WO2024071233A1 - Film optique - Google Patents

Film optique Download PDF

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Publication number
WO2024071233A1
WO2024071233A1 PCT/JP2023/035233 JP2023035233W WO2024071233A1 WO 2024071233 A1 WO2024071233 A1 WO 2024071233A1 JP 2023035233 W JP2023035233 W JP 2023035233W WO 2024071233 A1 WO2024071233 A1 WO 2024071233A1
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Prior art keywords
film
polycarbonate
less
optical film
easy
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PCT/JP2023/035233
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English (en)
Japanese (ja)
Inventor
克也 谷澤
匡弘 松本
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大倉工業株式会社
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Publication of WO2024071233A1 publication Critical patent/WO2024071233A1/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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements

Definitions

  • the present invention relates to an optical film having a resin film containing a (meth)acrylic resin as a main component and an easy-adhesion layer laminated on one surface of the resin film.
  • Acrylic resin films formed from (meth)acrylic polymers such as polymethyl methacrylate (PMMA) are known to have excellent optical properties such as light transmittance, as well as an excellent balance between mechanical strength and moldability. For this reason, acrylic resin films have been used in optical applications in recent years, and are increasingly being applied to optical films incorporated into image display devices such as liquid crystal displays (LCDs), plasma display panels (PDPs), and organic electroluminescent displays (OLEDs).
  • LCDs liquid crystal displays
  • PDPs plasma display panels
  • OLEDs organic electroluminescent displays
  • polarizer protective film which is a type of optical film, is used in image display devices in the form of a polarizing plate laminated to a polarizer and at least one surface of the polarizer via an adhesive layer made of a hydrophilic adhesive or an ultraviolet-curable adhesive, so it is necessary for the film to have good adhesion to the polarizer it is laminated on.
  • acrylic resin films have problems in that they have poor adhesion to hydrophilic adhesives and ultraviolet-curing adhesives, and do not adhere sufficiently to polarizers. Therefore, a method has been proposed in which an easy-adhesion layer made primarily of an adhesive-promoting resin (binder resin) such as polyester, acrylic, or urethane is provided on the surface of the acrylic resin film to impart easy-adhesion to the acrylic resin film.
  • an adhesive-promoting resin such as polyester, acrylic, or urethane
  • Patent Document 1 describes an optical film in which an easy-adhesion layer is formed on an acrylic film, the easy-adhesion layer being made of an easy-adhesion composition containing a polyurethane polymer having a weight-average molecular weight of 10,000 to 100,000, which is obtained by reacting a polycarbonate diol with an isocyanate, and describes that by using the polyurethane polymer as the easy-adhesion composition, an optical film with excellent adhesion can be obtained.
  • the optical films having the easy-adhesion layers disclosed in the above documents initially exhibit good adhesion, the adhesion inevitably decreases when used for long periods of time under high temperature and high humidity conditions, and there is a problem in that the initial performance (initial adhesion) is not maintained for long periods of time.
  • the acrylic resin film substrate is stretched to adjust the mechanical strength, etc., and from the viewpoint of increasing the production efficiency of the optical film, it is preferable to apply a coating liquid of an easy-adhesion composition to the surface of the acrylic resin film before stretching immediately before the continuously transported long unstretched acrylic resin film is fed to the stretching device, and to simultaneously dry the coating film and stretch the acrylic resin film before stretching in the preheating zone and stretching zone of the stretching device.
  • the easy-adhesion composition disclosed in the above document is used, there is a problem that when the easy-adhesion layer formed on the surface of the acrylic resin film is stretched, the easy-adhesion layer turns white, and the optical properties (light transmittance, haze, etc.) decrease.
  • the present invention has been made in consideration of these problems, and aims to provide an optical film that can suppress the deterioration of initial performance when used for long periods of time under high temperature and high humidity conditions, and can also suppress the whitening of the easy-adhesion layer due to stretching, etc., and the deterioration of optical properties.
  • the inventors conducted extensive research into an easy-adhesion layer that has excellent adhesion to acrylic resin films and can suppress the deterioration of initial performance and whitening of the easy-adhesion layer under high temperature and high humidity conditions. As a result, they discovered that the above problems could be solved by using a specific polycarbonate-based polyurethane as the binder resin for the easy-adhesion layer, and thus completed the present invention.
  • an optical film having a resin film containing an acrylic resin as a main component, and an easy-adhesion layer laminated on one surface of the resin film, the easy-adhesion layer containing a polycarbonate-based polyurethane as a main component, the polycarbonate-based polyurethane having a weight-average molecular weight of 200,000 or more and 2,500,000 or less, and a shear storage modulus ratio (E' 25 /E' 85 ) of a shear storage modulus at 25° C. (E' 25 ) to a shear storage modulus at 85° C.
  • the optical film according to (1) wherein the polycarbonate-based polyurethane has a shear loss modulus (E′′ 25 ) at 25° C. of 40 MPa or more and 150 MPa or less; (6) There is provided the optical film according to (1), wherein the acrylic resin has at least one unit selected from the group consisting of a glutarimide unit, a lactone ring unit, a maleic anhydride unit, a maleimide unit, and a glutaric anhydride unit; (7) There is provided a polarizing plate comprising the optical film according to any one of (1) to (6), an adhesive layer, and a polarizer, laminated in this order such that the easy-adhesion layer is in contact with the adhesive layer.
  • E′′ 25 shear loss modulus
  • the optical film of the present invention uses a specific polycarbonate-based polyurethane as the binder resin in the easy-adhesion layer, and thus has excellent adhesion to acrylic resin films and to other components such as polarizers. Furthermore, the optical film of the present invention is capable of suppressing the deterioration of initial performance when used for long periods of time under high temperature and high humidity conditions, and is also capable of suppressing the whitening of the easy-adhesion layer due to stretching, etc., and the deterioration of optical properties.
  • FIG. 1 is a cross-sectional view illustrating an example of an optical film of the present invention.
  • FIG. 1 is a cross-sectional view illustrating an example of a polarizing plate of the present invention.
  • the optical film of the present invention has an easy-adhesion layer containing a polycarbonate-based polyurethane as a main component on one surface of a resin film containing an acrylic resin as a main component.
  • the resin film is made of a thermoplastic resin containing an acrylic resin as a main component.
  • the term "main component” means that the composition ratio of the acrylic resin among the components constituting the resin film is 50% by weight or more, preferably 60% by weight or more, more preferably 80% by weight or more, even more preferably 90% by weight or more, and particularly preferably 95% by weight or more.
  • any suitable acrylic resin may be used.
  • the acrylic resin typically contains alkyl (meth)acrylate as the main component as a monomer unit.
  • (meth)acrylic means acrylic and/or methacrylic.
  • alkyl (meth)acrylate constituting the main skeleton of the (meth)acrylic resin include linear or branched alkyl groups having 1 to 18 carbon atoms. These can be used alone or in combination.
  • any suitable copolymerization monomer may be introduced into the (meth)acrylic resin by copolymerization. The type, number, copolymerization ratio, etc. of such copolymerization monomers can be appropriately set according to the purpose.
  • the acrylic resin preferably has at least one selected from a glutarimide unit, a lactone ring unit, a maleic anhydride unit, a maleimide unit, and a glutaric anhydride unit.
  • Acrylic resins having lactone ring units are described, for example, in JP 2008-181078 A, the disclosure of which is incorporated herein by reference.
  • the glutarimide unit is preferably represented by the following general formula (1):
  • R 1 and R 2 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
  • R 3 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or an aryl group having 6 to 10 carbon atoms.
  • R 1 and R 2 each independently represent a hydrogen atom or a methyl group
  • R 3 represents a hydrogen atom, a methyl group, a butyl group, or a cyclohexyl group. More preferably, R 1 is a methyl group, R 2 is a hydrogen atom, and R 3 is a methyl group.
