WO2013118720A1 - 光学用フィルム、並びにディスプレイ装置 - Google Patents

光学用フィルム、並びにディスプレイ装置 Download PDF

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Publication number
WO2013118720A1
WO2013118720A1 PCT/JP2013/052605 JP2013052605W WO2013118720A1 WO 2013118720 A1 WO2013118720 A1 WO 2013118720A1 JP 2013052605 W JP2013052605 W JP 2013052605W WO 2013118720 A1 WO2013118720 A1 WO 2013118720A1
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Prior art keywords
optical film
resin layer
film according
resin composition
adhesive
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PCT/JP2013/052605
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English (en)
French (fr)
Japanese (ja)
Inventor
那須　健司
佐藤　慶一
有記 本郷
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リンテック株式会社
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Priority to KR1020147021903A priority Critical patent/KR102148126B1/ko
Priority to CN201380008112.5A priority patent/CN104115036B/zh
Publication of WO2013118720A1 publication Critical patent/WO2013118720A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/062—Polyethers
    • 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

Definitions

  • the present invention relates to an optical film and a display device using the optical film.
  • an HC film having a hard coat (hereinafter also referred to as “HC”) layer is attached to the surface of a mobile device such as a mobile phone via an adhesive for the purpose of preventing scratches.
  • HC hard coat
  • the surface of the HC layer of the HC film may be subjected to decorative printing for the purpose of improving the design of the surface of the mobile device.
  • the HC layer is composed of a resin layer crosslinked at a high density by polymerization of a number of unsaturated bonds, the adhesion of a printing material such as ink to the HC layer tends to be low.
  • the material for forming the HC layer may be blended with a leveling agent such as silicone or fluorine for the purpose of smoothing the surface of the HC layer to be formed or for improving the coating property. Normally, when a leveling agent such as silicone or fluorine is blended, the surface of the formed HC layer becomes low polarity, so the affinity with the printing material is lowered and the adhesion to the printing material is further reduced. There is.
  • Patent Document 1 discloses a photopolymerization initiator, a (meth) acrylate monomer, and an alkylamide group (meth) for the purpose of providing an HC film having an HC layer excellent in scratch prevention performance and printability.
  • An HC film having an HC layer containing an acrylic monomer and / or phosphate (meth) acrylate at a specific mass ratio is disclosed.
  • Patent Document 2 discloses that a surface tension has a specific value on at least one surface of a base material for the purpose of providing an HC film that enables direct printing on an HC layer by a thermal transfer printing method using a thermal transfer printer.
  • An HC film provided with the above HC layer is disclosed.
  • Patent Document 2 does not disclose a specific means for setting the surface tension of the HC layer surface to a specific value or more.
  • the liquid crystal display when the HC film is used for a liquid crystal display, the liquid crystal display usually has a multilayer structure composed of multiple layers for improving various optical elements between the substrate and the liquid crystal. Therefore, the HC film used for the liquid crystal display is often attached to another layer (a layer made of an optical film) via a layer made of an adhesive.
  • the HC layer of a general HC film has an HC layer that can improve the adhesiveness to the adhesive because it has poor adhesiveness to the adhesive for the same reason that the adhesiveness to the printing material is low. HC film is desired.
  • the present invention is excellent in adhesion to the printing material and adhesiveness to the pressure-sensitive adhesive, and has good scratch resistance because of its high surface hardness. Even when left in a high temperature and high humidity environment for a long time, these An object is to provide an optical film having excellent durability in which characteristics are maintained, and a display device using the optical film.
  • the present inventors have determined that two types of polymerizable compounds having a specific structure are specified as a curable resin composition for forming a resin layer of an optical film that plays the role of an HC layer.
  • the present inventors have found that the above-mentioned problems can be solved by using a resin composition contained in a proportion, and have reached the present invention.
  • the present invention provides the following [1] to [8].
