more and less than 3 times.
  • the temperature increase rate of the surface temperature during stretching is preferably 60 ° C./min or less, more preferably 50 ° C./min or less, and even more preferably 40 ° C./min or less.
  • the temperature increase rate of the surface temperature during stretching is 60 ° C./min or less, the molecular chain is prevented from moving rapidly during stretching, and the shear plane normal stress and the shear plane yield stress are too low. It is suppressed.
  • Re which is effective in suppressing rainbow unevenness, is sufficiently increased, making it difficult to visually recognize rainbow unevenness.
  • the temperature increase rate of the surface temperature during stretching is 5 ° C./min to 60 ° C./min, 5 ° C./min to 50 ° C./min, or 5 ° C./min to 40 ° C./min. There may be.
  • ⁇ Heat setting> It includes a heat setting step in which the polyester film after transverse stretching is heat-set by heating to the maximum temperature in the transverse stretching apparatus. After stretching, a heat treatment called “heat setting” is performed to promote crystallization. By performing at a temperature exceeding the stretching temperature, crystallization can be promoted and the strength of the film can be increased. In heat setting, volume shrinks due to crystallization.
  • a heat fixing method several slits for sending hot air to the extending portion are provided in parallel to the width direction, and the temperature of the gas blown out from the slit can be increased by higher than that of the extending portion. Further, a heat source (IR heater, halogen heater, etc.) may be installed near the exit of the stretching (part) to raise the temperature.
  • the maximum surface temperature of the polyester film in the heat setting step is preferably 130 ° C. to 230 ° C., more preferably 150 ° C. to 210 ° C., and still more preferably 160 to 200 ° C. If the maximum surface temperature in the heat setting process is 130 ° C or higher, the shear surface normal stress and shear surface yield stress are prevented from excessively decreasing, and if it is 230 ° C or lower, the shear surface normal stress and shear surface yield stress increase. Too much is suppressed.
  • the heating rate of the surface temperature of the film from the end of the transverse stretching process until reaching the maximum temperature in the heat setting process is preferably 1000 ° C./min or less, more preferably 800 ° C./min or less, and still more preferably 700 ° C./min or less.
  • the “maximum temperature in the heat setting process” refers to the highest surface temperature reached by the film in the heat setting zone, and the surface temperature (film surface temperature) of the film in the heat setting zone is a radiation thermometer. It can be obtained by actually measuring with.
  • the temperature increase rate of the surface temperature of the film from the end of the transverse stretching process to the maximum temperature in the heat setting process is 50 ° C./min or more and 1000 ° C./min or less, 50 ° C./min or more and 800 ° C./min or less, or 50 It may be at least 700 ° C./min.
  • the time when the surface temperature exceeds 130 ° C. is preferably 180 seconds or shorter, more preferably 120 seconds or shorter, and even more preferably 60 seconds or shorter. If the surface temperature exceeds 130 ° C. for 180 seconds or less, crystallization does not proceed excessively, the shear plane normal stress and shear plane yield stress increase excessively, or Rth increases excessively and rainbow unevenness is visually recognized. Is suppressed.
  • the time during which the surface temperature exceeds 130 ° C. may be 10 seconds to 180 seconds, 10 seconds to 120 seconds, or 10 seconds to 60 seconds.
  • ⁇ Heat relaxation> It is preferable to include a thermal relaxation step of heating the polyester film after the heat setting step and reducing the length of at least the transverse direction (TD) of the polyester film.
  • TD transverse direction
  • the polyester film after transverse stretching is heated to the maximum temperature in the transverse stretching apparatus.
  • the heat relaxation step is not strictly limited to an embodiment performed after the heat setting step, and the heat setting step and the heat relaxation step may be performed simultaneously.
  • the heat setting process is performed until the maximum temperature in the transverse stretching apparatus is reached, and the heat relaxation is continued at a temperature not exceeding the maximum temperature in the transverse stretching apparatus.
  • Lateral relaxation can be achieved by reducing the width of the widened clip.
  • Such relaxation may be achieved, for example, by using a pantograph-like chuck for the tenter, reducing the interval between the pantographs, and driving the clip on the electromagnet to reduce the speed.
  • the MD relaxation rate which is a ratio of reducing the MD length of the heat-fixed polyester film, to 1 to 7% from the viewpoint of suppressing generation of scratches on the polyester film. % Is more preferable, and 3 to 5% is still more preferable.
  • the relaxation rate of MD is 1% or more, the thermal shrinkage rate of MD can be reduced, and wrinkles are less likely to occur. It is preferable that the MD relaxation rate is 7% or less because it is difficult for the MD to loosen during the relaxation treatment, and it is difficult to cause a planar failure.
  • the relaxation rate of TD which is a ratio of reducing the length of TD of the heat-set polyester film, to be 0 to 6%, from the viewpoint of suppressing generation of scratches on the polyester film, and more preferably 1 to 4%. 1 to 3% is more preferable. It is preferable that the relaxation rate of TD is 6% or less because it is difficult for TD to loosen during the relaxation treatment, and it is difficult to cause a planar failure.
  • the relaxation temperature of TD (transverse direction) is preferably in the above-mentioned range of the heat setting temperature, and the same temperature as the heat setting as long as the heat setting for heating the polyester film after the horizontal stretching to the maximum temperature in the horizontal stretching apparatus can be performed. However, it may be low (that is, even if the maximum temperature in the transverse stretching apparatus is reached).
  • Re, Rth, and Re / Rth of the polyester film according to the present embodiment can be easily achieved. It is easy to manufacture the polyester film according to the present embodiment that exhibits the effect of reduction.
  • the polyester film after heat setting or heat relaxation is preferably cooled before being released from the clip from the viewpoint of easily reducing the temperature of the clip when the polyester film is released from the clip.
  • the cooling temperature of the polyester film after heat setting or heat relaxation is preferably 80 ° C. or less, more preferably 70 ° C. or less, and particularly preferably 60 ° C. or less.
  • Specific examples of the method for cooling the polyester film after heat setting include a method in which cold air is applied to the polyester film.
  • the temperature control means for heating or cooling the polyester film spraying warm or cold air on the polyester film,
  • the surface of the metal plate which can be temperature-controlled is mentioned, or the vicinity of a metal plate is passed.
  • the surface temperature of the polyester film when the polyester film is detached from the clip is more preferably 50 ° C. or more and 120 ° C. or less, and further preferably 60 ° C. or more and 100 ° C. or less.
  • the thickness of the polyester film after completion of film formation is 40 ⁇ m or more and 500 ⁇ m or less, more preferably 60 ⁇ m or more and 400 ⁇ m or less, and 80 ⁇ m or more and 300 ⁇ m or less. Further preferred.
  • the reason why it is preferable to set the thickness of the polyester film in the above range is the same as the reason for the thickness of the polyester film according to this embodiment described above.
  • the film width after opening from the clip is preferably 0.8 to 6 m from the viewpoint of efficiently securing the film product width and preventing the apparatus size from becoming excessive. More preferably, it is more preferably ⁇ 5 m, and particularly preferably 1 to 4 m.
  • An optical film requiring accuracy is usually formed with a thickness of less than 3 m, but in the present embodiment, it is preferable to form with a width as described above.
  • the film formed into a wide film may be slit to preferably 2 or more, 6 or less, more preferably 2 or more and 5 or less, and still more preferably 3 or more and 4 or less, and then wound.
  • the winding is preferably performed at a diameter of 70 mm to 600 mm on a core having a diameter of 70 mm to 600 mm.
  • Winding tension per cross-sectional area of the film is preferably 3 ⁇ 30kgf / cm 2, more preferably 5 ⁇ 25kgf / cm 2, more preferably from 7 ⁇ 20kgf / cm 2. It is also preferable to bond a masking film before winding.
  • the polyester film according to the present embodiment can be suitably used for a base film of a hard coat film. That is, the hard coat film according to the present embodiment includes a base film including the polyester film according to the present embodiment described above and a hard coat layer laminated on at least one surface of the polyester film.
  • the hard coat layer may be formed by either a wet coating method or a dry coating method (vacuum film formation), but is preferably formed by a wet coating method having excellent productivity.
  • the hard coat layer for example, JP2013-45045A, JP2013-43352A, JP2012-232424A, JP2012-128157A, JP2011-131409A, JP JP2011-131404A, JP2011-126162A, JP2011-75705A, JP2009-286981, JP2009-263567, JP2009-75248, JP2007-. No.
  • the Dokoto layer can be used.
  • the thickness of the hard coat layer of the hard coat film according to this embodiment is preferably 5 ⁇ m or more. If the thickness of the hard coat layer is 5 ⁇ m or more, a hard coat film having high scratch resistance can be obtained. From this viewpoint, the thickness of the hard coat layer of the hard coat film according to this embodiment is more preferably 10 ⁇ m or more, and further preferably 15 ⁇ m or more. In addition, since the punching process tends to be difficult when the thickness of the hard coat layer is too thick, the thickness of the hard coat layer is preferably 40 ⁇ m or less, and more preferably 35 ⁇ m or less.
  • the hard coat layer of the hard coat film is At least a structure derived from a) below, a structure derived from b) below, c) and d) below,
  • the structure derived from the following a) is 15 to 70% by mass
  • the structure derived from the following b) is 25 to 80% by mass
  • the following c) It is preferable to contain 0.1 to 10% by mass and 0.1 to 10% by mass of the following d).
  • the hard coat film according to this embodiment has high pencil hardness, Excellent in smoothness, and changes in film appearance after wet heat aging are suppressed.
  • the hard coat layer preferably has hard coat properties.
  • the hard coat property means a pencil hardness of 7H or more from the viewpoint of being used as an outermost surface protective film of an image display device as a glass substitute hard coat film.
  • the hard coat layer preferably has a pencil hardness of 8H or higher.
  • the hard coat film according to this embodiment having such a configuration is preferably manufactured by a method for manufacturing a hard coat film according to this embodiment described later.
  • the hard coat film which concerns on this embodiment is the structure which coated the hard-coat layer on the at least one surface of the polyester film which concerns on this embodiment mentioned above.
  • the hard coat film according to the present embodiment is formed by curing a composition for forming a hard coat layer including a), b), c) and d), and the composition for forming a hard coat layer is a hard coat layer.
  • the total solid content of the forming composition is 100% by mass, a) is 15 to 70% by mass, b) is 25 to 80% by mass, c) is 0.1 to 10% by mass, and d) is 0.1% by mass. More preferably, the content is 1 to 10% by mass.
  • the hard coat layer contains 15 to 70% by mass of the structure derived from the following a) when the total solid content of the hard coat layer is 100% by mass. a) A compound having one alicyclic epoxy group and one ethylenically unsaturated double bond group in the molecule and having a molecular weight of 300 or less.
  • the hard coat layer is formed by curing a composition for forming a hard coat layer containing at least a), b), c) and d), and the composition for forming a hard coat layer is a composition for forming a hard coat layer.
  • a) is preferably contained in an amount of 15 to 70% by mass.
  • A) Contained in the composition for forming a hard coat layer a) a compound having one alicyclic epoxy group and one group containing an ethylenically unsaturated double bond in the molecule and having a molecular weight of 300 or less explain. a) A compound having one alicyclic epoxy group and one group containing an ethylenically unsaturated double bond in the molecule and having a molecular weight of 300 or less is also referred to as “a) component”.
  • Examples of the group containing an ethylenically unsaturated double bond include polymerizable functional groups such as a (meth) acryloyl group, a vinyl group, a styryl group, and an allyl group. Among them, a (meth) acryloyl group and —C (O) OCH ⁇ CH 2 is preferable, and a (meth) acryloyl group is particularly preferable.
  • a group containing an ethylenically unsaturated double bond high hardness can be maintained and heat and heat resistance can also be imparted.
  • (meth) acryloyl group includes “acryloyl group” and “methacryloyl group”
  • (meth) acrylate includes “acrylate” and “methacrylate”.
  • (Meth) acryl means “acryl” and “methacryl”.
  • the number of groups containing an epoxy group and an ethylenically unsaturated double bond in the molecule is one.
  • each functional group is 1
  • the number of functional groups (groups containing an epoxy group and an ethylenically unsaturated double bond) is reduced as compared to the case of 2 or more, thereby reducing the molecular weight and pencil hardness. This is because of the increase.
  • the molecular weight of the component a) is 300 or less, preferably 210 or less, and more preferably 200 or less.
  • the molecular weight of the component a) is preferably 100 or more, and more preferably 150 or more.
  • the component a) is not limited as long as it has one alicyclic epoxy group and one ethylenically unsaturated double bond group in the molecule and has a molecular weight of 300 or less. It is preferable that it is a compound represented by 7).
  • R represents a monocyclic hydrocarbon or a bridged hydrocarbon
  • L represents a single bond or a divalent linking group
  • Q represents a group containing an ethylenically unsaturated double bond.
  • R in the formula (7) is a monocyclic hydrocarbon, it is preferably an alicyclic hydrocarbon, more preferably an alicyclic group having 4 to 10 carbon atoms, and an alicyclic group having 5 to 7 carbon atoms. Group is more preferable, and an alicyclic group having 6 carbon atoms is particularly preferable. Specifically, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group are preferable, and a cyclohexyl group is particularly preferable.