  • Alkyl (meth)acrylate is typically represented by the following general formula (2):
  • R 4 represents a hydrogen atom or a methyl group
  • R 5 represents a hydrogen atom or an aliphatic or alicyclic hydrocarbon group having 1 to 6 carbon atoms which may be substituted. Examples of the substituent include halogen and a hydroxyl group.
  • alkyl (meth)acrylate examples include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, chloromethyl (meth)acrylate, 2-chloroethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2,3,4,5,6-pentahydroxyhexyl (meth)acrylate, and 2,3,4,5-tetrahydroxypentyl (meth)acrylate.
  • R 5 is preferably a hydrogen atom or a methyl group.
  • a particularly preferred alkyl (meth)acrylate is methyl acrylate or methyl methacrylate.
  • the acrylic resin may contain only a single glutarimide unit, or may contain a plurality of glutarimide units in which R 1 , R 2 and R 3 in the general formula (1) are different.
  • the content of the glutarimide unit in the acrylic resin is preferably 2 mol% to 50 mol%, more preferably 2 mol% to 45 mol%, even more preferably 2 mol% to 40 mol%, particularly preferably 2 mol% to 35 mol%, and most preferably 3 mol% to 30 mol%. If the content is less than 2 mol%, the effects derived from the glutarimide unit (e.g., high optical properties, high mechanical strength, excellent adhesion to a polarizer, thinning) may not be fully exhibited. If the content exceeds 50 mol%, for example, heat resistance and transparency may be insufficient.
  • the acrylic resin may contain only a single alkyl (meth)acrylate unit, or may contain a plurality of alkyl (meth)acrylate units in which R 4 and R 5 in the general formula (2) are different.
  • the content of the alkyl (meth)acrylate unit in the acrylic resin is preferably 50 mol% to 98 mol%, more preferably 55 mol% to 98 mol%, even more preferably 60 mol% to 98 mol%, particularly preferably 65 mol% to 98 mol%, and most preferably 70 mol% to 97 mol%. If the content is less than 50 mol%, the effects (e.g., high heat resistance, high transparency) derived from the alkyl (meth)acrylate unit may not be fully exhibited. If the content is more than 98 mol%, the resin may be brittle and easily cracked, and high mechanical strength may not be fully exhibited, resulting in poor productivity.
  • the acrylic resin may contain units other than glutarimide units and alkyl (meth)acrylate units.
  • the acrylic resin may contain, for example, 0 to 10% by weight of unsaturated carboxylic acid units that are not involved in the intramolecular imidization reaction described below.
  • the content of unsaturated carboxylic acid units is preferably 0 to 5% by weight, and more preferably 0 to 1% by weight. If the content is within such a range, transparency, retention stability, and moisture resistance can be maintained.
  • the acrylic resin may contain copolymerizable vinyl monomer units (other vinyl monomer units) other than those mentioned above.
  • vinyl monomers include acrylonitrile, methacrylonitrile, ethacrylonitrile, allyl glycidyl ether, maleic anhydride, itaconic anhydride, N-methylmaleimide, N-ethylmaleimide, N-cyclohexylmaleimide, aminoethyl acrylate, propylaminoethyl acrylate, dimethylaminoethyl methacrylate, ethylaminopropyl methacrylate, cyclohexylaminoethyl methacrylate, N-vinyldiethylamine, N-acetylvinylamine, allylamine, methallylamine, N-methylallylamine, 2-isopropenyl-oxazoline, 2-vinyl-oxazoline, 2-acroyl-ox
  • styrene-based monomers such as styrene and ⁇ -methylstyrene.
  • the content of other vinyl-based monomer units is preferably 0 to 5% by weight, more preferably 0 to 1% by weight, and even more preferably 0 to 0.1% by weight. Within these ranges, the appearance of undesired retardation and a decrease in transparency can be suppressed.
  • the imidization rate in the acrylic resin is preferably 2.5% to 20.0%. If the imidization rate is within such a range, a resin having excellent heat resistance, transparency, and moldability can be obtained, and the occurrence of scorching and the decrease in mechanical strength during film formation can be prevented.
  • the imidization rate is represented by the ratio of glutarimide units to alkyl (meth)acrylate units. This ratio can be obtained, for example, from the NMR spectrum, IR spectrum, etc. of the acrylic resin.
  • the imidization rate can be determined by 1 H-NMR measurement of the resin using a 1 HNMR BRUKER AvanceIII (400 MHz).
  • the imidization rate is determined by the following formula, where A is the peak area derived from the O-CH 3 proton of the alkyl (meth)acrylate around 3.5 to 3.8 ppm, and B is the peak area derived from the N-CH 3 proton of the glutarimide around 3.0 to 3.3 ppm.
  • Imidization rate Im (%) ⁇ B/(A+B) ⁇ x 100
  • the acid value of the acrylic resin is preferably 0.10 mmol/g to 0.50 mmol/g. If the acid value is within this range, a resin with an excellent balance of heat resistance, mechanical properties, and moldability can be obtained. If the acid value is too small, problems such as increased costs due to the use of a modifier to adjust the acid value to the desired value and generation of gel-like matter due to residual modifier may occur. If the acid value is too large, foaming is likely to occur during film molding (e.g., during melt extrusion), and the productivity of molded products tends to decrease.
  • the acid value is the content of carboxylic acid units and carboxylic anhydride units in the acrylic resin. In this embodiment, the acid value can be calculated, for example, by the titration method described in WO2005/054311 or JP2005-23272A.
  • the weight average molecular weight of the acrylic resin is preferably 1,000 to 2,000,000, more preferably 5,000 to 1,000,000, even more preferably 10,000 to 500,000, particularly preferably 50,000 to 500,000, and most preferably 60,000 to 150,000.
  • the weight average molecular weight can be determined, for example, using a gel permeation chromatograph (GPC system, manufactured by Tosoh Corporation) in terms of polystyrene. Tetrahydrofuran can be used as the solvent.
  • the Tg (glass transition temperature) of the acrylic resin is preferably 110°C or higher, more preferably 115°C or higher, even more preferably 120°C or higher, particularly preferably 125°C or higher, and most preferably 130°C or higher. If the Tg is 110°C or higher, a polarizing plate including a substrate film obtained from such a resin is likely to have excellent durability.
  • the upper limit of the Tg is preferably 300°C or lower, more preferably 290°C or lower, even more preferably 285°C or lower, particularly preferably 200°C or lower, and most preferably 160°C or lower. If the Tg is within this range, excellent moldability can be obtained.
  • the acrylic resin can be produced, for example, by the following method.
  • This method includes: (I) copolymerizing an alkyl (meth)acrylate monomer corresponding to the alkyl (meth)acrylate unit represented by the general formula (2) with an unsaturated carboxylic acid monomer and/or its precursor monomer to obtain a copolymer (a); and (II) treating the copolymer (a) with an imidizing agent to carry out an intramolecular imidization reaction between the alkyl (meth)acrylate monomer unit and the unsaturated carboxylic acid monomer and/or its precursor monomer unit in the copolymer (a), thereby introducing a glutarimide unit represented by the general formula (1) into the copolymer.
  • Examples of the unsaturated carboxylic acid monomer include acrylic acid, methacrylic acid, crotonic acid, ⁇ -substituted acrylic acid, and ⁇ -substituted methacrylic acid.
  • Examples of the precursor monomers include acrylamide and methacrylamide. These may be used alone or in combination.
  • a preferred unsaturated carboxylic acid monomer is acrylic acid or methacrylic acid, and a preferred precursor monomer is acrylamide.
  • any appropriate method can be used as the method for treating the copolymer (a) with an imidizing agent.
  • Specific examples include a method using an extruder and a method using a batch reaction tank (pressure vessel).