  • [1] An optical film provided with a resin layer containing a cured product of a curable resin composition on at least one surface of a substrate,
  • the curable resin composition has two or more groups represented by the following formula (1) in one molecule, and the remaining structure excluding the groups does not contain an alkylene oxide unit.
  • the compound (A) contains 3 or more polymerizable compounds (B) having a group represented by the following general formula (2) in one molecule, and a polymerization initiator (C).
  • B) An optical film having a mass ratio [(A) / (B)] to the component of 15/85 to 85/15.
  • R shows a hydrogen atom or a methyl group each independently, and * shows a coupling
  • each R 1 independently represents a hydrogen atom or a methyl group
  • each A independently represents an alkylene group having 1 to 5 carbon atoms.
  • n is an integer greater than or equal to 1 each independently. * Represents a binding moiety.
  • [2] The optical film as described in [1] above, wherein the total value of n in the general formula (2) in one molecule of the polymerizable compound (B) is 4 to 20.
  • a in the general formula (2) is independently an ethylene group or a propylene group.
  • the optical film of the present invention is excellent in adhesion with a printing material and adhesiveness with a pressure-sensitive adhesive, and has a good scratch resistance because of its high surface hardness, and is left for a long time in a high-temperature and high-humidity environment. Moreover, it has excellent durability that maintains these characteristics.
  • a resin layer containing a cured product of the curable resin composition is provided on at least one surface of a substrate.
  • the optical film of the present invention is not limited to the optical film 1 in which the resin layer 12 is provided on one surface of the substrate 11 as shown in FIG.
  • cured material of the said curable resin composition were provided on both surfaces is also contained.
  • the optical film of the present invention may be an optical film having a pressure-sensitive adhesive layer made of a pressure-sensitive adhesive on at least one surface on the opposite side and the same side as the surface on which the resin layer of the substrate is provided. Good. That is, the position of the pressure-sensitive adhesive layer may be provided on the surface of the substrate opposite to the surface on which the resin layer is provided, or may be provided on the surface of the resin layer. It may be provided on both sides.
  • FIG. 3 an example of the structure of the optical film of this invention which has an adhesive layer is shown.
  • the optical film 1a in FIG. 3A is an optical film having an adhesive layer 13 on the surface opposite to the surface on which the resin layer 12 of the substrate 11 is provided.
  • the optical film 1c in FIG. 3 (c) has an adhesive layer 13a, 13b on both the same side as the surface on which the resin layer 12 of the substrate 11 is provided and on the opposite side. It is a film, has an adhesive layer 13a on the surface of the resin layer 12, and has an adhesive layer 13b on the surface of the substrate 11 opposite to the surface on which the resin layer 12 is provided.
  • a release material may be further laminated on the pressure-sensitive adhesive layer.
  • the optical film in which the resin layer was provided on the both surfaces of the base material you may have an adhesive layer further on the surface of each resin layer.
  • the structure of the optical films 2a and 2b shown in FIG. 4 is mentioned, for example.
  • the optical film 2a is provided with resin layers 12a and 12b on both surfaces of the substrate 11, and further has an adhesive layer 13 only on the surface of the resin layer 12b.
  • the optical film 2 b has pressure-sensitive adhesive layers 13 a and 13 b on both surfaces of the resin layers 12 a and 12 b provided on both surfaces of the base material 11.
  • the base material used in the present invention is not particularly limited as long as it can be used as an optical film.
  • Examples of the material constituting such a substrate include polyethylene terephthalate (PET), polyethylene naphthalate, polyimide, polyetherimide, polyaramid, polyetherketone, polyetheretherketone, polyphenylene sulfide, and poly (4-methyl).
  • Pentene-1 polyethylene, polypropylene, polybutene, polybutadiene, polymethylpentene, polyvinyl chloride, vinyl chloride copolymer, polyurethane, ethylene-vinyl acetate copolymer, ionomer resin, ethylene (meth) acrylic acid copolymer
  • the resin film include polystyrene, polycarbonate, fluororesin, low density polyethylene, linear low density polyethylene, and triacetyl cellulose.