  • R in the formula (7) is a bridged hydrocarbon
  • a bicyclic bridge (bicyclo ring) or a tricyclic bridge (tricyclo ring) is preferable, and examples thereof include a bridged hydrocarbon having 5 to 20 carbon atoms, and a norbornyl group Bornyl group, isobornyl group, tricyclodecyl group, dicyclopentenyl group, dicyclopentanyl group, tricyclopentenyl group, tricyclopentanyl group, adamantyl group, lower alkyl group-substituted adamantyl group and the like.
  • L represents a divalent linking group
  • a divalent aliphatic hydrocarbon group is preferred.
  • the divalent aliphatic hydrocarbon group preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, and still more preferably 1.
  • a linear, branched or cyclic alkylene group is preferable, a linear or branched alkylene group is more preferable, and a linear alkylene group is still more preferable.
  • Q include polymerizable functional groups such as a (meth) acryloyl group, a vinyl group, a styryl group, and an allyl group. Among them, a (meth) acryloyl group and —C (O) OCH ⁇ CH 2 are preferable and particularly preferable. Is a (meth) acryloyl group.
  • a compound having one alicyclic epoxy group and one group containing an ethylenically unsaturated double bond in the molecule and having a molecular weight of 300 or less a compound described in paragraph [0015] of JP-A-10-17614, a compound represented by the following formula (1A) or (1B), 1,2-epoxy-4-vinylcyclohexane, or the like is used. Can do. Among these, a compound represented by the following formula (1A) or (1B) is more preferable, and a compound represented by the following formula (1A) having a low molecular weight is more preferable.
  • the compound represented by the following formula (1A) is also preferably an isomer thereof.
  • L 2 represents a divalent aliphatic hydrocarbon group having 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, and the component having 1 carbon atom (that is, a) is epoxycyclohexylmethyl. (Meth) acrylate) is more preferable from the viewpoint of improving smoothness. By using these compounds, both high pencil hardness and excellent smoothness can be achieved at a higher level.
  • R 1 represents a hydrogen atom or a methyl group
  • L 2 represents a divalent aliphatic hydrocarbon group having 1 to 6 carbon atoms.
  • R 1 represents a hydrogen atom or a methyl group
  • L 2 represents a divalent aliphatic hydrocarbon group having 1 to 6 carbon atoms.
  • the divalent aliphatic hydrocarbon group represented by L 2 in the formulas (1A) and (1B) has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, and still more preferably 1 carbon atom.
  • a linear, branched or cyclic alkylene group is preferable, a linear or branched alkylene group is more preferable, and a linear alkylene group is still more preferable.
  • the structure derived from a) is contained in an amount of 15 to 70% by mass when the total solid content of the hard coat layer is 100% by mass.
  • the component a) is contained in an amount of 15 to 70% by mass when the total solid content of the hard coat layer forming composition in the present embodiment is 100% by mass.
  • the surface smoothness is sufficiently improved.
  • the content of the structure derived from a) or the component a) relative to the hard coat layer or the hard coat layer forming composition is 70% by mass or less, the surface hardness can be sufficiently increased.
  • the structure derived from a) is preferably contained in an amount of 18 to 50% by mass, more preferably 22 to 40% by mass, when the total solid content of the hard coat layer is 100% by mass.
  • the component a) is preferably contained in an amount of 18 to 50% by mass, preferably 22 to 40% by mass, when the total solid content of the hard coat layer forming composition in the present embodiment is 100% by mass. Is more preferable.
  • the hard coat layer contains 25 to 80% by mass of the structure derived from b) below when the total solid content of the hard coat layer is 100% by mass.
  • the hard coat layer is formed by curing a composition for forming a hard coat layer containing at least a), b), c) and d), and the composition for forming a hard coat layer is a composition for forming a hard coat layer.
  • the total solid content of the product is 100% by mass, it is preferable to contain 25 to 80% by mass of b).
  • a compound having a group containing 3 or more ethylenically unsaturated double bonds in the molecule b) contained in the composition for forming a hard coat layer in this embodiment will be described.
  • a compound having a group containing three or more ethylenically unsaturated double bonds in the molecule is also referred to as “component b”.
  • the component b) can exhibit high hardness by having a group containing 3 or more ethylenically unsaturated double bonds in the molecule.
  • the component b) may have a group containing 3 or more and 20 or less ethylenically unsaturated double bonds in the molecule.
  • the component b) include esters of polyhydric alcohol and (meth) acrylic acid, vinylbenzene and its derivatives, vinyl sulfone, (meth) acrylamide and the like.
  • a compound having three or more (meth) acryloyl groups is preferable, and examples thereof include acrylate compounds that form a hardened cured product widely used in the industry.
  • An example of such a compound is an ester of polyhydric alcohol and (meth) acrylic acid having a group containing 3 or more ethylenically unsaturated double bonds in the molecule.
  • resin (oligomer or prepolymer) having 3 or more (meth) acryloyl groups, polyfunctional (meth) acrylate having 3 or more (meth) acryloyl groups, and urethane (meth) acrylate are also preferable.
  • the resin (oligomer or prepolymer) having three or more (meth) acryloyl groups include polyester resin, polyether resin, acrylic resin, epoxy resin, urethane resin, alkyd resin, spiroacetal resin, polybutadiene resin, and polythiol.
  • examples include oligomers or prepolymers such as polyene resins and polyfunctional compounds such as polyhydric alcohols.
  • polyfunctional (meth) acrylate having 3 or more (meth) acryloyl groups include the exemplified compounds shown in paragraph 0096 of JP-A-2007-256844.
  • polyfunctional acrylate compounds having three or more (meth) acryloyl groups include KAYARAD DPHA, DPHA-2C, PET-30, TMPTA, TPA-320, and TPA-330 manufactured by Nippon Kayaku Co., Ltd. RP-1040, T-1420, D-310, DPCA-20, DPCA-30, DPCA-60, GPO-303, Osaka Organic Chemical Co., Ltd. V # 400, V # 36095D ) An esterified product of acrylic acid can be mentioned.
  • UV-1400B UV-1700B, UV-6300B, UV-7550B, UV-7600B, UV-7605B, UV-7610B, UV-7620EA, UV-7630B, UV-7640B, UV-6630B, UV-7000B, UV-7510B, UV-7461TE, UV-3000B, UV-3200B, UV-3210EA, UV-3310EA, UV-3310B, UV-3500BA, UV-3520TL, UV-3700B, UV-6100B, UV-6640B, UV- 2000B, UV-2010B, UV-2250EA, UV-2750B (manufactured by Nippon Synthetic Chemical Co., Ltd.), UL-503LN (manufactured by Kyoeisha Chemical Co., Ltd.), Unidic 17-806, 17-813, V-4030, V -4000BA (DI EB-1290K, EB-220, EB-5129, EB-1830, EB-4358 (manufactured by Daicel UCB),
  • the structure derived from b) is contained in an amount of 25 to 80% by mass when the total solid content of the hard coat layer is 100% by mass.
  • the component b) is contained in an amount of 25 to 80% by mass when the total solid content of the hard coat layer forming composition in the present embodiment is 100% by mass.
  • the content of the structure derived from b) or the content of the component b) is 25% by mass or more with respect to the hard coat layer or the hard coat layer forming composition, sufficient hardness can be obtained.
  • the a derived structure or the content of the a) component is Since it decreases, the smoothness is sufficient.
  • the structure derived from b) is preferably contained in an amount of 40 to 75% by mass, more preferably 60 to 75% by mass, when the total solid content of the hard coat layer is 100% by mass.
  • the component b) is preferably contained in an amount of 40 to 75% by mass, preferably 60 to 75% by mass, when the total solid content of the composition for forming a hard coat layer in the present embodiment is 100% by mass. Is more preferable.
  • the composition for forming a hard coat layer may contain a curable compound other than the component a) and the component b) (hereinafter also referred to as “other curable compound”).
  • other curable compounds various compounds having a polymerizable group that can be cured (polymerized) by a curing treatment can be used.
  • the polymerizable group include a polymerizable group capable of undergoing a polymerization reaction upon irradiation with light, an electron beam or radiation, and a polymerizable group capable of undergoing a polymerization reaction upon heating, and a photopolymerizable group is preferred.
  • Other curable compounds can be monomers, oligomers, prepolymers, and the like.
  • polymerizable groups include polymerizable unsaturated groups such as (meth) acryloyl groups, vinyl groups, styryl groups, and allyl groups, and ring-opening polymerizable groups such as epoxy groups.
  • a (meth) acryloyl group is preferable from the viewpoint of curability and the like.
  • (Meth) acrylic diesters of alkylene glycols such as neopentyl glycol acrylate, 1,6-hexanediol (meth) acrylate, propylene glycol di (meth) acrylate; triethylene glycol di (meth) acrylate, dipropylene glycol di ( (Meth) acrylate diesters of polyoxyalkylene glycols such as (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate; (meth) of polyhydric alcohols such as pentaerythritol di (meth) acrylate Acrylic acid diesters; 2,2-bis ⁇ 4- (acryloxy-diethoxy) phenyl ⁇ propane, 2,2-bis ⁇ 4- (acryloxy-polypropoxy) phenyl ⁇ propane, etc.
  • urethane (meth) acrylate for example, an alcohol, a polyol, and / or a hydroxyl group-containing compound such as a hydroxyl group-containing acrylate is reacted with an isocyanate, or, if necessary, a polyurethane compound obtained by these reactions ( Mention may be made of urethane (meth) acrylates obtained by esterification with (meth) acrylic acid. Specific examples include various commercial products listed in paragraph 0017 of JP-A-2007-256844.
  • the composition for forming a hard coat layer can also contain an epoxy compound having an epoxy group as a polymerizable group as another curable compound from the viewpoint of reducing the shrinkage due to curing.
  • the epoxy compound is preferably a polyfunctional epoxy compound containing two or more epoxy groups in one molecule. Specific examples include JP-A-2004-264563, JP-A-2004-264564, JP-A-2005-37737, JP-A-2005-37738, JP-A-2005-140862, JP-A-2005-140862. And epoxy compounds described in JP-A No. 2005-140863 and JP-A No. 2002-322430. It is also preferable to use a compound having both an epoxy group and an acrylic polymerizable group such as glycidyl (meth) acrylate.
  • the content of the other curable compound with respect to the total solid content of the hard coat layer forming composition is determined when the total solid content of the hard coat layer forming composition is 100% by mass. 15% by mass or less, preferably 10% by mass or less, more preferably 1% by mass or less, still more preferably 0.01% by mass or less, substantially including It is particularly preferred not to.
  • the hard coat layer contains 0.1 to 10% by mass of c) radical polymerization initiator when the total solid content of the hard coat layer is 100% by mass.
  • the c) radical polymerization initiator contained in the hard coat layer or the hard coat layer forming composition in this embodiment will be described.
  • the c) radical polymerization initiator is also referred to as “c) component”. Polymerization of the compound having an ethylenically unsaturated group can be performed by irradiation with ionizing radiation or heating in the presence of a photo radical polymerization initiator or a thermal radical polymerization initiator.
  • an alkylphenone photopolymerization initiator (Irgacure 651, Irgacure 184, DAROCURE 1173, Irgacure 2959, Irgacure 127, DAROCURE MBF, Irgacure 907, Irgacure 369, Irgacure 369, Irgacure 369, Irgacure 369, Irgacure 369, Irgacure 369, Irgacure 369 Photopolymerization initiator , LUCIRIN TPO) and others (Irgacure 784, Irgacure OXE01, Irgacure OXE02, Irgacure 754) and the like can be used.
  • an alkylphenone photopolymerization initiator (Irgacure 651, Irgacure 184, DAROCURE 1173, Irgacure 2959, Irgacure
  • the amount of component c) added is in the range of 0.1 to 10% by mass, assuming that the total solid content of the hard coat layer or hard coat layer forming composition in this embodiment is 100% by mass. 5% by mass is preferable, and 2 to 4% by mass is more preferable.
  • c) When the added amount of the component is 0.1% by mass or more when the total solid content of the hard coat layer or the hard coat layer forming composition is 100% by mass, the polymerization proceeds sufficiently, and the hard coat layer The pencil hardness can be increased.
  • the addition amount of component c) is 10% by mass or less when the total solid content of the hard coat layer or the hard coat layer forming composition is 100% by mass, UV light reaches the inside of the film, The pencil hardness of the coat layer can be increased.
  • radical initiators may be used alone or in combination of two or more.
  • the hard coat film according to this embodiment includes 0.1 to 10% by mass of d) a cationic polymerization initiator when the hard coat layer has the total solid content of the hard coat layer as 100% by mass.
  • the d) cationic polymerization initiator contained in the hard coat layer or the hard coat layer forming composition in this embodiment will be described.
  • d) cationic polymerization initiator is also referred to as “d) component”.
  • component d known compounds such as photoinitiators for photocationic polymerization, photodecolorants for dyes, photochromic agents, known acid generators used in microresists, and the like, and mixtures thereof Etc. Examples thereof include onium compounds, organic halogen compounds, and disulfone compounds. Specific examples of these organic halogen compounds and disulfone compounds include the same compounds as those described above for the compounds that generate radicals.
  • onium compounds examples include diazonium salts, ammonium salts, iminium salts, phosphonium salts, iodonium salts, sulfonium salts, arsonium salts, selenonium salts, and the like.
  • diazonium salts ammonium salts, iminium salts, phosphonium salts, iodonium salts, sulfonium salts, arsonium salts, selenonium salts, and the like.
  • particularly preferred cationic polymerization initiators include onium salts, and diazonium salts, iodonium salts, sulfonium salts, and iminium salts are used for photopolymerization initiation photosensitivity, compound material stability, and the like.
  • iodonium salts are most preferable from the viewpoint of light resistance.
  • onium salts that can be suitably used in the present embodiment include, for example, an amylated sulfonium salt described in paragraph [0035] of JP-A-9-268205, and JP-A-2000-71366.