  • the method using an extruder involves using an extruder to heat and melt the copolymer (a) and treating it with an imidizing agent.
  • any appropriate extruder can be used as the extruder.
  • Specific examples include a single-screw extruder, a twin-screw extruder, and a multi-screw extruder.
  • any appropriate batch reaction tank (pressure vessel) can be used.
  • any suitable compound can be used as long as it can generate the glutarimide unit represented by the above general formula (1).
  • Specific examples of the imidizing agent include aliphatic hydrocarbon group-containing amines such as methylamine, ethylamine, n-propylamine, i-propylamine, n-butylamine, i-butylamine, tert-butylamine, and n-hexylamine, aromatic hydrocarbon group-containing amines such as aniline, benzylamine, toluidine, and trichloroaniline, and alicyclic hydrocarbon group-containing amines such as cyclohexylamine.
  • urea-based compounds that generate such amines by heating can also be used.
  • examples of urea compounds include urea, 1,3-dimethylurea, 1,3-diethylurea, and 1,3-dipropylurea.
  • the imidizing agent is preferably methylamine, ammonia, or cyclohexylamine, and more preferably methylamine.
  • a ring-closing promoter may be added as necessary.
  • the amount of the imidizing agent used in the imidization is preferably 0.5 to 10 parts by weight, more preferably 0.5 to 6 parts by weight, per 100 parts by weight of copolymer (a). If the amount of the imidizing agent used is less than 0.5 parts by weight, the desired imidization rate is often not achieved. As a result, the heat resistance of the resulting resin becomes extremely insufficient, which may induce appearance defects such as burnt spots after molding. If the amount of the imidizing agent used exceeds 10 parts by weight, the imidizing agent remains in the resin and may induce appearance defects such as burnt spots and foaming after molding.
  • the method for producing acrylic resins can include treatment with an esterifying agent in addition to the above imidization, if necessary.
  • the esterifying agent include dimethyl carbonate, 2,2-dimethoxypropane, dimethyl sulfoxide, triethyl orthoformate, trimethyl orthoacetate, trimethyl orthoformate, diphenyl carbonate, dimethyl sulfate, methyl toluene sulfonate, methyl trifluoromethanesulfonate, methyl acetate, methanol, ethanol, methyl isocyanate, p-chlorophenyl isocyanate, dimethylcarbodiimide, dimethyl-t-butylsilyl chloride, isopropenyl acetate, dimethylurea, tetramethylammonium hydroxide, dimethyldiethoxysilane, tetra-N-butoxysilane, dimethyl(trimethylsilane) phosphite, trimethyl phosphite,
  • the resin film may be made by using an acrylic resin in combination with another resin. That is, the monomer components constituting the acrylic resin may be copolymerized with the monomer components constituting the other resin, and the copolymer may be used for film formation, as described below; a blend of the acrylic resin and the other resin may be used for film formation.
  • the other resin include other thermoplastic resins such as styrene resins, polyethylene, polypropylene, polyamide, polyphenylene sulfide, polyether ether ketone, polyester, polysulfone, polyphenylene oxide, polyacetal, polyimide, and polyetherimide, and thermosetting resins such as phenol resins, melamine resins, polyester resins, silicone resins, and epoxy resins.
  • the type and amount of the resin used in combination may be appropriately set according to the purpose and the desired properties of the resulting film.
  • a styrene resin (preferably an acrylonitrile-styrene copolymer) may be used in combination as a retardation control agent.
  • the content of the acrylic resin in the blend of the acrylic resin and the other resin is preferably 50% by weight to 100% by weight, more preferably 60% by weight to 100% by weight, even more preferably 70% by weight to 100% by weight, and particularly preferably 80% by weight to 100% by weight. If the content is less than 50% by weight, the high heat resistance and high transparency inherent to the acrylic resin may not be fully reflected.
  • the resin film may be an acrylic resin blended with core-shell particles, preferably 5 to 50 parts by weight, more preferably 5 to 40 parts by weight, per 100 parts by weight of the acrylic resin.
  • Core-shell particles typically have a core made of a rubber-like polymer and a coating layer made of a glassy polymer that coats the core.
  • Core-shell particles may have one or more layers made of a glassy polymer as the innermost layer or intermediate layer.
  • the Tg of the rubbery polymer that constitutes the core is preferably 20°C or lower, more preferably -60°C to 20°C, and even more preferably -60°C to 10°C. If the Tg of the rubbery polymer that constitutes the core exceeds 20°C, the improvement in mechanical strength of the acrylic resin may not be sufficient.
  • the Tg of the glassy polymer (hard polymer) that constitutes the coating layer is preferably 50°C or higher, more preferably 50°C to 140°C, and even more preferably 60°C to 130°C. If the Tg of the glassy polymer that constitutes the coating layer is lower than 50°C, the heat resistance of the acrylic resin may decrease.
  • the content of the core in the core-shell type particle is preferably 30% by weight to 95% by weight, more preferably 50% by weight to 90% by weight.
  • the content of the glassy polymer layer in the core is 0% by weight to 60% by weight, preferably 0% by weight to 45% by weight, more preferably 10% by weight to 40% by weight, based on 100% by weight of the total amount of the core.
  • the content of the coating layer in the core-shell type particle is preferably 5% by weight to 70% by weight, more preferably 10% by weight to 50% by weight.
  • the thickness of the resin film is preferably 5 ⁇ m or more, more preferably 8 ⁇ m or more, even more preferably 10 ⁇ m or more, and is preferably 200 ⁇ m or less, more preferably 100 ⁇ m or less, even more preferably 70 ⁇ m or less, and particularly preferably 60 ⁇ m or less.
  • any suitable method can be used to form the resin film.
  • suitable method include cast coating (e.g., casting), extrusion molding, injection molding, compression molding, transfer molding, blow molding, powder molding, FRP molding, calendar molding, and heat pressing.
  • Extrusion molding or cast coating is preferred, as it can improve the smoothness of the resulting film and provide good optical uniformity.
  • Extrusion molding is particularly preferred. Among these, extrusion molding using a T-die is preferred from the viewpoints of film productivity and ease of subsequent stretching. Molding conditions can be set appropriately depending on the composition and type of resin used, the properties desired for the resulting film, and the like.
  • stretching method any appropriate stretching method and stretching conditions (e.g., stretching temperature, stretching ratio, stretching speed, stretching direction) can be adopted.
  • stretching methods include free end stretching, fixed end stretching, free end shrinkage, and fixed end shrinkage. These may be used alone, simultaneously, or sequentially.
  • the stretching direction may be an appropriate direction depending on the purpose. Specific examples include the length direction, width direction, thickness direction, and oblique direction.
  • the stretching direction may be one direction (uniaxial stretching), two directions (biaxial stretching), or three or more directions. In the embodiment of the present invention, typically, uniaxial stretching in the length direction, simultaneous biaxial stretching in the length direction and width direction, and sequential biaxial stretching in the length direction and width direction may be used. Biaxial stretching (simultaneous or sequential) is preferable, which makes it easy to control the in-plane retardation and to achieve optical isotropy.
  • the stretching temperature can vary depending on the optical properties, mechanical properties and thickness desired for the base film, the type of resin used, the thickness of the film used, the stretching method (uniaxial stretching or biaxial stretching), the stretching ratio, the stretching speed, etc.
  • the stretching temperature is preferably Tg to Tg + 50°C, more preferably Tg + 15°C to Tg + 50°C, and most preferably Tg + 35°C to Tg + 50°C.
  • a specific stretching temperature is, for example, 110°C to 200°C, preferably 120°C to 190°C, and more preferably 150°C to 190°C.