  • polyethylene terephthalate is preferable from the viewpoints of optical properties such as processability and transparency, versatility, and cost.
  • the surface of the substrate may be subjected to easy adhesion treatment such as primer treatment or corona treatment.
  • the thickness of the substrate is appropriately selected depending on the application, but is preferably 5 to 300 ⁇ m, more preferably 10 to 200 ⁇ m, and still more preferably 20 to 100 ⁇ m.
  • the resin layer constituting the optical film of the present invention is a layer containing a cured product of a curable resin composition containing components (A) to (C) (hereinafter also simply referred to as “resin composition”).
  • the said resin layer may also contain resin components other than the hardened
  • the content of the cured product of the curable resin composition in the resin layer is preferably 70 to 100% by mass, more preferably 80 to 100% by mass, and still more preferably 90 to 100% with respect to the total mass of the resin layer. It is 100 mass%, More preferably, it is 100 mass%.
  • the curable resin composition used in the present invention has two or more groups represented by the general formula (1) in one molecule, and an alkylene oxide unit in the remaining structure excluding the group.
  • a polymerizable compound (A) not contained, a polymerizable compound (B) having three or more groups represented by the general formula (2) in one molecule, and a polymerization initiator (C) are contained.
  • the said resin composition may contain a leveling agent (D) and another additive further.
  • the resin composition used in the present invention contains the polymerizable compound (B) together with the polymerizable compound (A), thereby increasing the surface hardness of the resin layer formed from the resin composition and improving the durability. Adhesiveness with the printing material of a resin layer and adhesiveness with an adhesive can be made favorable.
  • Component (A) a polymerizable compound having two or more groups represented by the general formula (1) in one molecule and having no alkylene oxide unit in the remaining structure excluding the group ( A)
  • the resin composition used in the present invention has two or more groups represented by the following general formula (1) in one molecule and does not contain an alkylene oxide unit in the remaining structure excluding the groups.
  • R shows a hydrogen atom or a methyl group each independently, and * shows a coupling
  • the number of groups represented by the general formula (1) in one molecule of the polymerizable compound (A) is 2 or more, preferably 2 to 16, more preferably 2 to 12, and still more preferably. Is 3 to 10, more preferably 3 to 8. If the number of the groups is less than 2, it is not preferable because a sufficient cross-linked structure is not formed and the surface hardness of the resin layer formed from the resin composition tends to decrease. On the other hand, if the number of the groups is 16 or less, it is possible to suppress a decrease in printing characteristics and adhesion of the resin layer formed from the resin composition due to the excessively high crosslinking density. Further, curling due to curing shrinkage can also be suppressed.
  • the polymerizable compound (A) is a compound that does not contain an alkylene oxide unit in the remaining structure excluding the group represented by the general formula (1). Since the compound containing an alkylene oxide unit has a long chain length of the alkylene oxide structure, the distance between the cross-linking points is increased, and the structure of the entire resin layer formed from the resin composition tends to be sparse, and as a result, the resin layer This is considered to cause a decrease in the surface hardness of the steel. Therefore, in this invention, it is thought that the surface hardness of the resin layer formed from a resin composition is raised by using the polymeric compound which does not contain an alkylene oxide unit as (A) component.
  • Examples of such a polymerizable compound (A) include trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipenta.
  • the group Remaining in the structure does not include the alkylene oxide units oligoester (meth) acrylates with the exception, oligo ether (meth) acrylates, oligourethane (meth) acrylates, and oligo epoxy (meth) acrylates.
  • the resin composition used in the present invention contains three or more polymerizable compounds (B) having a group represented by the following general formula (2) in one molecule.
  • R ⁇ 1 > shows a hydrogen atom or a methyl group each independently.
  • * shows a coupling
  • Each A independently represents an alkylene group having 1 to 5 carbon atoms, preferably an ethylene group or a propylene group, and more preferably an ethylene group.