  • organometallic / organic halides described in paragraphs [0059] to [0062] of JP-A-2002-29162, photoacid generators having o-nitrobenzyl type protecting groups, photodecomposition And compounds that generate sulfonic acid (iminosulfonate, etc.).
  • Specific compounds of the iodonium salt-based cationic polymerization initiator include B2380 (manufactured by Tokyo Chemical Industry), BBI-102 (manufactured by Midori Chemical), WPI-113 (manufactured by Wako Pure Chemical Industries), WPI-124 (manufactured by Wako Pure Chemical Industries). Industrial product), WPI-169 (manufactured by Wako Pure Chemical Industries), WPI-170 (manufactured by Wako Pure Chemical Industries), DTBPI-PFBS (manufactured by Toyo Gosei) can be used.
  • iodonium salt-based cationic polymerization initiator include the following compounds FK-1 and FK-2.
  • the component d) is added in a range of 0.1 to 10% by mass, preferably 0.1 to 10% by mass, when the total solid content of the hard coat layer or hard coat layer forming composition in this embodiment is 100% by mass. It can be added at a ratio of 5 to 3.0% by mass. The addition amount is preferably in the above range from the viewpoint of stability of the coating solution, polymerization reactivity, and the like.
  • Inorganic particles having reactivity with an epoxy group or a group containing an ethylenically unsaturated double bond it is preferable to add e) inorganic particles having reactivity with an epoxy group or a group containing an ethylenically unsaturated double bond.
  • e) inorganic particles having reactivity with an epoxy group or a group containing an ethylenically unsaturated double bond are also referred to as “e) component”. Since the amount of curing shrinkage of the hard coat layer (cured layer) can be reduced by adding inorganic particles, smoothness can be improved.
  • inorganic particles having reactivity with an epoxy group or a group containing an ethylenically unsaturated double bond examples include silica particles, titanium dioxide particles, zirconium oxide particles, and aluminum oxide particles.
  • e) inorganic particles having reactivity with an epoxy group or a group containing an ethylenically unsaturated double bond are preferably silica particles.
  • inorganic particles have low affinity with organic components such as polyfunctional vinyl monomers, they may form aggregates or crack the hard coat layer after curing by simply mixing them. Therefore, in the component e), in order to increase the affinity between the inorganic particles and the organic component, it is preferable to treat the surface of the inorganic particles with a surface modifier containing an organic segment.
  • the surface modifier is preferably a surface modifier having a functional group capable of forming a bond with the inorganic particle or adsorbing to the inorganic particle and a functional group having high affinity with the organic component in the same molecule.
  • Examples of the surface modifier having a functional group capable of binding or adsorbing to inorganic particles include metal alkoxide surface modifiers such as silane, aluminum, titanium, and zirconium, or phosphoric acid groups, sulfuric acid groups, sulfonic acid groups, and carboxylic acid groups.
  • a surface modifier having an anionic group is preferred.
  • the functional group having a high affinity with the organic component may be a functional group that is simply combined with the organic component and hydrophilicity / hydrophobicity. A group containing a heavy bond or a ring-opening polymerizable group is preferred.
  • a preferable surface modifier for inorganic particles is a curable resin having a metal alkoxide or an anionic group and a group containing an ethylenically unsaturated double bond or a ring-opening polymerizable group in the same molecule.
  • Representative examples of these surface modifiers include the following unsaturated double bond-containing coupling agents, phosphoric acid group-containing organic curable resins, sulfuric acid group-containing organic curable resins, and carboxylic acid group-containing organic curable resins. .
  • X
  • the surface modification of these inorganic particles is preferably performed in a solution.
  • the surface modifier is present together, or after the inorganic particles are finely dispersed, the surface modifier is added and stirred, or before the inorganic particles are finely dispersed.
  • the surface may be modified (if necessary, heated, dried and then heated, or pH changed), and then finely dispersed.
  • an organic solvent having a large polarity is preferable. Specific examples include known solvents such as alcohols, ketones and esters.
  • the amount of the component added is 5 when the total solid content of the hard coat layer or the hard coat layer forming composition in this embodiment is 100% by mass in consideration of the balance between hardness and brittleness of the coating film. -40% by mass is preferable, and 10-30% by mass is more preferable.
  • the size of the inorganic particles (average primary particle size) is preferably 10 nm to 100 nm, more preferably 10 to 60 nm. The average particle diameter of the particles can be determined from an electron micrograph. If the particle size of the inorganic particles is equal to or greater than the lower limit value, an effect of improving the hardness is obtained, and if the particle size is equal to or smaller than the upper limit value, an increase in haze can be suppressed.
  • the shape of the inorganic particles may be spherical or non-spherical, but a non-spherical shape in which 2 to 10 inorganic particles are connected is preferable from the viewpoint of imparting hardness. It is presumed that by using inorganic particles in which several particles are linked in a chain, a firm particle network structure is formed and the hardness is improved.
  • the inorganic particles include ELECOM V-8802 (spherical silica particles having an average primary particle size of 12 nm manufactured by JGC Corporation), ELECOM V-8803 (modified silica particles manufactured by JGC Corporation), MiBK- SD (spherical silica particles having an average primary particle diameter of 10 to 20 nm manufactured by Nissan Chemical Industries, Ltd.), MEK-AC-2140Z (spherical silica particles having an average primary particle diameter of 10 to 20 nm manufactured by Nissan Chemical Industries, Ltd.), MEK-AC-4130 (spherical silica particles with an average primary particle size of 40-50 nm manufactured by Nissan Chemical Industries, Ltd.), MiBK-SD-L (spherical particles with an average primary particle size of 40-50 nm manufactured by Nissan Chemical Industries, Ltd.) Silica particles), MEK-AC-5140Z (spherical silica particles having an average primary particle size of 70 to 100 nm manufactured by Nissan Chemical Industries, Ltd.), and the like.
  • the hard coat layer or the hard coat layer forming composition preferably contains f) polyester urethane from the viewpoint of increasing brittleness.
  • f) polyester urethane is also referred to as “f) component”.
  • Polyester urethane is a polymer containing an ester bond and a urethane bond (—O—CO—NH—) in one molecule.
  • the polyester urethane is preferably a polyester urethane having a tensile strength of 25 MPa or more and a tensile elongation of 200% or more.
  • polyester urethane having a tensile strength of 25 MPa or more and a tensile elongation of 200% or more can contribute to increasing the hardness of the hard coat layer and imparting appropriate flexibility. It is inferred that this contributes to increasing the hardness and improving brittleness of the hard coat layer. Moreover, if the polyester urethane content is 1 part by mass or more with respect to 100 parts by mass of the solid content of the hard coat layer or the composition for forming a hard coat layer, the above-described effect due to the addition of the polyester urethane can be sufficiently obtained. The hardness of the cured layer can be maintained as long as it is at most parts.
  • the content of the polyester urethane with respect to 100 parts by mass of the solid content of the hard coat layer or the hard coat layer forming composition is in the range of 1 to 10 parts by mass. From the viewpoint of improving brittleness and suppressing the decrease in transparency, it is more preferably 2 parts by mass or more, and from the viewpoint of maintaining the hardness of the hard coat layer, it is more preferably 8 parts by mass or less.
  • polyester urethane exhibiting the above-described tensile strength and tensile elongation as the polyester urethane contributes to achieving both high hardness and improved brittleness by imparting appropriate flexibility to the hard coat layer. More preferably, the tensile strength is 40 MPa or more, and further preferably 50 MPa or more. Moreover, it is preferable that a tensile strength is 70 Mpa or less from a viewpoint of the compatibility stability in the composition for hard-coat layer formation. On the other hand, the tensile elongation is preferably 450% or more, and more preferably 600% or more.
  • the tensile elongation is preferably 1000% or less.
  • the tensile strength and tensile elongation of the polyester urethane are values measured using a tensile strength tester according to JIS K 6251.
  • Polyester urethane can be obtained by polymerization of monomer components containing at least diol, dicarboxylic acid, and diisocyanate.
  • polyester urethanes having a hydroxyl group (—OH), a carboxyl group (—COOH), and an isocyanate group (—NCO) at both ends of a hydrocarbon group having an unbranched structure are preferable.
  • the hydrocarbon group having an unbranched structure is preferably an alkylene group, an alkenylene group, an alkynylene group, an arylene group, or a combination thereof.
  • the alkylene group, alkenylene group and alkynylene group preferably have a linear structure.
  • the hydrocarbon group is an alkylene group, an alkenylene group or an alkynylene group
  • the number of carbon atoms is preferably 1 to 8, more preferably 2 to 6, and further preferably 2 to 4.
  • the arylene group may have an alkyl group having 1 to 8 carbon atoms as a substituent.
  • the arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and further preferably a p-phenylene group.
  • the hydrocarbon group the alkylene group, the arylene group, or a combination thereof is particularly preferable.
  • Diols used as polyester urethane monomers include ethylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, and 1,5- Pentanediol is preferred.
  • dicarboxylic acid terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, succinic acid, glutaric acid, adipic acid, oxalic acid and malonic acid are preferable.
  • Diisocyanates include ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, m-xylylene diisocyanate, p-phenylene diisocyanate, tolylene diisocyanate, p, p'-diphenylmethane diisocyanate and 1,5-naphthylene diisocyanate. preferable.
  • the number average molecular weight (Mn) of the polyester urethane is preferably 5000 or more from the viewpoint of affinity with inorganic particles, preferably 10,000 or more, and 50,000 or less from the viewpoint of compatibility with the curable compound. It is preferable that
  • the polyester urethane may have a reactive group.
  • the reactive group is preferably a polymerizable unsaturated group.
  • it is as having described about the functional group which an inorganic particle may have previously.
  • polyester urethane As the polyester urethane described above, a polyester urethane synthesized by a known method may be used, or a commercially available product may be used.
  • Commercially available products include Byron (registered trademark) series (trade name) manufactured by Toyobo Co., Ltd., Byron UR-2300, Byron UR-3200, Byron UR-3210, Byron UR-3260, Byron UR-5537.
  • Byron UR-8300, Byron UR-8700 and the like can be preferably used.
  • the hard coat layer or the hard coat layer forming composition in the present embodiment contains g) an antifouling agent because adhesion of fingerprints and dirt is reduced, and the attached dirt can be easily wiped off. . Moreover, it is also preferable from the viewpoint of improving the scratch resistance by improving the slip property of the surface.
  • g) antifouling agent is also referred to as “g) component”.
  • the antifouling agent contains a fluorine-containing compound, the fluorine-containing compound has a perfluoropolyether group and a polymerizable unsaturated group, and the polymerizable unsaturated group. It is preferable to have plural in one molecule.
  • the g) antifouling agent that can be used in this embodiment will be described.
  • Antifouling agent contains a fluorine-containing compound, this fluorine-containing compound has a perfluoropolyether group and a polymerizable unsaturated group, and a compound having a plurality of polymerizable unsaturated groups in one molecule ( Hereinafter, the case of “fluorinated antifouling agent”) will be described.
  • the fluorine-containing antifouling agent is preferably a fluorine-based compound having a structure represented by the following formula (F).
  • Rf represents a (per) fluoroalkyl group or (per) fluoropolyether group
  • W represents a linking group
  • RA represents a polymerizable unsaturated group
  • n represents an integer of 1 to 3.
  • m represents an integer of 1 to 3.
  • the fluorine-containing antifouling agent is considered to have the following effects (1) to (3) because it has a polymerizable unsaturated group.
  • Solubility in an organic solvent and compatibility with a compound having an unsaturated double bond increase, so that the antifouling agent can be uniformly localized on the surface without forming an aggregate. Conceivable. Moreover, generation
  • Loss of antifouling property and deterioration of appearance due to bleedout of the antifouling agent and precipitation can be prevented.
  • R A represents a polymerizable unsaturated group.
  • the polymerizable unsaturated group is not particularly limited as long as it is a group capable of causing a radical polymerization reaction by irradiation with active energy rays such as ultraviolet rays or an electron beam.
  • Active energy rays such as ultraviolet rays or an electron beam.
  • Groups, allyl groups, and the like, and (meth) acryloyl groups, (meth) acryloyloxy groups, and groups in which any hydrogen atom in these groups is substituted with a fluorine atom are preferably used.
  • a group having the structure shown below is preferable.
  • Rf represents a (per) fluoroalkyl group or a (per) fluoropolyether group.
  • the (per) fluoroalkyl group represents at least one of a fluoroalkyl group and a perfluoroalkyl group
  • the (per) fluoropolyether group is at least one of a fluoropolyether group and a perfluoropolyether group.
  • the (per) fluoroalkyl group is preferably a group having 1 to 20 carbon atoms, more preferably a group having 1 to 10 carbon atoms.
  • the (per) fluoroalkyl group is a straight chain (for example, —CF 2 CF 3 , —CH 2 (CF 2 ) 4 H, —CH 2 (CF 2 ) 8 CF 3 , —CH 2 CH 2 (CF 2 ) 4 H Etc.) even in the branched structure (for example, CH (CF 3 ) 2 , CH 2 CF (CF 3 ) 2 , CH (CH 3 ) CF 2 CF 3 , CH (CH 3 ) (CF 2 ) 5 CF 2 H Or an alicyclic structure (preferably a 5- or 6-membered ring such as a perfluorocyclohexyl group, a perfluorocyclopentyl group, or an alkyl group substituted with these).