  • the stretching ratio can vary depending on the optical properties, mechanical properties and thickness, the type of resin used, the thickness of the film used, the stretching method (uniaxial or biaxial stretching), the stretching temperature, the stretching speed, etc.
  • the ratio (TD/MD) of the stretching ratio in the width direction (TD) to the stretching ratio in the length direction (MD) is preferably 1.0 to 1.5, more preferably 1.0 to 1.4, and even more preferably 1.0 to 1.3.
  • the areal ratio (the product of the stretching ratio in the length direction and the stretching ratio in the width direction) is preferably 2.0 to 6.0, more preferably 3.0 to 5.5, and even more preferably 3.5 to 5.2.
  • the stretching speed can vary depending on the optical properties, mechanical properties and thickness, the type of resin used, the thickness of the film used, the stretching method (uniaxial or biaxial stretching), the stretching temperature, the stretching ratio, etc.
  • the stretching speed is preferably 3%/sec to 20%/sec, more preferably 3%/sec to 15%/sec, and even more preferably 3%/sec to 10%/sec.
  • the stretching speed in one direction may be the same as or different from the stretching speed in the other direction.
  • the easy-adhesion layer contains a polycarbonate-based polyurethane having the characteristics described below as a main component.
  • the "main component” means that the composition ratio of the components constituting the easy-adhesion layer is 50% by weight or more, preferably 60% by weight or more, more preferably 80% by weight or more, even more preferably 90% by weight or more, and particularly preferably 95% by weight or more.
  • the optical film of the present invention can suppress the deterioration of initial performance during long-term use under high temperature and high humidity conditions, and can suppress the whitening of the easy-adhesion layer due to stretching, etc., and the deterioration of optical properties.
  • the polycarbonate-based polyurethane preferably has a weight-average molecular weight of 200,000 or more and 2,500,000 or less.
  • the lower limit of the weight-average molecular weight is preferably 250,000 or more, more preferably 300,000 or more, even more preferably 400,000 or more, particularly preferably 500,000 or more, and most preferably 600,000 or more.
  • the upper limit of the weight-average molecular weight is preferably 2,200,000 or less, more preferably 2,000,000 or less, even more preferably 1,900,000 or less, particularly preferably 1,800,000 or less, and most preferably 1,500,000 or less.
  • the weight-average molecular weight is less than 200,000, the initial adhesion to the acrylic resin film is poor, and the adhesion may decrease during long-term use under high temperature and high humidity. If the weight-average molecular weight exceeds 2,500,000, it may be difficult to manufacture a water-dispersible urethane resin. The reason for this is unclear, but it is presumed that polycarbonate-based polyurethane with a large molecular weight has a high density of entanglement of molecular chains and a tendency to have a high elastic modulus, which leads to strong tensile strength (tension due to material breakage caused by pulling) and excellent initial adhesion.
  • polycarbonate-based polyurethanes with large molecular weights have a relatively large proportion of hard segments (crystalline portions) that contribute to adhesion, have high tensile strength, and suppress hydrolysis under high temperature and high humidity.
  • the weight average molecular weight of polycarbonate-based polyurethanes can be measured by conventionally known measuring methods, for example, gel permeation chromatography (GPC).
  • the polycarbonate polyurethane preferably has a shear storage modulus ratio (E' 25 /E' 85 ) of the shear storage modulus (E' 25 ) at 25° C. to the shear storage modulus (E' 85 ) at 85° C. of the dried film of 5 or less.
  • the shear storage modulus (E' 25 /E' 85 ) is more preferably 4.5 or less, even more preferably 4.0 or less, particularly preferably 3.5 or less, and most preferably 2.5 or less.
  • the shear storage modulus ratio (E' 25 /E' 85 ) at room temperature (25° C.) and at high temperature (85° C.) is small, the initial adhesion to the acrylic resin film is excellent, and the deterioration of initial performance and whitening of the easy-adhesion layer under high temperature and high humidity can be suppressed. Since the storage modulus is an index of the hardness of a viscoelastic body, it is considered that a polycarbonate-based polyurethane having a small dependency of the shear storage modulus on temperature suppresses hydrolysis under high temperature and high humidity conditions and maintains high tensile strength.
  • a polycarbonate-based polyurethane having a small dependency of the shear storage modulus on temperature has a wide tolerance range for the load (stretching speed and stretching ratio) applied during hot stretching, and whitening during stretching is suppressed.
  • the lower limit is not particularly limited, but is, for example, 0.1 or more and 0.5 or more.
  • the shear storage modulus (E' 25 ) at 25° C. and the shear storage modulus (E' 85 ) at 85° C. of a polycarbonate-based polyurethane can be measured by a conventionally known measurement method, for example, by dynamic mechanical analysis (DMA).
  • the polycarbonate polyurethane preferably has a shear loss modulus ratio (E'' 25 /E'' 85 ) of the shear loss modulus (E'' 25 ) at 25° C and the shear loss modulus (E'' 85 ) at 85°C of the dried coating of 2 or less.
  • the shear loss modulus ratio (E'' 25 / E ' ' 85 ) is more preferably 1.8 or less, even more preferably 1.6 or less, particularly preferably 1.4 or less, and most preferably 1.2 or less.
  • the shear loss modulus ratio (E'' 25 /E'' 85 ) at room temperature (25°C) and at high temperature (85°C) is small, the initial adhesion to the acrylic resin film is excellent, and the deterioration of initial performance and whitening of the easy-adhesion layer under high temperature and high humidity can be suppressed.
  • the lower limit is not particularly limited, but is, for example, 0.1 or more, 0.5 or more.
  • the shear loss modulus at 25° C. (E′′ 25 ) and the shear loss modulus at 85° C. (E′′ 85 ) can be measured by the above-mentioned method.
  • the polycarbonate-based polyurethane preferably has a shear loss tangent (tan ⁇ 25 ) of 0.1 or less at 25° C. of the dried film.
  • the shear loss tangent (tan ⁇ 25 ) is more preferably 0.09 or less, even more preferably 0.08 or less, particularly preferably 0.07 or less, and most preferably 0.06 or less.
  • the lower limit is not particularly limited, but is, for example, 0.01 or more.
  • the polycarbonate-based polyurethane preferably has a shear loss tangent (tan ⁇ 85 ) of 0.5 or less at 85° C.
  • the shear loss tangent (tan ⁇ 85 ) is preferably 0.4 or less, more preferably 0.3 or less, even more preferably 0.25 or less, particularly preferably 0.2 or less, and most preferably 0.15 or less.
  • the lower limit is not particularly limited, but is, for example, 0.01 or more, 0.05 or more. If the shear loss tangent (tan ⁇ 25 ) and the shear loss tangent (tan ⁇ 85 ) are within this range, the initial adhesion to the acrylic resin film is excellent, and the deterioration of the initial performance and the whitening of the adhesive layer under high temperature and high humidity can be suppressed.
  • the shear loss tangent (tan ⁇ 25 ) at 25° C. and the shear loss tangent (tan ⁇ 85 ) at 85° C. can be measured by the method described above.
  • the polycarbonate-based polyurethane preferably has a shear storage modulus (E' 25 ) of 500 MPa or more and 1500 MPa or less at 25° C. in the dried coating.
  • the lower limit is more preferably 550 MPa or more, even more preferably 600 MPa or more, particularly preferably 650 MPa, and most preferably 700 MPa.
  • the upper limit is more preferably 1400 MPa, even more preferably 1300 MPa, particularly preferably 1250 MPa, and most preferably 1200 MPa.
  • the polycarbonate-based polyurethane preferably has a shear loss modulus (E'' 85 ) of 80 MPa or more and 1000 MPa or less at 85° C.
  • the lower limit is more preferably 100 MPa or more, even more preferably 150 MPa or more, particularly preferably 200 MPa or more, and most preferably 250 MPa or more.