  • the content of the ethylene oxide unit with respect to all the alkylene oxide units contained in one molecule of the polymerizable compound (B) is preferably from the viewpoint of improving the adhesiveness with the printing material and the adhesive. It is 60 to 100 mol%, more preferably 75 to 100 mol%, still more preferably 85 to 100 mol%, still more preferably 95 to 100 mol%.
  • n represents the number of alkylene oxide units, and each independently represents an integer of 1 or more.
  • the total value of n in the general formula (2) (the total number of alkylene oxide units in one molecule of the polymerizable compound (B)) in one molecule of the polymerizable compound (B) is 3 or more.
  • it is preferably 4 to 20, more preferably 6 to 16, and still more preferably. 8-14. If the said total value is 4 or more, the crosslinking density of the resin layer formed from a resin composition can be reduced moderately, and adhesiveness with a printing material and adhesiveness with an adhesive can be improved. On the other hand, if the total value is 20 or less, the crosslinking density is not excessively lowered, and therefore, a certain degree of surface hardness can be maintained, which is preferable.
  • the number of groups represented by the general formula (2) in one molecule of the polymerizable compound (B) is 3 or more, preferably 3 to 16, more preferably 3 to 12, and still more preferably. Is from 3 to 10, more preferably from 3 to 8, even more preferably from 5 to 8.
  • the number of the groups is less than 3, the crosslinking density of the resin layer formed from the resin composition is lowered, and the surface hardness is lowered, which is not preferable. In addition, the durability of the resin layer is reduced. On the other hand, if it is 16 or less, since the fall of the printing characteristic and adhesiveness by a crosslinking density becoming high too much can be suppressed, it is preferable.
  • Examples of such a polymerizable compound (B) include alkylene oxide-modified glycerin tri (meth) acrylate, alkylene oxide-modified dipentaerythritol tetra (meth) acrylate, alkylene oxide-modified dipentaerythritol hexa (meth) acrylate, and the like. It is done. In addition, you may use these (B) components individually or in combination of 2 or more types.
  • the mass ratio [(A) / (B)] of the component (A) to the component (B) is 15/85 to 85/15, preferably 20/80 to 80/20, more preferably 28/72 to 72/28, more preferably 35/65 to 65/35, still more preferably 41/59 to 59/41, still more preferably 46/54 to 54/46 . If the mass ratio is less than 15/85, the amount of the component (B) is too large, so that the surface hardness of the resin layer formed from the resin composition is not preferable. In addition, the durability of the resin layer tends to decrease. On the other hand, when the mass ratio exceeds 85/15, since the amount of the component (A) is too large, the adhesion of the resin layer formed from the resin composition to the printing material and the adhesiveness to the pressure-sensitive adhesive are inferior.
  • the total content of the component (A) and the component (B) with respect to all components contained in the resin composition used in the present invention is preferably 70 to 99.9% by mass, more preferably 80 to 99% by mass, and still more preferably Is 90 to 98% by mass.
  • the polymerization initiator (C) used in the present invention is not particularly limited as long as it accelerates the polymerization reaction of the polymerizable compounds of the components (A) and (B), and is a photopolymerization initiator or thermal polymerization. Any initiator can be used, and these may be used in combination.
  • photopolymerization initiator examples include acetophenone series, benzophenone series, benzoin series, thioxanthone series, and imidazole series photopolymerization initiators.
  • acetophenone photopolymerization initiator examples include diethoxyacetophenone, 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl] -2-methylpropan-1-one, 2-benzyl-2-dimethylamino.
  • benzophenone photopolymerization initiator examples include benzophenone, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl) benzophenone, Examples include 2,4,6-trimethylbenzophenone and 4,4′-bis-dimethylaminobenzophenone.
  • benzoin photopolymerization initiator examples include benzoin compounds such as benzoin, methylbenzoin, and ethylbenzoin, and benzoin ether compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether, and benzoin phenyl ether.