  • the (per) fluoropolyether group refers to a case where the (per) fluoroalkyl group has an ether bond, and may be a monovalent or divalent group.
  • the fluoropolyether group include —CH 2 OCH 2 CF 2 CF 3 , —CH 2 CH 2 OCH 2 C 4 F 8 H, —CH 2 CH 2 OCH 2 CH 2 C 8 F 17 , —CH 2 CH 2 OCF 2 CF 2 OCF 2 CF 2 H, C 4-20 fluorocycloalkyl group having 4 or more fluorine atoms, and the like can be given.
  • perfluoropolyether group for example, — (CF 2 O) p — (CF 2 CF 2 O) q —, — [CF (CF 3 ) CF 2 O] p — [CF 2 (CF 3 )] ] —, — (CF 2 CF 2 CF 2 O) p —, — (CF 2 CF 2 O) p — and the like.
  • the total of p and q is preferably 1 to 83, more preferably 1 to 43, and most preferably 5 to 23.
  • the fluorine-containing antifouling agent particularly preferably has a perfluoropolyether group represented by — (CF 2 O) p — (CF 2 CF 2 O) q — from the viewpoint of excellent antifouling properties.
  • P and q each independently represents an integer of 0 to 20. However, p + q is an integer of 1 or more.
  • the fluorine-containing antifouling agent has a perfluoropolyether group and has a polymerizable unsaturated group in one molecule. It is preferable to have a plurality.
  • W represents a linking group.
  • W include an alkylene group, an arylene group, a heteroalkylene group, and a linking group obtained by combining these. These linking groups may further have a functional group such as an oxy group, a carbonyl group, a carbonyloxy group, a carbonylimino group, a sulfonamide group, etc., or a combination thereof.
  • W is preferably an ethylene group, more preferably an ethylene group bonded to a carbonylimino group.
  • the product of n and m (n ⁇ m) is preferably 2 or more, more preferably 4 or more. .
  • Rf 2 represents either a fluorine atom or a fluoroalkyl group having 1 to 10 carbon atoms
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents a single bond or Represents an alkylene group
  • R ′ 2 represents a single bond or a divalent linking group
  • p is an integer indicating the degree of polymerization
  • the degree of polymerization p is k (k is an integer of 3 or more) or more.
  • R ′ 2 represents a divalent linking group
  • examples of the divalent linking group include the same linking groups as W.
  • telomer acrylate containing a fluorine atom in the formula (F-1) examples include a (meth) acrylic acid moiety or a fully fluorinated alkyl ester derivative.
  • the group Rf 2 of the formula (F-1) depends on the conditions of telomerization, the separation conditions of the reaction mixture, and the like.
  • P of (CF 2 CF 2 ) p R ′ 2 CH 2 CH 2 R 2 O— may contain a plurality of fluorine-containing (meth) acrylic esters such as k, k + 1, k + 2,.
  • Formula (F-2) F (CF 2 ) q —CH 2 —CHX—CH 2 Y
  • q is an integer of 1 to 20
  • X and Y are each independently either a (meth) acryloyloxy group or a hydroxyl group, and at least one is a (meth) acryloyloxy group.
  • the fluorine-containing (meth) acrylic acid ester represented by the formula (F-2) has a fluoroalkyl group having 1 to 20 carbon atoms having a trifluoromethyl group (CF 3 —) at the terminal. Even if a small amount of fluorine (meth) acrylate is used, the trifluoromethyl group is effectively oriented on the surface.
  • Q is preferably 6 to 20 and more preferably 8 to 10 in terms of antifouling properties and ease of production.
  • the fluorine-containing (meth) acrylic acid ester having a fluoroalkyl group having 8 to 10 carbon atoms is superior to other fluorine-containing (meth) acrylic acid esters having a fluoroalkyl group having a chain length. Because it exhibits oiliness, it has excellent antifouling properties.
  • fluorine-containing (meth) acrylic acid ester represented by the formula (F-2) include 1- (meth) acryloyloxy-2-hydroxy-4,4,5,5,6,6,7, 7,8,8,9,9,10,10,11,11,12,12,13,13,13-heneicosafluorotridecane, 2- (meth) acryloyloxy-1-hydroxy-4,4 5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,13,13,13-heneicosafluorotridecane and 1,2- Bis (meth) acryloyloxy 4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,13,13,13-heneico Examples include safluorotridecane.
  • R 3 represents a hydrogen atom or a methyl group
  • s represents an integer of 1 to 20
  • r represents an integer of 1 to 4.
  • the fluorine atom-containing monofunctional (meth) acrylate represented by the above formula (F-3) is obtained by reacting a fluorine atom-containing alcohol compound represented by the following formula (FG-3) with a (meth) acrylic acid halide. Can be obtained.
  • Formula (FG-3) F (CF 2) r O ( CF 2 CF 2 O) s CF 2 CH 2 OH
  • s represents an integer of 1 to 20
  • r represents an integer of 1 to 4.
  • fluorine atom-containing alcohol compound represented by the formula (FG-3) include, for example, 1H, 1H-perfluoro-3,6-dioxaheptan-1-ol, 1H, 1H-perfluoro-3,6.
  • Examples of the (meth) acrylic acid halide to be reacted with the fluorine atom-containing alcohol compound represented by the formula (FG-3) include (meth) acrylic acid fluoride, (meth) acrylic acid chloride, (meth) acrylic acid bromide, (Meth) acrylic acid iodide can be mentioned. From the viewpoint of easy availability, (meth) acrylic acid chloride is preferred.
  • a compound represented by the following formula (F-3A) can also be preferably used.
  • X 1 and X 2 each independently represent H or F
  • X 3 represents H, F, CH 3 or CF 3
  • X 4 and X 5 each independently represent H, F, or CF 3
  • a, b, and c each independently represent 0 or 1
  • Rf 3 represents a fluorine-containing alkyl group containing an ether bond having 18 to 200 carbon atoms)
  • Rf 3 includes , Formula (FG-3A): -(CX 6 2 CF 2 CF 2 O)- (Wherein, X 6 is F or H) fluorine-containing unsaturated compound having 6 or more repeating units represented by.
  • a group having the following structure is preferable.
  • the definition of each symbol in (c-1) to (c-3) is the same as in formula (F-3A).
  • the fluorine-containing polyether compound represented by the formula (F-3A) may have a plurality of polymerizable unsaturated groups
  • a compound having a structure of —O (C ⁇ O) CF ⁇ CH 2 is preferable because it has a particularly high polymerization (curing) reactivity and can efficiently obtain a cured product.
  • Rf 3 group in the fluorine-containing polyether compound represented by the formula (F-3A) is important to contain in 6 or more Rf 3 in the unit repeatedly fluoropolyether chain of formula (FG-3A) Thus, antifouling properties can be imparted. More specifically, it may be a mixture in which the repeating unit of the fluorine-containing polyether chain contains 6 or more compounds. However, when used in the form of a mixture, the fluorine-containing unsaturated compound having less than 6 repeating units and 6 In a distribution with one or more fluorine-containing unsaturated compounds, a mixture having the highest abundance ratio of the fluorine-containing unsaturated compounds having 6 or more polyether chain repeating units is preferable.
  • the number of repeating units of the fluorine-containing polyether chain of the formula (FG-3A) is preferably 6 or more, more preferably 10 or more, still more preferably 18 or more, and particularly preferably 20 or more.
  • the fluorine-containing polyether chain may be present at the end of the Rf 3 group or in the middle of the chain.
  • Rf 3 group is: Formula (c-4): R 4 - (CX 6 2 CF 2 CF 2 O) t - (R 5) e - (Wherein X 6 is the same as formula (FG-3A), R 4 is selected from a hydrogen atom, a halogen atom or an alkyl group, a fluorine-containing alkyl group, an alkyl group containing an ether bond and a fluorine-containing alkyl group containing an ether bond) And at least one kind, R 5 is a divalent or higher organic group, t is an integer of 6 to 66, and e is 0 or 1.
  • R 5 is a fluorine-containing organic group which is bonded to a reactive carbon-carbon double bond via a divalent or higher-valent organic group R 5 and further has R 4 at the terminal.
  • R 5 may be any organic group as long as it can bind the fluorine-containing polyether chain of the formula (FG-3A) to a reactive carbon-carbon double bond.
  • it is selected from an alkylene group, a fluorine-containing alkylene group, an alkylene group containing an ether bond and a fluorine-containing alkylene group containing an ether bond.
  • a fluorine-containing alkylene group and a fluorine-containing alkylene group containing an ether bond are preferable in terms of transparency and low refractive index.
  • fluorine-containing polyether compound represented by the formula (F-3A) compounds exemplified in WO2003 / 022906 pamphlet are preferably used.
  • CH 2 ⁇ CF—COO—CH 2 CF 2 CF 2 — (OCF 2 CF 2 CF 2 ) 7 —OC 3 F 7 can be used particularly preferably.
  • Rf 1 represents a (per) fluoroalkyl group or (per) fluoropolyether group
  • W represents a linking group
  • R A represents a functional group having an unsaturated double bond.
  • -3 and m represent an integer of 1 to 3, and n and m are not 1 at the same time.
  • n is preferably 2 to 3
  • m is preferably 1 to 3
  • n is 2 to 3
  • n is 2 to 3
  • m is 2 Is more preferably 3
  • n is 3 and m is most preferably 2 to 3.
  • Rf 1 may be a monovalent to trivalent group.
  • terminal groups include (C n F 2n + 1 )-, (C n F 2n + 1 O)-, (XC n F 2n O)-, (XC n F 2n + 1 )-(wherein X is Hydrogen, chlorine, or bromine, and n is preferably an integer of 1 to 10.
  • CF 3 O (C 2 F 4 O) p CF 2 —, C 3 F 7 O (CF 2 CF 2 CF 2 O) p CF 2 CF 2 —, C 3 F 7 O (CF (CF 3 ) CF 2 O) p CF (CF 3 ) —, F (CF (CF 3 ) CF 2 O) p CF (CF 3 ) — and the like can be preferably used.
  • the average value of p is 0-50. It is preferably 3 to 30, more preferably 3 to 20, and most preferably 4 to 15.
  • Rf 1 is divalent, — (CF 2 O) q (C 2 F 4 O) r CF 2 —, — (CF 2 ) 3 O (C 4 F 8 O) r (CF 2 ) 3 —, —CF 2 O (C 2 F 4 O) r CF 2 —, —C 2 F 4 O (C 3 F 6 O) r C 2 F 4 —, —CF (CF 3 ) (OCF 2 CF (CF 3 ) ) s OC t F 2t O ( CF (CF 3) CF 2 O) r CF (CF 3) - and the like can be preferably used.
  • the average value of q, r, and s in the formula is 0-50. It is preferably 3 to 30, more preferably 3 to 20, and most preferably 4 to 15. t is an integer of 2 to 6.
  • Preferred specific examples or synthesis methods of the compound represented by the formula (F-4) are described in International Publication No. 2005/113690.
  • HFPO- a compound having an average value of p of 6 to 7 in F (CF (CF 3 ) CF 2 O) p CF (CF 3 ) —
  • —HFPO— a compound having an average value of p of 6 to 7
  • F-4 a specific compound of the formula (F-4), but is not limited thereto.
  • the compound in which the polymerizable unsaturated group is a (meth) acryloyloxy group may have a plurality of (meth) acryloyloxy groups. Since the fluorine-containing antifouling agent has a plurality of (meth) acryloyloxy groups, when cured, it exhibits a three-dimensional network structure, a high glass transition temperature, and a low transferability of the antifouling agent. In addition, durability against repeated wiping of dirt can be improved. Furthermore, a cured film excellent in heat resistance, weather resistance and the like can be obtained.
  • Specific examples of the compound represented by the formula (F-5) include, for example, di (meth) acrylic acid-2,2,2-trifluoroethylethylene glycol, di (meth) acrylic acid-2,2,3 , 3,3-pentafluoropropylethylene glycol, di (meth) acrylic acid-2,2,3,3,4,4,4-heptafluorobutylethylene glycol, di (meth) acrylic acid-2,2,3 , 3,4,4,5,5,5-nonafluoropentylethylene glycol, di (meth) acrylic acid-2,2,3,3,4,4,5,5,6,6,6-undeca Fluorohexylethylene glycol, di (meth) acrylic acid-2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptylethylene glycol, di (meth) acrylic Acid-2,2,3,3 , 4,5,5,6,6,7,7,8,8,8-pentadecafluorooctylethylene glycol, di (meth)
  • di (meth) acrylic acid ester can be produced by a known method as described in JP-A-6-306326.
  • diacrylic acid-2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-heptadecafluorononylethylene glycol is Preferably used.
  • a compound having a plurality of (per) fluoroalkyl groups or (per) fluoropolyether groups in one molecule as the compound in which the polymerizable unsaturated group is a (meth) acryloyloxy group It may be.
  • the fluorine-containing antifouling agent in this embodiment may be any of a monomer, an oligomer, or a polymer.
  • the fluorine-containing antifouling agent preferably further has a substituent that contributes to bond formation or compatibility in the hard coat layer film. These substituents may be the same or different, and a plurality of substituents are preferable. Examples of preferred substituents include acryloyl group, methacryloyl group, vinyl group, allyl group, cinnamoyl group, epoxy group, oxetanyl group, hydroxyl group, polyoxyalkylene group, carboxyl group, amino group and the like.
  • the fluorine-containing antifouling agent may be a polymer or an oligomer with a compound containing no fluorine atom.
  • the fluorine-containing compound may contain a silicon atom in the molecule, may contain a siloxane structure, or may have a structure other than the siloxane structure.
  • the weight average molecular weight is less than 15,000.
  • the fluorine-containing compound contains a siloxane structure
  • the fluorine-containing compound is preferably represented by the following formula (F-6).
  • R a R f b R A c SiO (4-abc) / 2 (In the formula, R is a hydrogen atom, a methyl group, an ethyl group, a propyl group, or a phenyl group, R f is an organic group containing a fluorine atom, and R A is an organic group containing a polymerizable unsaturated group. Yes, 0 ⁇ a, 0 ⁇ b, 0 ⁇ c, a + b + c ⁇ 4.)
  • a is preferably 1 to 1.75, more preferably 1 to 1.5, and if it is 1 or more, the synthesis of the compound is industrially easy, and if it is 1.75 or less, curability and antifouling properties are improved. Coexistence is easy.
  • the polymerizable unsaturated group in R A include the same polymerizable unsaturated group and R A in formula (F), in preferably (meth) acryloyl group, (meth) acryloyloxy group, and these groups A group in which an arbitrary hydrogen atom is substituted with a fluorine atom.
  • a preferred example of the siloxane structure is a structure having a substituent at the terminal and / or side chain of a compound chain containing a plurality of dimethylsilyloxy units as repeating units.
  • the compound chain containing dimethylsilyloxy as a repeating unit may contain a structural unit other than dimethylsilyloxy.
  • the substituents may be the same or different, and a plurality of substituents are preferable.
  • substituents examples include (meth) acryloyl group, (meth) acryloyloxy group, vinyl group, allyl group, cinnamoyl group, epoxy group, oxetanyl group, hydroxyl group, fluoroalkyl group, polyoxyalkylene group, carboxyl group, amino group
  • substituents include a group containing a group, and a (meth) acryloyloxy group is particularly preferable from the viewpoint of suppressing bleed-out of the antifouling agent.
  • the number of substituents is preferably 1500 to 20000 g ⁇ mol ⁇ 1 as the functional group equivalent from the viewpoint of improving the uneven distribution of the antifouling agent and suppressing bleeding out.