  • the upper limit is more preferably 900 MPa or less, even more preferably 800 MPa or less, particularly preferably 700 MPa or less, and most preferably 600 MPa or less.
  • the polycarbonate-based polyurethane preferably has a shear loss modulus (E'' 25 ) of 40 MPa or more and 150 MPa or less at 25°C.
  • the lower limit is more preferably 45 MPa or more, even more preferably 50 MPa or more, and particularly preferably 55 MPa or more.
  • the upper limit is more preferably 130 MPa or less, even more preferably 110 MPa or less, and particularly preferably 90 MPa or less.
  • the polycarbonate-based polyurethane preferably has a shear loss modulus (E'' 85 ) of 20 MPa or more and 150 MPa or less at 85°C.
  • the lower limit is more preferably 25 MPa or more, even more preferably 30 MPa or more, and particularly preferably 35 MPa or more.
  • the upper limit is more preferably 130 MPa or less, even more preferably 110 MPa or less, and particularly preferably 90 MPa or less.
  • the shear loss modulus (E'' 25 ) or the shear loss modulus (E'' 85 ) is within this range, the initial adhesion to the acrylic resin film is excellent, and deterioration of the initial performance under high temperature and high humidity conditions and whitening of the adhesive layer can be suppressed.
  • the Tg of the polycarbonate polyurethane is preferably 25°C or more and 160°C or less.
  • the lower limit is more preferably 50°C or more, even more preferably 70°C or more, particularly preferably 80°C or more, and most preferably 100°C or more.
  • the upper limit is more preferably 150°C or less, even more preferably 145°C or less, and particularly preferably 140°C or less. If the Tg is within this range, the initial adhesion to the acrylic resin film is excellent, and the deterioration of initial performance under high temperature and high humidity conditions and the whitening of the easy-adhesion layer can be suppressed.
  • the Tg can be measured by a conventional method. For example, the dynamic viscoelasticity is measured by a dynamic mechanical analysis (DMA) method, and the temperature at which the shear loss tangent (tan ⁇ ) in the dynamic viscoelasticity is maximized can be taken as the Tg.
  • DMA dynamic mechanical analysis
  • the Young's modulus of the polycarbonate-based polyurethane in the dried coating is 400 MPa or more and 1500 MPa or less.
  • the lower limit is more preferably 450 MPa or more, even more preferably 550 MPa or more, and particularly preferably 650 MPa or more.
  • the upper limit is more preferably 1300 MPa or less, even more preferably 1100 MPa or less, and particularly preferably 900 MPa or less. If the Young's modulus of the polycarbonate-based polyurethane is within this range, it will have excellent initial adhesion to the acrylic resin film, and it will be possible to suppress a decrease in initial performance and whitening of the easy-adhesion layer under high temperature and high humidity conditions.
  • the polycarbonate-based polyurethane has a breaking elongation of less than 300% in the dried coating.
  • the breaking elongation is more preferably less than 250%, even more preferably less than 200%, particularly preferably less than 100%, and most preferably less than 50%. If the breaking elongation of the polycarbonate-based polyurethane is within this range, it will have excellent initial adhesion to the acrylic resin film, and it will be possible to suppress a decrease in initial performance under high temperature and high humidity conditions and whitening of the easy-adhesion layer.
  • Polycarbonate-based polyurethane is a polyurethane with a carbonate skeleton in its molecular structure, and is obtained by reacting a polyisocyanate component with an average of two or more isocyanate groups per molecule with a polycarbonate polyol component with an average of two or more hydroxyl groups per molecule.
  • Polycarbonate-based polyurethane can be obtained, for example, by reacting a polyisocyanate with a polycarbonate polyol in an organic solvent that is inactive to isocyanates and compatible with water to form an isocyanate-terminated prepolymer, which is then reacted with a chain extender having free carboxyl groups to obtain a linear urethane prepolymer, which is chain-extended with water in the presence of a neutralizing agent and simultaneously made aqueous, by adjusting the molecular weight, molar ratio, degree of polymerization, etc. of each component.
  • aqueous here refers to stably dispersing or emulsifying the resin in water.
  • the polycarbonate-based polyurethane has a carboxyl group in the molecule, and the presence of the carboxyl group provides excellent adhesion to the acrylic resin film and to other components such as a polarizer.
  • polycarbonate polyols examples include compounds represented by the formula HO-R-(O-C(O)-O-R) X -OH (wherein R represents a saturated fatty acid polyol residue having 1 to 12 carbon atoms. X represents the number of structural units of the molecule, and is usually an integer of 5 to 50).
  • Such polycarbonate polyols can be obtained, for example, by a transesterification method in which a saturated aliphatic polyol is reacted with a substituted carbonate under conditions of excess hydroxyl groups; a method in which a saturated aliphatic polyol is reacted with phosgene, or, if necessary, further reacted with a saturated aliphatic polyol thereafter; or the like.
  • diethyl carbonate or diphenyl carbonate can be used as the substituted carbonate.
  • Polyisocyanates include aliphatic polyisocyanate compounds containing two or more isocyanate groups in one molecule, alicyclic polyisocyanate compounds, and aromatic polyisocyanate compounds.
  • Aliphatic polyisocyanate compounds are preferably aliphatic diisocyanates having 1 to 12 carbon atoms, such as hexamethylene diisocyanate, 2,2,4-trimethylhexane diisocyanate, and hexane diisocyanate (HDI).
  • Alicyclic polyisocyanate compounds are preferably alicyclic diisocyanates having 4 to 18 carbon atoms, such as 1,4-cyclohexane diisocyanate, methylcyclohexylene diisocyanate, isophorone diisocyanate (IPDI), and dicyclohexylmethane diisocyanate (HMDI).
  • aromatic polyisocyanate compound aromatic diisocyanates are preferred, such as tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, etc.
  • the polyisocyanate compound may be used alone or in combination of two or more types in any ratio.
  • chain extenders having a free carboxyl group include dihydroxycarboxylic acids and dihydroxysuccinic acid.
  • dihydroxycarboxylic acids include dialkylolalkanoic acids such as dimethylolalkanoic acids (e.g., dimethylolacetic acid, dimethylolbutanoic acid, dimethylolpropionic acid, dimethylolbutyric acid, and dimethylolpentanoic acid). These can be used alone or in combination of two or more.
  • neutralizing agents examples include ammonia, N-methylmorpholine, triethylamine, dimethylethanolamine, methyldiethanolamine, triethanolamine, morpholine, tripropylamine, ethanolamine, triisopropanolamine, 2-amino-2-methyl-1-propanol, etc. These can be used alone or in combination of two or more.
  • chain extenders include low molecular weight diol compounds such as ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, furan diethanol, diethylene glycol, triethylene glycol, and tetraethylene glycol, and polyether diol compounds obtained by addition polymerization of these with ethylene oxide, propylene oxide, tetrahydrofuran, and the like; polyester diols having hydroxyl groups at the ends obtained from the above low molecular weight diol compounds and dicarboxylic acids such as succinic acid (anhydride), adipic acid, and phthalic acid (anhydride), and the anhydrides thereof; polyhydric alcohols such as trimethylolethane and trimethylolpropane; amino alcohols such as monoethanolamine, diethanolamine, and triethanolamine; diamine compounds such as ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine,
  • the acid value of the polycarbonate-based polyurethane is not particularly limited, but is preferably, for example, 50 mgKOH/g or less.
  • the acid value is more preferably 5 mgKOH/g to 45 mgKOH/g, even more preferably 15 mgKOH/g to 40 mgKOH/g, and particularly preferably 20 mgKOH/g to 35 mgKOH/g. If the acid value is within this range, the initial adhesion to the acrylic resin film is excellent, and the deterioration of initial performance and whitening of the easy-adhesion layer under high temperature and high humidity conditions can be suppressed.