  • Examples of the thioxanthone photopolymerization initiator include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 1-chloro-4-propoxythioxanthone, 2,4-dichlorothioxanthone, and the like.
  • imidazole photopolymerization initiator examples include 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbisimidazolyl, 2,2′-bis (o-chlorophenyl)- 4,4 ′, 5,5′-tetra- (p-methoxyphenyl) bisimidazolyl, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2 ′ -Hexaarylbisimidazole compounds such as biimidazole.
  • photopolymerization initiators may be used alone or in combination of two or more.
  • thermal polymerization initiator examples include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, and di (2-ethoxyethyl).
  • the blending amount of the polymerization initiator (C) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, and still more preferably with respect to 100 parts by mass of the total amount of the components (A) and (B). Is 3 to 15 parts by mass, more preferably 3.5 to 8 parts by mass.
  • a leveling agent (D) is preferably further blended from the viewpoint of improving the smoothness and coating properties of the obtained HC layer.
  • the leveling agent (D) include an acrylic leveling agent, a silicone leveling agent, a fluorine leveling agent, an acrylic leveling agent, a vinyl leveling agent, and a siloxane-modified acrylic leveling agent.
  • silicone leveling agent a copolymer of polyoxyalkylene and polydimethylsiloxane can be used.
  • Commercially available silicone leveling agents include FZ-2118, FZ-77, FZ-2161 (trade names, manufactured by Toray Dow Corning Co., Ltd.), KP321, KP323, KP324, KP326, KP340, KP341 (trade names, Manufactured by Shin-Etsu Chemical Co., Ltd.), TSF4440, TSF4441, TSF4445, TSF4450, TSF4446, TSF4452, TSF4453, TSF4460 (trade name, manufactured by Momentive Performance Materials Japan GK), etc., BYK-300, BYK-302, BYK-306, BYK-307, BYK-320, BYK-325, BYK-330, BYK-331, BYK-333, BYK-337, BYK-341, BYK-344, BYK-345, BYK-3
  • fluorine leveling agent a copolymer of polyoxyalkylene and fluorocarbon can be used.
  • fluorine leveling agents include MEGAFAC series manufactured by DIC Corporation, FC series manufactured by Sumitomo 3M Corporation, and the like.
  • acrylic leveling agents include BYK-350, BYK-352, BYK-354, BYK-355, BYK358N, BYK-361N, BYK-380N, BYK-382, BYK-392 (trade name, Big Chemie Japan Etc.).
  • siloxane-modified acrylic leveling agents include BYK-3550 (trade name, manufactured by Big Chemie Japan Co., Ltd.).
  • leveling agents may be used alone or in combination of two or more.
  • an acrylic leveling agent or a siloxane-modified acrylic leveling agent is preferable, and a siloxane-modified acrylic leveling agent is more preferable from the viewpoint of improving the smoothness and coating properties of the resin layer formed from the resin composition.
  • the amount of the leveling agent (D) is preferably 0.01 to 10 parts by weight, more preferably 0.03 to 5 parts by weight, more preferably 100 parts by weight of the total amount of the components (A) and (B).
  • the amount is preferably 0.06 to 3 parts by mass.
  • additives You may mix
  • additives include antifoaming agents, thickeners, surfactants, organic lubricants, organic fine particles, inorganic fine particles, antioxidants, ultraviolet absorbers, foaming agents, dyes, pigments, An antistatic agent etc. are mentioned.
  • the total amount of additives is preferably 0.01 to 10% by mass, more preferably 0.1 to 7% by mass, based on all components contained in the resin composition. %, More preferably 0.3 to 3% by mass.
  • the resin composition used in the present invention may be further diluted with an organic solvent to prepare a coating solution for forming a resin layer in order to facilitate application to a base material and improve workability.