  • R f is an organic group containing a fluorine atom, and is a group represented by C x F 2x + 1 (CH 2 ) p — (wherein x is an integer of 1 to 8, and p is an integer of 2 to 10). Or it is preferably a perfluoropolyether-substituted alkyl group.
  • b is preferably from 0.2 to 0.4, more preferably from 0.2 to 0.25. When it is 0.2 or more, the antifouling property is improved, and when it is 0.4 or less, the curability is improved. To do.
  • R f is preferably a C 8 perfluoroalkyl group.
  • R A is an organic group containing a (meth) acryl group, and the bond to the Si atom is more preferably a Si—O—C bond from the viewpoint of easy industrial synthesis.
  • c is preferably 0.4 to 0.8, more preferably 0.6 to 0.8. When 0.4 or more, the curability is improved, and when 0.8 or less, the antifouling property is improved. To do.
  • a + b + c is preferably 2 to 2.7, more preferably 2 to 2.5.
  • a + b + c is preferably 2 to 2.7, more preferably 2 to 2.5.
  • the fluorine-containing compound contains a siloxane structure
  • the fluorine-containing compound has 3 or more F atoms and 3 or more Si atoms, preferably 3 to 17 F atoms and 3 to 8 Si atoms in one molecule. It is preferable to contain them.
  • the antifouling property is sufficient
  • the antifouling property is sufficient
  • the antifouling property is sufficient
  • the antifouling property is sufficient
  • Si atoms uneven distribution on the surface is promoted and the antifouling property is sufficient.
  • the fluorine-containing compound contains a siloxane structure
  • the fluorine-containing compound can be produced using a known method described in JP-A-2007-14584.
  • the siloxane structure may be any of linear, branched, and cyclic, and among these, compounds having a branched or cyclic structure are particularly described below. It is preferable because it is compatible with a compound having a double bond, has no repelling, and tends to be unevenly distributed on the surface.
  • the compound having a branched siloxane structure is preferably a compound represented by the following formula (F-7).
  • a compound represented by the following formula (F-8) is preferable.
  • fluorine-containing polysiloxane compounds include the following compounds.
  • the weight average molecular weight (Mw) of the fluorine-containing antifouling agent can be measured using molecular exclusion chromatography such as gel permeation chromatography (GPC).
  • Mw of the fluorine-containing antifouling agent used in this embodiment is preferably 400 or more and less than 5000, more preferably 1000 or more and less than 5000, and still more preferably 1000 or more and less than 3500. It is preferable that Mw is 400 or more because the surface migration property of the antifouling agent becomes high. Further, when the Mw is less than 5000, the surface migration of the fluorine-containing antifouling agent is not hindered during the process of curing from coating, and it is easy to orient uniformly on the hard coat layer surface. This is preferable because the hardness is improved. However, when the fluorine-containing compound contains a siloxane structure, Mw is less than 15000, preferably 1000 or more and less than 5000, and more preferably 1000 or more and less than 3500.
  • the addition amount of the fluorine-containing antifouling agent is preferably 1 to 20% by mass, more preferably 1 to 15% by mass with respect to the total solid content in the hard coat layer or the hard coat layer forming composition. More preferred is 10% by mass.
  • the addition amount of the fluorine-containing antifouling agent is 1% by mass or more with respect to the total solid content in the hard coat layer or the hard coat layer forming composition, the ratio of the antifouling agent having water and oil repellency is moderate. Thus, sufficient antifouling property can be obtained.
  • the addition amount of the fluorine-containing antifouling agent is 20% by mass or less based on the total solid content in the hard coat layer or the hard coat layer forming composition, an antifouling agent that cannot be mixed with the resin component is deposited on the surface.
  • the film is not whitened or white powder is not generated on the surface, which is preferable.
  • the fluorine atom content of the fluorine-containing antifouling agent is not particularly limited, but is preferably 20% by mass or more, particularly preferably 30 to 70% by mass, and most preferably 40 to 70% by mass. preferable.
  • fluorine-containing antifouling agents examples include Daikin Chemical Industries, Ltd., R-2020, M-2020, R-3833, M-3833, Optool DAC (trade name), DIC Corporation, MegaFac F- 171, F-172, F-179A, defender MCF-300, MCF-323 (trade name) and the like, but are not limited thereto.
  • Polysiloxane compound having a polymerizable unsaturated group and a weight average molecular weight of 15000 or more Next, a polysiloxane compound having a polymerizable unsaturated group and having a weight average molecular weight of 15000 or more that can be used as the component g) will be described.
  • a polysiloxane compound having a molecular weight of 15000 or more is referred to as a “polysiloxane antifouling agent”.
  • polysiloxane antifouling agent is a compound represented by the above formula (F-6).
  • the polysiloxane antifouling agent include compounds having a substituent at the terminal and / or side chain of a compound chain containing a plurality of dimethylsilyloxy units as repeating units.
  • the compound chain containing dimethylsilyloxy as a repeating unit may contain a structural unit other than dimethylsilyloxy.
  • the substituents may be the same or different, and a plurality of substituents are preferable.
  • substituents examples include (meth) acryloyl group, (meth) acryloyloxy group, vinyl group, allyl group, cinnamoyl group, epoxy group, oxetanyl group, hydroxyl group, fluoroalkyl group, polyoxyalkylene group, carboxyl group, amino group
  • substituents include a group containing a group, and a (meth) acryloyloxy group is particularly preferable from the viewpoint of suppressing bleed-out of the antifouling agent.
  • the number of substituents is preferably 1500 to 20000 g ⁇ mol ⁇ 1 as the functional group equivalent from the viewpoint of improving the uneven distribution of the antifouling agent and suppressing bleeding out.
  • the polysiloxane antifouling agent is preferably a compound containing 3 or more F atoms and 3 or more Si atoms, preferably 3 to 17 F atoms and 3 to 8 Si atoms in one molecule. .
  • the antifouling property is sufficient
  • the antifouling property is sufficient
  • the antifouling property is sufficient
  • the antifouling property is sufficient
  • the antifouling property is sufficient
  • the antifouling property uneven distribution on the surface is promoted and the antifouling property is sufficient.
  • the polysiloxane antifouling agent can be produced using a known method described in JP-A-2007-14584.
  • Examples of the additive having a polysiloxane structure include reactive group-containing polysiloxanes ⁇ eg, “KF-100T”, “X-22-169AS”, “KF-102”, “X-22-3701IE”, “X-22”.
  • the siloxane structure contained in the polysiloxane antifouling agent may be linear, branched, or cyclic, and among these, a compound having a branched or cyclic structure is an unsaturated double bond described later. It is preferable because it has good compatibility with a compound having an alkenyl group, has no repelling, and tends to be unevenly distributed on the surface.
  • the weight average molecular weight of the polysiloxane antifouling agent is 15000 or more, preferably 15000 or more and 50000 or less, more preferably 18000 or more and 30000 or less. If the weight average molecular weight of the polysiloxane antifouling agent is less than 15,000, the surface uneven distribution of the polysiloxane is reduced, which is not preferable from the viewpoint of causing deterioration of the antifouling property and a decrease in hardness. However, the above problem does not occur when the fluorine-containing compound having a polymerizable unsaturated group has a polysiloxane structure.
  • the weight average molecular weight of the polysiloxane antifouling agent can be measured using molecular exclusion chromatography such as gel permeation chromatography (GPC).
  • the addition amount of the polysiloxane antifouling agent is preferably 1% by mass or more and less than 25% by mass with respect to the total solid content in the hard coat layer or the hard coat layer forming composition, and is preferably 1% by mass or more and 20% by mass. Is more preferably 1% by mass or more and less than 15% by mass, and most preferably 1% by mass or more and less than 10% by mass.
  • the addition amount of the polysiloxane antifouling agent is 1% by mass or more with respect to the total solid content in the hard coat layer or the hard coat layer forming composition, the ratio of the antifouling agent having water and oil repellency is moderate. Thus, sufficient antifouling property can be obtained.
  • the addition amount of the polysiloxane antifouling agent is less than 25% by mass with respect to the total solid content in the hard coat layer or the hard coat layer forming composition, an antifouling agent that cannot be mixed with the resin component is deposited on the surface.
  • the film is not whitened or white powder is not generated on the surface, which is preferable.
  • the distribution state in the film thickness direction of the antifouling agent in the hard coat layer is 51 when X is the amount of fluorine or silicone in the vicinity of the surface of the hard coat layer, and Y is the amount of fluorine or silicone in the entire hard coat layer. % ⁇ X / Y ⁇ 100% is preferably satisfied. When X / Y is greater than 51%, the antifouling agent is not distributed to the inside of the hard coat layer, which is preferable in terms of antifouling properties and film hardness.
  • the vicinity of the surface refers to the area from the surface of less than 1 ⁇ m depth of the hard coat layer was measured by time-of-flight secondary ion mass spectrometry (TOF-SIMS) F - fragment or Si 2 C 5 H 15 O + It can be measured by the ratio of fragments.
  • TOF-SIMS time-of-flight secondary ion mass spectrometry
  • the antifouling agent is preferably an antifouling agent that dissolves in a liquid or solvent at 20 ° C.
  • the solvent can be appropriately selected depending on the polarity of the compound, but is preferably an organic solvent miscible with dimethyl carbonate, and examples thereof include aliphatic or aromatic alcohols, ketones, esters, and ether solvents. It is particularly preferred if it is dissolved in dimethyl carbonate.
  • the surface tension of the antifouling agent is preferably 25.0 mN / m or less, more preferably 23.0 mN / m or less, and 16.0 mN / m. More preferably, it is as follows.
  • the surface tension of the antifouling agent is the surface tension of a single film and can be measured as follows.
  • the angle formed between the tangent to the liquid surface and the film surface at the point where the film and the liquid are in contact with each other, and the angle on the side containing the liquid was defined as the contact angle. Further, the contact angle was measured using methylene iodide instead of water, and the surface free energy was obtained from the following equation. What is surface free energy ( ⁇ s v : unit, mN / m)? K. Owens: J.M. Appl. Polym. Sci.
  • the antifouling agent a compound synthesized by a known method may be used, or a commercially available product may be used.
  • a commercially available product RS-90, RS-78 manufactured by DIC, etc. can be preferably used.
  • the composition for forming a hard coat layer in the present embodiment may contain a solvent.
  • the solvent is selected from the viewpoints of being able to dissolve or disperse each component, easily forming a uniform surface in the coating process and the drying process, ensuring liquid storage stability, having an appropriate saturated vapor pressure, and the like.
  • Various solvents can be used.
  • the solvent can be used by mixing two or more kinds of solvents.
  • the main component is a solvent having a boiling point of 100 ° C. or lower at normal pressure and room temperature, and a small amount of solvent having a boiling point of more than 100 ° C. is included for adjusting the drying speed.
  • the composition for forming a hard coat layer in the present embodiment it is preferable to contain a solvent having a boiling point of 80 ° C. or lower in an amount of 30 to 80% by mass in the total solvent of the coating composition in order to prevent the particles from sedimenting. More preferably, it is contained by mass.
  • Examples of the solvent having a boiling point of 100 ° C. or lower include hydrocarbons such as hexane (boiling point 68.7 ° C.), heptane (98.4 ° C.), cyclohexane (80.7 ° C.), benzene (80.1 ° C.), Halogenated carbonization such as dichloromethane (39.8 ° C), chloroform (61.2 ° C), carbon tetrachloride (76.8 ° C), 1,2-dichloroethane (83.5 ° C), trichloroethylene (87.2 ° C) Hydrogens, diethyl ether (34.6 ° C), diisopropyl ether (68.5 ° C), dipropyl ether (90.5 ° C), tetrahydrofuran (66 ° C) and other ethers, ethyl formate (54.2 ° C), Esters such as methyl acetate (57.8 ° C.), ethyl a
  • Examples of the solvent having a boiling point exceeding 100 ° C. include octane (125.7 ° C.), toluene (110.6 ° C.), xylene (138 ° C.), tetrachloroethylene (121.2 ° C.), chlorobenzene (131.7 ° C.), Dioxane (101.3 ° C.), dibutyl ether (142.4 ° C.), isobutyl acetate (118 ° C.), cyclohexanone (155.7 ° C.), 2-methyl-4-pentanone (same as MIBK, 115.9 ° C.), Examples include 1-butanol (117.7 ° C.), N, N-dimethylformamide (153 ° C.), N, N-dimethylacetamide (166 ° C.), and dimethyl sulfoxide (189 ° C.). Cyclohexanone and 2-methyl-4-pentanone are preferable.
  • surfactant In the present embodiment, it is also preferable to use various surfactants and / or wind unevenness inhibitors (hereinafter, collectively referred to as surfactants) in the hard coat layer or the hard coat layer forming composition.
  • surfactants and / or wind unevenness inhibitors can suppress film thickness unevenness due to drying variations due to local distribution of dry air.
  • the surfactant preferably contains a fluorine-based surfactant, a silicone-based surfactant, or both. Further, the surfactant is preferably an oligomer or a polymer rather than a low molecular compound.
  • fluorosurfactant examples include a fluoroaliphatic group-containing copolymer (hereinafter sometimes abbreviated as “fluorine polymer”), and the fluoropolymer includes the following (i): An acrylic resin, a methacrylic resin, and a copolymerizable copolymer containing a repeating unit corresponding to the monomer or a repeating unit corresponding to the monomer (i) and a repeating unit corresponding to the monomer (ii) below.
  • Copolymers with vinyl monomers are useful.
  • R 11 represents a hydrogen atom or a methyl group
  • X represents an oxygen atom, a sulfur atom or —N (R 12 ) —
  • m is an integer of 1 to 6
  • n is an integer of 2 to 4 Represents.