  • the easy-adhesion layer may contain a resin component other than the polycarbonate-based polyurethane as long as it does not impair the effects of the present invention.
  • resin components other than polycarbonate-based polyurethane include polyurethane obtained by reacting a polyisocyanate component with a polyester polyol component, polyurethane obtained by reacting a polyisocyanate component with a polyether polyol component, polyurethane obtained by reacting a polyisocyanate component with a polyether ester polyol component, polyurethane obtained by reacting a polyisocyanate component with a polyacrylic polyol component, polyolefin, polyester, acrylic polymer, etc. These can be used alone or in combination of two or more.
  • the easy-adhesion layer may contain a crosslinking agent to improve the resistance to moisture and heat under high temperature and high humidity.
  • a crosslinking agent to improve the resistance to moisture and heat under high temperature and high humidity.
  • Any suitable crosslinking agent can be used, such as urea compounds, epoxy compounds, melamine compounds, isocyanate compounds, oxazoline compounds, silanol compounds, carbodiimide compounds, etc. These can be used alone or in combination of two or more.
  • the content of the crosslinking agent is not particularly limited, but is preferably 0.1 to 35 parts by weight per 100 parts by weight of polycarbonate-based polyurethane in total, calculated as solid content. More preferably, it is 0.5 to 30 parts by weight, even more preferably, it is 3 to 25 parts by weight, and particularly preferably, it is 5 to 20 parts by weight.
  • the crosslinking agent may be blended with respect to 100 parts by weight of solid content including other resin components. Note that blending a crosslinking agent in the easy-adhesion layer may reduce the initial adhesion with the acrylic resin film.
  • the polycarbonate-based polyurethane used in the present invention has excellent initial adhesion to the acrylic resin film without the addition of a crosslinking agent, and can suppress the deterioration of initial performance and whitening of the easy-adhesion layer under high temperature and high humidity conditions, the amount of crosslinking agent may be as small as possible.
  • the amount of crosslinking agent is preferably 5 parts by weight or less, more preferably 3 parts by weight or less, even more preferably 1.5 parts by weight or less, and particularly preferably 0.5 parts by weight or less, per 100 parts by weight of the total polycarbonate-based polyurethane.
  • the easy-adhesion layer may contain any suitable fine particles according to the function. Moreover, water-dispersible fine particles are preferable.
  • inorganic fine particles include, for example, inorganic oxides such as silica, titania, alumina, and zirconia, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate, and calcium phosphate.
  • organic fine particles include, for example, silicone resins, fluorine resins, (meth)acrylic resins, and (meth)acrylonitrile resins. Among these, silica is preferable. Silica-based fine particles have excellent blocking suppression ability, excellent transparency, do not cause haze, and are not colored, so that the easy-adhesion layer has a smaller effect on the optical properties.
  • the average particle size of the microparticles is not particularly limited, but from the viewpoint of maintaining the transparency of the easy-adhesion layer, it is preferably 1 to 500 nm, more preferably 5 to 300 nm, and even more preferably 100 to 100 nm.
  • the average particle size of the microparticles is not particularly limited, but from the viewpoint of maintaining the transparency of the easy-adhesion layer, it is preferably 1 to 500 nm, more preferably 5 to 300 nm, and even more preferably 100 to 100 nm.
  • the easy-adhesion layer may further contain any suitable additive.
  • additives include dispersion stabilizers, thixotropic agents, antioxidants, UV absorbers, defoamers, thickeners, dispersants, surfactants, catalysts, lubricants, and antistatic agents.
  • the thickness of the easy-adhesion layer is not particularly limited, but is preferably, for example, 0.01 ⁇ m or more and 10 ⁇ m or less.
  • the lower limit is more preferably 0.03 ⁇ m or more, even more preferably 0.05 ⁇ m or more, particularly preferably 0.1 ⁇ m or more, and most preferably 0.15 ⁇ m or more
  • the upper limit is more preferably 3 ⁇ m or less, even more preferably 2 ⁇ m or less, particularly preferably 1 ⁇ m or less, and most preferably 0.5 ⁇ m or less.
  • optical film An example of the optical film of the present invention is shown in Figure 1.
  • the optical film 1 shown in Figure 1 has an easy-adhesion layer 3 containing a polycarbonate-based polyurethane as a main component on one surface of a resin film 2 containing an acrylic resin as a main component.
  • the specific configurations of the resin film 2 and the easy-adhesion layer 3 are as described above.
  • the easy-adhesion layer 3 may be formed on at least one surface of the resin film 2, and may be formed on both surfaces of the resin film 2.
  • the total light transmittance is 80% or more, more preferably 85% or more, and even more preferably 90% or more.
  • the light transmittance can be measured in accordance with JIS K0115 using a spectrophotometer (V-570 ultraviolet-visible-near infrared spectrophotometer manufactured by JASCO Corporation).
  • the haze of the optical film is not particularly limited, but is preferably 2.0% or less, more preferably 1.0% or less, even more preferably 0.8% or less, and particularly preferably 0.5% or less. Haze can be measured using a turbidity meter NDH-300A manufactured by Nippon Denshoku Industries Co., Ltd. in accordance with JIS K7361-1997.
  • the total thickness of the optical film is preferably 5 ⁇ m or more, more preferably 8 ⁇ m or more, even more preferably 10 ⁇ m or more, and is preferably 200 ⁇ m or less, more preferably 100 ⁇ m or less, and particularly preferably 70 ⁇ m or less.
  • various functional layers may be formed on the surface opposite to the surface on which the easy-adhesion layer is formed, as necessary.
  • functional layers include an antistatic layer, a pressure-sensitive adhesive layer, an adhesive layer, an easy-adhesion layer, an anti-glare layer, an anti-fouling layer such as a photocatalyst layer, an anti-reflection layer, a hard coat layer, an ultraviolet shielding layer, a heat ray shielding layer, an electromagnetic wave shielding layer, and a gas barrier layer.
  • the optical film of the present invention is, for example, a polarizer protection film, a phase difference film, a viewing angle compensation film, a light diffusion film, a reflection film, an anti-reflection film, an anti-glare film, a brightness enhancement film, or a conductive film for a touch panel.
  • the optical film of the present invention may be an optically isotropic film, or may be an optically anisotropic film (for example, a film that exhibits birefringence such as phase difference).
  • the method for producing the optical film of the present invention includes a step of forming a coating film by applying a coating liquid containing an aqueous solvent and a polycarbonate-based polyurethane to at least one surface of a resin film containing an acrylic resin as a main component, and a step of forming an easy-adhesion layer by drying or curing the coating film.
  • the optical film is preferably produced by the following first or second production method.
  • a first manufacturing method for an optical film preferred in the present invention includes a step of applying a coating liquid containing an aqueous solvent and a polycarbonate-based polyurethane to at least one surface of an unstretched resin film made of a thermoplastic resin containing an acrylic resin as a main component to form a coating film, a step of drying or curing the coating film to form an easy-adhesion layer, and a step of stretching the unstretched resin film to obtain a stretched film.
  • the first manufacturing method of the optical film of the present invention involves a step of preparing a resin film before stretching.
  • the resin film before stretching is a raw film that will become a stretched film when stretched, and is made of a thermoplastic resin that contains an acrylic resin as the main component.
  • the surface of the resin film before stretching on which the coating film is formed may be subjected to a surface modification treatment in order to improve the adhesion between the resin film and the easy-adhesion layer.
  • the hydrophilicity of the treated surface is usually improved to set the average water contact angle and the standard deviation of the water contact angle of the surface to a desired range.
  • the desired range of the average water contact angle is preferably 20° to 80°, more preferably 20° to 75°, and even more preferably 20° to 50°.
  • Examples of the surface modification treatment include energy ray irradiation treatment and chemical treatment.