  • organic solvent include methyl ethyl ketone, acetone, ethyl acetate, tetrahydrofuran, dioxane, cyclohexane, n-hexane, toluene, xylene, n-propanol, isopropanol, propylene glycol monomethyl ether and the like.
  • the solid content concentration of the resin layer forming coating solution is preferably 10 to 60% by mass, more preferably 10 to 45% by mass, and still more preferably 15 to 30% by mass. If it is 10% by mass or more, the amount of the solvent used is sufficient, and if it is 60% by mass or less, the viscosity becomes appropriate and the coating operation becomes easy.
  • a known method can be used as a method for applying the resin layer forming coating solution to a substrate.
  • a gravure coating method for example, a gravure coating method, a bar coating method, a spray coating method, a spin coating method, a roll coating method, a die coating method. , Knife coating method, air knife coating method, curtain coating method and the like.
  • the formed coating film is heated at a temperature of about 80 ° C. to 150 ° C. for 30 seconds to It is preferable to dry for about 5 minutes.
  • the resin layer can be formed by curing the coating film.
  • a curing method when a photopolymerization initiator is used as the component (C), it is allowed to proceed by irradiation with active energy rays, and when a thermal polymerization initiator is used as the component (C), it is advanced by heating.
  • active energy rays include ultraviolet rays, electron beams, ⁇ rays, ⁇ rays, and the like, and ultraviolet rays are preferable.
  • the accumulated light quantity of ultraviolet light is preferably 100mJ / cm 2 ⁇ 2000mJ / cm 2, more preferably 150mJ / cm 2 ⁇ 1000mJ / cm 2.
  • the thickness of the resin layer thus obtained is preferably 1 to 20 ⁇ m, more preferably 1 to 15 ⁇ m, and still more preferably, from the viewpoints of hard coat properties and cost, and from the viewpoint of reducing shrinkage and suppressing the occurrence of curling. Is 1 to 10 ⁇ m.
  • the surface tension of the resin layer is preferably 30 mN / m or more, more preferably 33 mN / m or more, and still more preferably 35 mN / m or more, from the viewpoint of suppressing the repelling of a printing material such as ink.
  • the value of the surface tension of the resin layer is a value measured according to the wetting tension test method of “JIS K6768: 1999”, specifically, a value measured based on the description of the examples. It is.
  • the pencil hardness indicating the surface hardness of the resin layer is preferably F or higher, more preferably H or higher, and even more preferably 2H or higher.
  • the pencil hardness of the resin layer is measured according to JIS K 5600-5-4, and specifically, is measured based on the description of the examples.
  • the optical film of the present invention may be provided with an adhesive layer made of an adhesive.
  • the pressure-sensitive adhesive to be used is not particularly limited, and can be appropriately selected from those commonly used according to the purpose. Examples of such adhesives include acrylic adhesives, polyurethane adhesives, polyester adhesives, rubber adhesives, silicone adhesives, and the like. Moreover, any of an emulsion type, a solvent type, and a solventless type may be sufficient as an adhesive, and any of a crosslinking type or a non-crosslinking type may be sufficient as it.
  • the thickness of the pressure-sensitive adhesive is appropriately selected depending on the application, but is preferably 3 to 100 ⁇ m, more preferably 5 to 80 ⁇ m.
  • the optical film of the present invention having the above-described configuration is excellent in adhesion with a printing material and adhesiveness with a pressure-sensitive adhesive, and has good scratch resistance because of high surface hardness, and has excellent durability.
  • Examples of the use of the optical film having such characteristics include a display device such as a liquid crystal display using the optical film as a protective member for an image display portion. Since the optical film of the present invention is used as the protective member for the image display portion, the display device has good damage prevention performance for the image display portion and has excellent durability.
  • Examples 1 to 12, Comparative Examples 1 to 13 After preparing the curable resin composition by mixing the components (A) to (D) at the blending amounts shown in Tables 1 and 2 (both parts by mass (solid content ratio)), dilute with propylene glycol monomethyl ether Thus, a coating solution for forming a resin layer having a solid concentration of 30% by mass was obtained. And one side of a polyethylene terephthalate (PET) film (trade name “Lumirror U48” manufactured by Toray Industries, Inc., film thickness 100 ⁇ m) with an easy-adhesion layer on both sides used as a base material.