  • R 12 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, specifically a methyl group, an ethyl group, a propyl group or a butyl group, preferably a hydrogen atom or a methyl group.
  • X is preferably an oxygen atom.
  • R 13 represents a hydrogen atom or a methyl group
  • Y represents an oxygen atom, a sulfur atom or —N (R 15 ) —
  • R 15 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Specifically, it represents a methyl group, an ethyl group, a propyl group or a butyl group, preferably a hydrogen atom or a methyl group.
  • Y is preferably an oxygen atom, —N (H) —, and —N (CH 3 ) —.
  • R 14 represents a linear, branched or cyclic alkyl group having 4 to 20 carbon atoms which may have a substituent.
  • Examples of the substituent for the alkyl group represented by R 14 include a hydroxyl group, an alkylcarbonyl group, an arylcarbonyl group, a carboxyl group, an alkyl ether group, an aryl ether group, a halogen atom such as a fluorine atom, a chlorine atom, and a bromine atom, a nitro group, and a cyano group. , Amino groups and the like, but not limited thereto.
  • linear, branched or cyclic alkyl group having 4 to 20 carbon atoms examples include a butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and undecyl group which may be linear or branched.
  • a polycyclic cycloalkyl group such as a tetracyclododecyl group, an adamantyl group, a norbornyl group, a tetracyclodecyl group, or the like is preferably used.
  • the amount of the fluoroaliphatic group-containing monomer represented by the formula (i) used in the fluoropolymer is 10 mol% or more based on each monomer of the fluoropolymer, preferably 15 to 70 mol. %, And more preferably in the range of 20 to 60 mol%.
  • the preferred mass average molecular weight of the fluoropolymer is preferably 3000 to 100,000, more preferably 5,000 to 80,000. Further, the preferred addition amount of the fluorine-based polymer is in the range of 0.001 to 5 parts by mass, more preferably in the range of 0.005 to 3 parts by mass, more preferably 0 to 100 parts by mass of the coating solution. The range is from 0.01 to 1 part by mass. If the addition amount of the fluorine-based polymer is 0.001 part by mass or more, the effect of adding the fluorine-based polymer is sufficiently obtained, and if the addition amount is 5 parts by mass or less, the coating film cannot be sufficiently dried or applied. There is no problem of adversely affecting the performance as a film.
  • silicone compounds examples include X-22-174DX, X-22-2426, X22-164C, X-22-176D (trade names) manufactured by Shin-Etsu Chemical Co., Ltd .; FM-7725, FM-5521, FM-6621 (named above); DMS-U22 manufactured by Gelest, RMS-033 (named above); SH200, DC11PA, ST80PA, L7604 made by Toray Dow Corning Co., Ltd. , FZ-2105, L-7604, Y-7006, SS-2801 (trade name); TSF400 (trade name) manufactured by Momentive Performance Materials Japan, but not limited thereto.
  • the silicone-based surfactant is preferably contained in an amount of 0.01 to 0.5% by mass when the total solid content of the composition for forming a hard coat layer in this embodiment is 100% by mass. More preferable is 0.3 mass%.
  • the hard coat layer or the composition for forming a hard coat layer has matte particles having an average particle size of 1.0 to 15.0 ⁇ m, preferably 1.5 to 10.0 ⁇ m for the purpose of imparting internal scattering properties or surface irregularities. It may contain. Moreover, in order to adjust the viscosity of a coating liquid, a high molecular compound, an inorganic layered compound, etc. can also be included. e) may be used as matte particles.
  • the hard coat film according to one aspect of the present disclosure may include other layers (arbitrary layers) in addition to the polyester film and the hard coat layer according to the embodiment described above.
  • Examples of such an arbitrary layer include an easy adhesion layer, an antireflection layer (a laminated film of one or more high refractive index layers and one or more low refractive index layers), an antiglare layer, an antistatic layer, and the like.
  • an easy adhesion layer an antireflection layer (a laminated film of one or more high refractive index layers and one or more low refractive index layers), an antiglare layer, an antistatic layer, and the like.
  • it is not limited to these.
  • a low refractive index layer can be formed on the hard coat layer for the purpose of providing a reflectance reduction effect.
  • the low refractive index layer has a lower refractive index than the hard coat layer, and the thickness is preferably 50 to 200 nm, more preferably 70 to 150 nm, and most preferably 80 to 120 nm.
  • the refractive index of the low refractive index layer is lower than the refractive index of the layer immediately below, preferably 1.20 to 1.55, more preferably 1.25 to 1.46, and 1.30 to 1. .40 is particularly preferred.
  • the thickness of the low refractive index layer is preferably 50 to 200 nm, and more preferably 70 to 100 nm.
  • the low refractive index layer is preferably obtained by curing a curable composition for forming the low refractive index layer.
  • the curable composition of the low refractive index layer As a preferred embodiment of the curable composition of the low refractive index layer, (1) A composition containing a fluorine-containing compound having a crosslinkable or polymerizable functional group, (2) a composition comprising as a main component a hydrolysis-condensation product of a fluorine-containing organosilane material; (3) a composition containing a monomer having two or more ethylenically unsaturated groups and inorganic particles (in particular, inorganic particles having a hollow structure are preferred); Etc.
  • compositions (1) and (2) it is preferable to contain inorganic particles, and when inorganic particles having a hollow structure with a low refractive index are used, the refractive index is lowered or the amount of inorganic particles added and the refraction. It is particularly preferable from the viewpoint of adjusting the rate.
  • Composition containing a fluorine-containing compound having a crosslinkable or polymerizable functional group As the fluorine-containing compound having a crosslinkable or polymerizable functional group, a fluorine-containing monomer and a crosslinkable or polymerizable functional group are used. Mention may be made of a fluorine-containing polymer which is a copolymer with the monomer it has. Specific examples of these fluoropolymers are described in JP2003-222702A, JP2003-183322A, and the like.
  • the above fluorine-containing polymer may be used in combination with a curing agent having a polymerizable unsaturated group as appropriate.
  • a curing agent having a polymerizable unsaturated group as appropriate.
  • combined use with a compound having a fluorine-containing polyfunctional polymerizable unsaturated group is also preferable.
  • the compound having a polyfunctional polymerizable unsaturated group include monomers having two or more ethylenically unsaturated groups described as the curable resin compound for the low refractive index layer.
  • hydrolysis-condensation product of organolane described in JP-A-2004-170901 is preferable, and the hydrolysis-condensation product of organosilane containing a (meth) acryloyl group is particularly preferable.
  • organosilane containing a (meth) acryloyl group is particularly preferable.
  • the necessary curability can be imparted by blending a crosslinkable compound.
  • various amino compounds are preferably used as the curing agent.
  • the amino compound used as the crosslinkable compound is, for example, a compound containing one or both of a hydroxyalkylamino group and an alkoxyalkylamino group in total, specifically, for example, a melamine compound, Examples include urea compounds, benzoguanamine compounds, glycoluril compounds, and the like.
  • an organic acid or a salt thereof is preferably used.
  • composition mainly composed of hydrolyzed condensate of fluorine-containing organosilane material The composition mainly composed of hydrolyzed condensate of fluorine-containing organosilane compound also has a low refractive index and the hardness of the coating surface. Is preferable. A condensate of a tetraalkoxysilane with a hydrolyzable silanol-containing compound at one or both ends with respect to the fluorinated alkyl group is preferred. Specific compositions are described in JP-A Nos. 2002-265866 and 317152.
  • a composition containing a monomer having two or more ethylenically unsaturated groups and inorganic particles having a hollow structure As still another preferred embodiment, a low refractive index layer comprising a low refractive index particle and a resin can be mentioned. .
  • the low refractive index particles may be organic or inorganic, but particles having pores inside are preferable.
  • Specific examples of the hollow particles include silica-based particles described in JP-A No. 2002-79616.
  • the particle refractive index is preferably from 1.15 to 1.40, more preferably from 1.20 to 1.30.
  • the resin include monomers having two or more ethylenically unsaturated groups described on the page of the antiglare layer.
  • a photoradical polymerization initiator or a thermal radical polymerization initiator it is preferable to add a photoradical polymerization initiator or a thermal radical polymerization initiator to the composition for forming a low refractive index layer used in the present embodiment.
  • a radically polymerizable compound 1 to 10 parts by mass, preferably 1 to 5 parts by mass of a polymerization initiator can be used with respect to the above compound.
  • inorganic particles can be used in combination.
  • particles having a particle size of 15% to 150%, preferably 30% to 100%, more preferably 45% to 60% of the thickness of the low refractive index layer can be used. .
  • the low refractive index layer used in the present embodiment is a known polysiloxane-based or fluorine-based antifouling agent or slipping agent for the purpose of imparting antifouling properties, water resistance, chemical resistance, slipping properties and the like. Etc. can be suitably added.
  • Examples of the additive having a polysiloxane structure include reactive group-containing polysiloxane ⁇ for example, KF-100T, X-22-169AS, KF-102, X-22-37-01IE, X-22-164B, X-22- 5002, X-22-173B, X-22-174D, X-22-167B, X-22-161AS (trade name), manufactured by Shin-Etsu Chemical Co., Ltd .; AK-5, AK-30, AK- 32 (trade name), manufactured by Toa Gosei Co., Ltd .; “Silaplane FM0725”, “Silaplane FM0721” (trade name), manufactured by JNC Co., Ltd., etc. ⁇ are also preferably added.
  • silicone compounds described in Tables 2 and 3 of JP-A-2003-112383 can also be preferably used.
  • the fluorine compound a compound having a fluoroalkyl group is preferable.
  • the fluoroalkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and a straight chain (eg, —CF 2 CF 3 , —CH 2 (CF 2 ) 4 H, —CH 2 (CF 2 ) 8 CF 3 , —CH 2 CH 2 (CF 2 ) 4 H, etc.), even branched structures (eg, CH (CF 3 ) 2 , CH 2 CF (CF 3 ) 2 , CH (CH 3 ) CF 2 CF 3 , CH (CH 3 ) (CF 2 ) 5 CF 2 H, etc.), alicyclic structures (preferably 5-membered or 6-membered rings such as perfluorocyclohexyl group, perfluorocyclopentyl, etc.
  • Group or an alkyl group substituted with these may have an ether bond (for example, CH 2 OCH 2 CF 2 CF 3 , CH 2 CH 2 OCH 2 C 4 F 8 H, CH 2 CH 2 O H 2 CH 2 C 8 F 17 , CH 2 CH 2 OCF 2 CF 2 OCF 2 CF 2 H , etc.).
  • a plurality of the fluoroalkyl groups may be contained in the same molecule.
  • the fluorine-based compound further has a substituent that contributes to bond formation or compatibility with the low refractive index layer film.
  • the above substituents may be the same or different, and a plurality of substituents are preferable.
  • Examples of preferred substituents include acryloyl group, methacryloyl group, vinyl group, aryl group, cinnamoyl group, epoxy group, oxetanyl group, hydroxyl group, polyoxyalkylene group, carboxyl group, amino group and the like.
  • the fluorine-based compound may be a polymer or an oligomer with a compound not containing a fluorine atom, and the molecular weight is not particularly limited.
  • the fluorine atom content of the fluorine-based compound is not particularly limited, but is preferably 20% by mass or more, particularly preferably 30 to 70% by mass, and most preferably 40 to 70% by mass.
  • preferable fluorine-based compounds include Daikin Chemical Industries, Ltd., R-2020, M-2020, R-3833, M-3833, Optool DAC (trade name), DIC Corporation, MegaFuck F-171, Examples include, but are not limited to, F-172, F-179A, defender MCF-300, MCF-323 (named above).
  • polysiloxane fluorine-based compounds or compounds having a polysiloxane structure are preferably added in the range of 0.1 to 10% by mass, particularly preferably 1 to 5% by mass of the total solid content of the low refractive index layer. It is.
  • the hard coat layer according to the hard coat film of the present disclosure can be formed by the following method. First, a composition for forming a hard coat layer is prepared. Next, the composition is applied onto a polyester film (base film) by dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, die coating, etc., and heated. ⁇ dry. A micro gravure coating method, a wire bar coating method, and a die coating method (see US Pat. No. 2,681,294 and JP-A-2006-122889) are more preferable, and a die coating method is particularly preferable.
  • the hard coat layer is applied on a base film and then conveyed by a web to a heated zone to dry the solvent.
  • the temperature of the drying zone at that time is preferably 25 ° C. to 140 ° C.
  • the first half of the drying zone is preferably a relatively low temperature
  • the latter half is preferably a relatively high temperature.
  • it is preferably below the temperature at which components other than the solvent contained in the coating composition of each layer start to volatilize.
  • some of the commercially available photo radical generators used in combination with ultraviolet curable resins volatilize around several tens of percent within a few minutes in warm air at 120 ° C. Some acrylate monomers and the like undergo volatilization in warm air at 100 ° C.
  • the temperature is preferably equal to or lower than the temperature at which components other than the solvent contained in the hard coat layer coating composition start to volatilize.
  • the drying wind after the hard coat layer coating composition is coated on the base film has a wind speed of 0.1 to 2 m on the coating surface while the solid content concentration of the coating composition is 1 to 50%. / Second is preferable in order to prevent unevenness in drying.
  • the temperature difference between the transport roll and the base film contacting the surface opposite to the coating surface of the base film in the drying zone is 0 ° C. When the temperature is within -20 ° C, drying unevenness due to heat transfer unevenness on the transport roll can be prevented, which is preferable.
  • the web is passed through a zone where the hard coat layer is cured by irradiation with ionizing radiation, and the coating film is cured.
  • the coating film is ultraviolet curable, it is preferable to cure the coating film by irradiating with an ultraviolet lamp at an irradiation amount of 10 mJ / cm 2 to 1000 mJ / cm 2 .