  • Examples of the energy ray irradiation treatment include corona discharge treatment, plasma treatment, electron beam irradiation treatment, ultraviolet irradiation treatment, etc., and from the viewpoint of treatment efficiency, corona discharge treatment and plasma treatment are preferred, and corona discharge treatment is particularly preferred.
  • Examples of the chemical treatment include saponification treatment, and treatment in which the film is immersed in an aqueous solution of an oxidizing agent such as a potassium dichromate solution or concentrated sulfuric acid, followed by washing with water.
  • a coating solution containing an aqueous solvent and a polycarbonate-based polyurethane is applied to at least one surface of an unstretched resin film to form a coating film.
  • coating methods include wire bar coating, dipping, spraying, spin coating, roll coating, gravure coating, air knife coating, curtain coating, slide coating, and extrusion coating.
  • a coating film is formed on the surface of the resin film before stretching, and then the coating film is dried or cured to obtain an easy-adhesion layer.
  • the coating film is cured by drying the solvent contained in the coating liquid.
  • the heating temperature and heating time may be appropriately set within a range in which a desired reaction such as a processing reaction proceeds.
  • the first manufacturing method after forming an easy-adhesion layer on the surface of the resin film before stretching, a step is performed in which the resin film before stretching is stretched to obtain a stretched film.
  • the stretching method the above-mentioned stretching methods can be used.
  • the step of drying or curing the coating film to obtain an easy-adhesion layer and the step of stretching the unstretched resin film to obtain a stretched film may be performed in either order, or both steps may be performed simultaneously. From the viewpoint of increasing the adhesion between the stretched film and the easy-adhesion layer, it is preferable to simultaneously perform the step of drying or curing the coating film to obtain an easy-adhesion layer and the step of stretching the unstretched resin film to obtain a stretched film.
  • the coating film is usually heated by the heat applied when stretching the unstretched resin film, and the drying or curing of the layer of the coating liquid proceeds.
  • the optical film is preferable to manufacture the optical film as a long film.
  • a coating liquid containing a polycarbonate-based polyurethane
  • a second manufacturing method for an optical film preferred in the present invention includes a step of applying a coating liquid containing an aqueous solvent and a polycarbonate-based polyurethane to at least one surface of a stretched film made of a thermoplastic resin containing an acrylic resin as a main component to form a coating film, and a step of drying or curing the coating film to obtain an easy-adhesion layer.
  • the second manufacturing method of the optical film of the present invention involves the step of preparing a stretched film.
  • the stretched film can be manufactured by a manufacturing method including the steps of preparing a resin film before stretching and stretching the prepared resin film before stretching to obtain a stretched film.
  • the surface of the stretched film on which the coating film is formed may be subjected to the above-mentioned surface modification treatment in order to improve adhesion between the stretched film and the easy-adhesion layer.
  • a coating solution containing an aqueous solvent and a polycarbonate-based polyurethane is applied to at least one surface of the stretched film to form a coating film.
  • the coating method can be any of the above-mentioned coating methods.
  • the layer of the coating liquid formed on the surface of the stretched film is dried or cured to obtain an easy-adhesion layer.
  • the coating film is usually cured by drying the solvent contained in the coating liquid. During this curing, it is preferable to carry out a heat treatment.
  • an optical film is obtained that includes a stretched film and an easy-adhesion layer provided on at least one side of the stretched film.
  • the optical film As in the first manufacturing method, in the second manufacturing method, it is preferable to manufacture the optical film as a long film from the viewpoint of increasing the manufacturing efficiency of the optical film.
  • a polarizing plate will be described as an example of the optical member of the present invention.
  • Fig. 2 shows a polarizing plate as an example of the optical member of the present invention.
  • the polarizing plate 10 shown in Fig. 2 has a structure in which a polarizer 6 is laminated via an adhesive 5 on the surface of an optical film 4 having an easy-adhesion layer 3 containing a polycarbonate-based polyurethane as a main component on one surface of a resin film 2 containing an acrylic resin as a main component.
  • the polarizing plate may have another polarizer protective film, a retardation film, or the like laminated via an adhesive layer on the opposite side of the polarizer to the optical film.
  • the polarizing plate has a structure in which a polarizer is laminated via an adhesive layer on the surface of an easy-adhesion layer of an optical film having an easy-adhesion layer on the surface of a resin film containing an acrylic resin as a main component.
  • the easy-adhesion layer formed on the optical film has excellent strength and adhesion, so that a polarizing plate having excellent adhesion between the polarizer and the optical film can be obtained.
  • any suitable polarizer can be used depending on the purpose.
  • hydrophilic polymer films such as polyvinyl alcohol films, partially formalized polyvinyl alcohol films, and partially saponified ethylene-vinyl acetate copolymer films, which have been uniaxially stretched after adsorbing a dichroic substance such as iodine or a dichroic dye
  • polyene-based oriented films such as dehydrated polyvinyl alcohol and dehydrochlorinated polyvinyl chloride.
  • a polarizer formed by adsorbing a dichroic substance such as iodine on a polyvinyl alcohol film and uniaxially stretching it is particularly preferred, as it has a high polarization dichroic ratio.
  • the thickness of these polarizers is generally about 1 to 80 ⁇ m.
  • the adhesive layer is formed from an adhesive composition that contains a polyvinyl alcohol resin or an ultraviolet-curable adhesive composition that contains an acrylic resin.
  • Water-dispersible urethane resin The properties of the water-dispersible urethane resin are shown in Table 1, including the weight average molecular weight, the shear storage modulus, the shear loss modulus, and the shear loss tangent.
  • Water-dispersible urethane resin > Water-dispersible urethane resin emulsion (1) [Polycarbonate-based polyurethane, manufactured by ADEKA Corporation, SPX-1139-5, solid content 30% by weight] Water-dispersible urethane resin emulsion (2) [Polycarbonate-based polyurethane, manufactured by ADEKA Corporation, SPX-1139-6, solid content 30% by weight] Water-dispersible urethane resin emulsion (3) [Polycarbonate-based polyurethane, manufactured by ADEKA Corporation, SPX-1139-7, solid content 30% by weight] Water-dispersible urethane resin emulsion (4) [Polycarbonate-based polyurethane, manufactured by ADEKA Corporation, SPX-1139-8, solid
  • Weight average molecular weight (Mw) The weight average molecular weight (Mw) of the water-dispersible urethane resin was measured using a gel permeation chromatograph (GPC) under the following conditions.
  • the sample solution was prepared by adding 5 ml of solvent to 17 mg of sample, gently stirring at room temperature to confirm dissolution, and then filtering through a 0.45 ⁇ m filter.
  • the Mw was calculated in terms of standard polystyrene.
  • the shear storage modulus (E'), shear loss modulus (E'') and shear loss tangent (tan ⁇ ) of the water-dispersible urethane resin were measured by the following method. First, the water-dispersible emulsion was divided into a container such as a petri dish so that the film thickness after drying would be 300 ⁇ m, and dried to prepare a polyurethane film, which was then cut into a size of 40 mm length x 10 mm width to obtain a measurement sample.
  • the chuck distance was set to 20 mm in tension mode, and the temperature was raised at a constant frequency (1 Hz) at a rate of 2°C/min to measure in the temperature range of -50 to 160°C.
  • the film was uniaxially stretched with fixed ends using a table stretching machine (stretching temperature: 145°C, stretching ratio: 3.0 times), and an optical film having an easy-adhesion layer having a thickness of 0.3 ⁇ m was produced on the surface of a methacrylic resin film having a thickness of 40 ⁇ m.
  • Examples 2 to 4 Comparative Examples 1 to 3
  • An optical film was produced under the same conditions as in Example 1, except that the adhesive composition was changed to that shown in Table 2.