  • the irradiation distribution in the width direction of the web is preferably 50 to 100%, more preferably 80 to 100%, including both ends with respect to the central maximum irradiation.
  • the oxygen concentration is preferably 0.01% to 5%, and the distribution in the width direction is 2% or less in terms of oxygen concentration. Is preferred.
  • ultraviolet irradiation ultraviolet rays emitted from light such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, a metal halide lamp, etc. can be used.
  • the temperature can be increased during curing, preferably 25 to 100 ° C., more preferably 30 to 80 ° C., and most preferably 40 to 70 ° C.
  • the use of the polyester film according to the present embodiment is not particularly limited, and can be suitably used for uses that are required to suppress the formation of recesses when a load is applied.
  • the polyester film which concerns on this embodiment can be used suitably as a base film of various functional films, such as a sensor film for touch panels, a scattering prevention film, an antireflection film other than the base film of a hard coat film, for example.
  • the scattering prevention film according to this embodiment is a scattering prevention film in which an adhesive layer is laminated on at least one surface of the polyester film according to this embodiment.
  • the polyester film according to this embodiment can be used as a scattering prevention film.
  • a hard coat layer and an adhesive layer are laminated on a polyester film.
  • the adhesive layer may be formed by either a wet coating method or a dry coating method.
  • an acrylic adhesive composition such as a solvent-based acrylic polymer or solvent-based acrylic syrup, solvent-free acrylic syrup, or solvent-free urethane acrylate can be used.
  • the antireflection film according to this embodiment is an antireflection film in which an antiglare layer is laminated on at least one surface of the polyester film according to this embodiment.
  • the polyester film according to this embodiment can be used for an antireflection film.
  • the antiglare layer may be formed by either a wet coating method or a dry coating method. JP-A-2014-059334, JP-A-2014-026122, JP-A-2014-016602, JP-A-2014-016476, JP-A-2014-041206, JP-A-2014-032317, JP-A-2014-026123, JP-A
  • the antiglare layer described in 2014-010316 can be used.
  • the sensor film for a touch panel according to the present embodiment is a sensor film for a touch panel including the polyester film according to the present embodiment.
  • the polyester film according to this embodiment can be used for a sensor film for a touch panel.
  • a hard coat layer and a transparent conductive layer are laminated on a polyester film.
  • Common methods for forming a transparent conductive layer include PVD (Physical Vapor Deposition) methods such as sputtering, vacuum deposition, and ion plating, or CVD (Chemical Vapor Deposition), coating, and printing. is there.
  • the material for forming the transparent conductive layer is not particularly limited, and examples thereof include indium / tin composite oxide (ITO), tin oxide, copper, silver, aluminum, nickel, and chromium. May be formed.
  • the undercoat layer for improving transparency or an optical characteristic may be provided before forming a transparent conductive layer.
  • a metal layer made of a single metal element or an alloy of two or more metal elements may be provided between the undercoat layer and the polyester film. It is desirable to use a metal selected from the group consisting of silicon, titanium, tin and zinc for the metal layer.
  • the image display apparatus includes an image display element and the hard coat film according to the present embodiment, and the hard coat film is disposed on the outermost surface.
  • Examples of the image display device according to this embodiment include an image display device such as a liquid crystal display (LCD), a plasma display panel, an electroluminescence display, and a cathode tube display.
  • LCD liquid crystal display
  • plasma display panel a plasma display panel
  • electroluminescence display a cathode tube display.
  • the liquid crystal display device As the liquid crystal display device, a TN (Twisted Nematic) type, a STN (Super-Twisted Nematic) type, a TSTN (Triple Super Twisted Nematic) type, a multi-domain type, a VA (Vertical Alignment In) type, an IPS type, an IPS type OCB (Optically Compensated Bend) type etc. are mentioned.
  • the image display device includes a liquid crystal cell and a polarizing plate according to the present embodiment disposed on at least one surface of the liquid crystal cell, and the hard coat film according to the present embodiment is disposed on the outermost surface.
  • An apparatus is preferred.
  • the image display element is a liquid crystal display element.
  • the image display element is preferably an organic electroluminescence display element.
  • the touch panel according to the present embodiment includes the hard coat film according to the present embodiment, and the hard coat film is disposed on the outermost surface.
  • the touch panel to which the hard coat film according to this embodiment can be applied is not particularly limited and can be appropriately selected depending on the purpose.
  • a surface capacitive touch panel, a projected capacitive touch panel, a resistive touch panel, and the like can be given. Details will be described later as the resistive touch panel according to the present embodiment and the capacitive touch panel according to the present embodiment.
  • the touch panel includes so-called touch sensors and touch pads.
  • the layer structure of the touch panel sensor electrode part in the touch panel is a bonding method in which two transparent electrodes are bonded, a method in which transparent electrodes are provided on both surfaces of a single substrate, a single-sided jumper or through-hole method, or a single-area layer method. Either is acceptable.
  • the projected capacitive touch panel is preferably AC (Alternating Current) drive than DC (Direct Current) drive, and more preferably a drive method in which the voltage application time to the electrodes is short.
  • the resistive film type touch panel according to the present embodiment is a resistive film type touch panel including the hard coat film according to the present embodiment.
  • the resistive touch panel has a basic configuration in which a conductive film of a pair of upper and lower substrates having a conductive film is disposed via a spacer so that the conductive films face each other.
  • the configuration of the resistive film type touch panel is well known, and any known technique can be applied without any limitation in the present embodiment.
  • the capacitive touch panel according to the present embodiment is a capacitive touch panel including the hard coat film according to the present embodiment.
  • Examples of the capacitive touch panel system include a surface capacitive type and a projected capacitive type.
  • the projected capacitive touch panel has a basic configuration in which an X-axis electrode and a Y-axis electrode orthogonal to the X-axis electrode are arranged via an insulator.
  • an aspect in which the X electrode and the Y electrode are formed on different surfaces on one substrate, an aspect in which the X electrode, the insulator layer, and the Y electrode are formed in this order on the single substrate.
  • Examples include an embodiment in which an X electrode is formed on one substrate and a Y electrode is formed on another substrate (in this embodiment, a configuration in which two substrates are bonded together is the above basic configuration).
  • the configuration of the capacitive touch panel is known, and any known technique can be applied without any limitation in the present embodiment.
  • the reaction product was transferred to a second esterification reaction vessel, and reacted with stirring at a temperature in the reaction vessel of 250 ° C. and an average residence time of 1.2 hours.
  • the second esterification reaction tank is continuously supplied with an ethylene glycol solution of magnesium acetate and an ethylene glycol solution of trimethyl phosphate so that the Mg addition amount and the P addition amount are 65 ppm and 35 ppm in terms of element, respectively. did.
  • reaction tank temperature was 276 ° C.
  • reaction tank pressure was 5 torr (6.67 ⁇ 10 ⁇ 4 MPa)
  • residence time was about 1.2 hours.
  • the reaction (polycondensation) was performed under the conditions.
  • the reaction product (polyethylene terephthalate; PET) was obtained by reaction (polycondensation) under the following conditions.
  • reaction product was discharged into cold water in a strand shape and immediately cut to prepare a polyester pellet “cross section: major axis: about 4 mm, minor axis: about 2 mm, length: about 3 mm”.
  • the back pressure was increased by 1% with respect to the average pressure in the barrel of the extruder, and the piping temperature of the extruder was made 2% higher than the average temperature in the barrel of the extruder.
  • the molten resin extruded from the die was extruded onto a cooling cast drum set at a temperature of 25 ° C., and adhered to the cooling cast drum using an electrostatic application method. It peeled using the peeling roll arrange
  • Polyester resin (IC) 60 parts by mass Acrylic resin: (II) 25 parts by mass Melamine compound: (VIB) 10 parts by mass Particles: (VII) 5 parts by mass Details of the compounds used for forming the easy adhesion layer are shown below. .
  • the surface temperature at the starting point of stretching is the position of the central part in the film width direction at the point of starting stretching, a radiation thermometer (manufactured by Hayashi Denko, model number: RT61-2, used at an emissivity of 0.95) It was measured by.
  • Heat fixing part and heat relaxation part Subsequently, hot fixing from the up-down direction was applied to the film from the hot air blowing nozzle to the film, and heat fixing and heat relaxation treatment were performed while controlling the surface temperature of the polyester film within the following range.
  • the film was cooled by applying cold air from above and below to the film from a cold air blowing nozzle.
  • the film was cooled so that the surface temperature when the film was released from the tenter clip was 40 ° C.
  • the surface temperature was measured with a radiation thermometer (manufactured by Hayashi Denko, model number: RT61-2, used at an emissivity of 0.95) at the central position in the film width direction.
  • both ends of the polyester film were trimmed by 20 cm.
  • the film width after trimming was 2 m.
  • a film having a length of 10,000 m was wound up in a roll form with a tension of 18 kg / m.
  • the polyester film of Example 1 having a thickness of 200 ⁇ m wound in a roll form was produced.
  • Example 2 [Examples 2 to 11, 13, 14 and Comparative Examples 1 to 3, 5]
  • Example 1 the conditions of the transverse stretching process, the easy-adhesion layer, and the hard coat layer were the same as in Example 1 except that the polyesters of the examples and comparative examples were changed as described in Table 1 below. A film was produced.
  • Example 12 A polyester film of Example 12 was produced in the same manner as Example 1 except that the easy adhesion layer was not provided. Moreover, the polyester film of the comparative example 4 was manufactured like Example 1 except having changed the conditions and film thickness of the horizontal extending
  • the thickness of the polyester film of each Example and Comparative Example obtained was determined as follows. Using a contact-type film thickness meter (manufactured by Anritsu) for the polyester film of each example and comparative example, 50 points were sampled at equal intervals over 0.5 m in the longitudinally stretched direction (longitudinal direction). After sampling 50 points at equal intervals (50 equal parts in the width direction) over the entire width of the film in the film width direction (direction perpendicular to the longitudinal direction), the thicknesses of these 100 points were measured. The average thickness of these 100 points was determined and used as the thickness of the polyester film.
  • Re and Rth of the film obtained in each example were determined by the method described above. From the obtained Re and Rth, the Re / Rth ratio was calculated.
  • a coating liquid for forming a hard coat layer having the following composition was prepared.
  • ⁇ Cyclomer M100 3,4-epoxycyclohexylmethyl methacrylate (manufactured by Daicel Corporation) 40 parts by mass
  • Irgacure 127 alkylphenone photopolymerization started Agent (BASF (manufactured)) 2.5 parts by mass-Irgacure 290: Sulfonium salt-based cationic polymerization initiator (BASF (manufactured)) 2.0 parts by mass-Wind unevenness inhibitor
  • FP-1 Fluorine-containing compound having the following structure 1 part by mass / solvent 1 MEK 100 parts by mass / solvent 2 MIBK 50 parts by mass
  • the uniaxially stretched polyester films wound up in the form of rolls were unwound and applied as a post-process by applying the hard coat layer forming coating solution by the following method.
  • a coating solution for forming a hard coat layer is formed by a die coating method using a slot die described in Example 1 of Japanese Patent Application Laid-Open No. 2006-122889 on one side of the film (when the easy adhesion layer is provided), a conveyance speed of 30 m.
  • the coating was performed under the conditions of / min. After drying at 60 ° C.
  • the coating layer (hard coat layer) was cured by irradiating with / cm 2 of ultraviolet rays and wound up.
  • the thickness of the hard coat layer is 22 ⁇ m.
  • the hard coat layer The thickness was 5 ⁇ m.
  • the film thickness of the hard coat layer was calculated by measuring the film thickness of the hard coat film prepared with a contact-type film thickness meter, and subtracting the thickness of the polyester film measured in the same manner.
  • ⁇ Surface deformation evaluation> A dent when the hard coat film surface (hard coat layer side) was pressed with a force of 10 N / mm 2 with an iron brush was observed and evaluated according to the following criteria. A: No dent occurs at all. B: The dent is not visually recognized, but can be recognized by microscopic observation. C: The dent is slightly visible. D: The dent is clearly visible.
  • DPHA KAYARD DPHA (manufactured by Nippon Kayaku Co., Ltd.) 3,4-epoxy CHMA: 3,4-epoxycyclohexylmethyl acrylate 3,4-epoxy CHMM: 3,4-epoxycyclohexylmethyl methacrylate
  • IRG127 Irgacure 127 (alkylphenone photopolymerization initiator, manufactured by BASF)
  • IRG290 Irgacure 290 (sulfonium salt-based cationic polymerization initiator, manufactured by BASF)
  • RS-90 Anti-fouling agent, manufactured by DIC Corporation)
  • the hard coat film of the example suppressed both the occurrence of cracks and peeling of the hard coat layer and the occurrence of dents as compared with the hard coat film of the comparative example.
  • Cutting blade 12 Polyester film 20 Clip (gripping member)