  • the optical films obtained in the Examples, Comparative Examples, and Reference Examples were evaluated as follows. The evaluation results are shown in Table 2.
  • [Initial adhesion] A polyvinyl alcohol-based adhesive composition (manufactured by Mitsubishi Chemical Corporation, "GOHSENEX (registered trademark) Z-200") was applied to the easy-adhesion layer side of the optical film obtained in the Examples, Comparative Examples, and Reference Examples, and a 60 ⁇ m-thick iodine-based polarizer was laminated via the adhesive composition, and the laminate was then placed in a hot air dryer (80° C.) and dried for 10 minutes to obtain a laminate in which the polarizer and the laminate were bonded together.
  • a hot air dryer 80° C.
  • a sample piece having a size of 25 mm ⁇ 250 mm was cut out from the laminate obtained above, and the surface of the optical film was subjected to an adhesive treatment and attached to a glass plate. Thereafter, the polarizer of the laminate was gripped, and the peel strength at 90 degrees was measured according to the floating roller method of the Japanese Adhesive Industry Standard JAI 13-1996. The unit of peel strength was expressed as (N/25 mm).
  • a polyvinyl alcohol-based adhesive composition (manufactured by Mitsubishi Chemical Corporation, "GOHSENEX (registered trademark) Z-200") was applied to the easy-adhesion layer side of the optical film obtained in the Examples, Comparative Examples, and Reference Examples, and a 60 ⁇ m-thick iodine-based polarizer was laminated via the adhesive composition, and then the laminate was placed in a hot air dryer (80° C.) and dried for 10 minutes to obtain a laminate bonded to the polarizer. The laminate was then placed in a thermohygrostat at a temperature of 85° C.
  • ⁇ There is no change in the easy-adhesion layer before and after stretching of the optical film, and no whitening is observed in the easy-adhesion layer in the optical film after stretching.
  • ⁇ There is a slight change in the easy-adhesion layer before and after stretching of the optical film, and slight whitening is observed in the easy-adhesion layer in the optical film after stretching.
  • &#10005 There is a change in the easy-adhesion layer before and after stretching of the optical film, and whitening is observed in the easy-adhesion layer in the optical film after stretching.
  • the optical films of Examples 1 to 4 using an easy-adhesion layer containing a polycarbonate-based polyurethane having a weight-average molecular weight of 200,000 or more and 2,500,000 or less and a shear storage modulus ratio (E' 25 /E' 85 ) between the shear storage modulus at 25°C (E' 25 ) and the shear storage modulus at 85° C (E' 85 ) of 5 or less exhibited excellent initial adhesion and adhesion during long-term use under high temperature and high humidity environments, and no whitening of the easy-adhesion layer due to stretching was observed, showing excellent optical properties.
  • the optical films of Comparative Examples 1 to 4 which use an easy-adhesion layer containing a polycarbonate-based polyurethane with a weight-average molecular weight of 10,000 to 30,000, show poor adhesion when used for long periods of time under high temperature and high humidity, and the easy-adhesion layer turns white when stretched.
  • the optical film of Comparative Example 5 which uses an easy-adhesion layer containing a polycarbonate-based polyurethane with a weight-average molecular weight of 30,000 to 100,000, has initial adhesion comparable to that of the Examples, but shows poor adhesion when used for long periods of time under high temperature and high humidity, and the easy-adhesion layer turns white when stretched.
  • optical film of the Reference Example which uses an easy-adhesion layer containing a polyester-based polyurethane, also shows initial adhesion comparable to that of the Examples, but shows poor adhesion when used for long periods of time under high temperature and high humidity.
  • Optical film 2 Resin film 3: Easy-adhesion layer 4: Optical film 5: Adhesive layer 6: Polarizer 10: Polarizing plate

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  • Polarising Elements (AREA)

Abstract

Le but de la présente invention est de fournir un film optique qui supprime une diminution de l'adhérence initiale dans une utilisation à long terme à des températures élevées et à une humidité élevée, et qui peut supprimer le blanchiment d'une couche facilement adhésive et une détérioration des propriétés optiques due à l'étirement ou similaire. La solution selon l'invention porte sur un film optique comprenant un film de résine qui contient une résine acrylique en tant que composant principal de celui-ci, et une couche facilement adhésive qui est stratifiée sur une surface du film de résine, ledit film optique étant caractérisé en ce que la couche facilement adhésive contient un polyuréthane à base de polycarbonate en tant que composant principal de celui-ci, le polyuréthane à base de polycarbonate a un poids moléculaire moyen en poids de 200 000 à 2 500 000, et le rapport de module de stockage de cisaillement (E'25/E'85) du module de stockage de cisaillement (E'25) à 25 °C et le module de stockage de cisaillement (E'85) à 85 °C n'est pas supérieur à 5.
PCT/JP2023/035233 2022-09-29 2023-09-27 Film optique WO2024071233A1 (fr)

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WO2010119755A1 (fr) * 2009-04-16 2010-10-21 株式会社トクヤマ Composition d'apprêt pour articles optiques, et article optique
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JP2016164668A (ja) * 2016-03-28 2016-09-08 東洋紡株式会社 偏光子保護用ポリエステルフィルム
JP2016531314A (ja) * 2013-07-26 2016-10-06 エルジー・ケム・リミテッド 高輝度偏光板及びこれを含む液晶表示装置
WO2018079627A1 (fr) * 2016-10-31 2018-05-03 日本ゼオン株式会社 Film optique, son procédé de fabrication et film multicouche
WO2020162120A1 (fr) * 2019-02-08 2020-08-13 東洋紡株式会社 Écran pliable et équipement terminal portable
JP2021505949A (ja) * 2017-12-15 2021-02-18 エルジー・ケム・リミテッド 偏光板、偏光板−キャリアフィルム積層体、偏光板−キャリアフィルム積層体の製造方法、偏光板の製造方法および活性エネルギー線硬化型組成物
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003292928A (ja) * 2002-02-04 2003-10-15 Toyo Ink Mfg Co Ltd ウレタン樹脂粘着剤及び積層体
WO2010119755A1 (fr) * 2009-04-16 2010-10-21 株式会社トクヤマ Composition d'apprêt pour articles optiques, et article optique
JP4623239B1 (ja) * 2009-09-29 2011-02-02 東洋紡績株式会社 積層フィルム
WO2012165579A1 (fr) * 2011-06-03 2012-12-06 Hoya株式会社 Lentille en matière plastique
US20140125926A1 (en) * 2011-07-06 2014-05-08 Lg Chem, Ltd. Retardation film, manufacturing method thereof, and liquid crystal display device including the same
JP2015520793A (ja) * 2013-04-30 2015-07-23 エルジー・ケム・リミテッド ポリエステル系プライマー組成物、これを用いた光学フィルム、及びこれを含む偏光板
JP2016531314A (ja) * 2013-07-26 2016-10-06 エルジー・ケム・リミテッド 高輝度偏光板及びこれを含む液晶表示装置
JP2016164668A (ja) * 2016-03-28 2016-09-08 東洋紡株式会社 偏光子保護用ポリエステルフィルム
WO2018079627A1 (fr) * 2016-10-31 2018-05-03 日本ゼオン株式会社 Film optique, son procédé de fabrication et film multicouche
JP2021505949A (ja) * 2017-12-15 2021-02-18 エルジー・ケム・リミテッド 偏光板、偏光板−キャリアフィルム積層体、偏光板−キャリアフィルム積層体の製造方法、偏光板の製造方法および活性エネルギー線硬化型組成物
WO2020162120A1 (fr) * 2019-02-08 2020-08-13 東洋紡株式会社 Écran pliable et équipement terminal portable
WO2022114000A1 (fr) * 2020-11-27 2022-06-02 大倉工業株式会社 Film optique et son procédé de production

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