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  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Manufacture Of Switches (AREA)
  • Surface Treatment Of Optical Elements (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
  • Polarising Elements (AREA)

Abstract

La présente invention concerne un film de polyester qui ne risque pas d'être enfoncé même si une charge est appliquée localement dans le sens de l'épaisseur du film. Le film de polyester présente une épaisseur de 40 à 500 µm et une valeur moyenne de contrainte normale de plan de cisaillement A dans un sens de l'axe de phase lente dans une couche superficielle de 1 μm et de contrainte normale de plan de cisaillement B dans un sens orthogonal au sens de l'axe de phase lente dans le plan du film qui est de 30 à 100 MPa.
PCT/JP2017/003241 2016-02-15 2017-01-30 Film de polyester et son procédé de fabrication, film de revêtement dur et son procédé de fabrication, appareil d'affichage d'image et écran tactile WO2017141680A1 (fr)

Priority Applications (4)

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KR1020187023552A KR102222794B1 (ko) 2016-02-15 2017-01-30 폴리에스터 필름 및 그 제조 방법, 하드 코트 필름 및 그 제조 방법, 화상 표시 장치와 터치 패널
KR1020217005601A KR102455947B1 (ko) 2016-02-15 2017-01-30 폴리에스터 필름 및 그 제조 방법, 하드 코트 필름 및 그 제조 방법, 화상 표시 장치와 터치 패널
CN201780010643.6A CN108602237A (zh) 2016-02-15 2017-01-30 聚酯薄膜及其制造方法、硬涂膜及其制造方法、图像显示装置以及触摸面板
JP2018500014A JP6594518B2 (ja) 2016-02-15 2017-01-30 ポリエステルフィルム及びその製造方法、ハードコートフィルム及びその製造方法、画像表示装置並びにタッチパネル

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JP2016-026351 2016-02-15
JP2016026351 2016-02-15

Publications (1)

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WO2017141680A1 true WO2017141680A1 (fr) 2017-08-24

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PCT/JP2017/003241 WO2017141680A1 (fr) 2016-02-15 2017-01-30 Film de polyester et son procédé de fabrication, film de revêtement dur et son procédé de fabrication, appareil d'affichage d'image et écran tactile

Country Status (5)

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JP (1) JP6594518B2 (fr)
KR (2) KR102455947B1 (fr)
CN (1) CN108602237A (fr)
TW (1) TWI769147B (fr)
WO (1) WO2017141680A1 (fr)

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KR102348955B1 (ko) * 2020-06-26 2022-01-11 재단법인대구경북과학기술원 함침상태 복합전극의 결착력 측정 방법
CN114153017B (zh) * 2021-12-16 2023-08-15 云阳金田塑业有限公司 一种照明反射膜的制备方法

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Publication number Priority date Publication date Assignee Title
CN114674260A (zh) * 2022-03-28 2022-06-28 沈阳建筑大学 一种全断面隧道掘进机刮刀磨损检测方法
CN114674260B (zh) * 2022-03-28 2023-12-26 沈阳建筑大学 一种全断面隧道掘进机刮刀磨损检测方法

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KR102455947B1 (ko) 2022-10-17
TW201800262A (zh) 2018-01-01
KR20210024230A (ko) 2021-03-04
TWI769147B (zh) 2022-07-01
JPWO2017141680A1 (ja) 2018-08-16
KR20180104012A (ko) 2018-09-19
JP6594518B2 (ja) 2019-10-23
KR102222794B1 (ko) 2021-03-03
CN108602237A (zh) 2018-09-28

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