  • PET polyethylene terephthalate
  • the prepared coating solution for resin layer formation was applied using a Mayer bar so that the film thickness after drying was 3 ⁇ m to form a coating film. Thereafter, the coating film is dried at 80 ° C. for 1 minute, and then irradiated with ultraviolet rays at 300 mJ / cm 2 (integrated light amount) using a high-pressure mercury lamp to cure the coating film, so that an optical film having a resin layer with a thickness of 3 ⁇ m is obtained.
  • a film was prepared.
  • A-TMN-3L pentaerythritol triacrylate represented by the following formula (A-1) (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name, group represented by the above general formula (1) (R: hydrogen) Acrylate having 3 atoms).
  • A-DPH dipentaerythritol hexaacrylate represented by the following formula (A-2) (made by Shin-Nakamura Chemical Co., Ltd., trade name, group represented by the above general formula (1) (R: hydrogen atom) Acrylate having 6).
  • A-DPH-12E ethylene oxide-modified dipentaerythritol hexaacrylate represented by the following formula (B-1) (made by Shin-Nakamura Chemical Co., Ltd., trade name, group represented by the above general formula (2) (R 1 : acrylate having 6 hydrogen atoms and A: ethylene group) (the total value of n in the general formula (2) in one molecule is 12)).
  • A-GLY-9E ethylene oxide-modified glycerin triacrylate represented by the following formula (B-2) (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name, group represented by the above general formula (2) (R 1 : An acrylate having three hydrogen atoms and A: an ethylene group (the total value of n in the general formula (2) in one molecule is 9)).
  • DMAA dimethylacrylamide
  • A-200 polyethylene glycol diacrylate represented by the following formula (b-1) (made by Shin-Nakamura Chemical Co., Ltd., trade name, group represented by the above general formula (2) (R 1 : hydrogen atom)
  • R 1 hydrogen atom
  • A an acrylate having two ethylene groups (the total value of n in the general formula (2) in one molecule is 4)).
  • A-BPE-6 ethylene oxide-modified bisphenol A diacrylate represented by the following formula (b-2) (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name, group represented by the above general formula (2) ( An acrylate having two R 1 : hydrogen atom and A: ethylene group (the total value of n in the general formula (2) in one molecule is 6)).
  • Component (C) Irgacure 184: 1-hydroxycyclohexyl phenyl ketone (trade name, acetophenone photopolymerization initiator, manufactured by BASF).
  • An ultraviolet curable ink (trade name “UVPAL911 Black”, manufactured by Teikoku Ink Co., Ltd.) is applied to the surface of the resin layer of the optical film, and the ink is cured by irradiating with ultraviolet rays to form a printed layer having a thickness of 1 ⁇ m. A formed optical film was obtained. Then, the surface of the printed layer is subjected to a cross cut with a 1 mm width in a grid pattern, and an adhesive tape (trade name “Cero Tape (registered trademark)” manufactured by Nichiban Co., Ltd.) is applied to the surface of the printed layer that is cross-cut in the grid pattern.
  • an adhesive tape (trade name “Cero Tape (registered trademark)” manufactured by Nichiban Co., Ltd.) is applied to the surface of the printed layer that is cross-cut in the grid pattern.
  • the ratio of the part that is clearly influenced by the cross cut part is more than 5% and not more than 15%.
  • C Large peeling occurred partially or entirely along the edge of the cut line formed by cross-cutting the surface of the printing layer, and / or several eyes formed were partially or completely formed It is peeled off.
  • the ratio of the part that is clearly influenced by the crosscut part is more than 15% and not more than 35%.
  • D Large peeling occurs partially or entirely along the edge of the cut line formed by cross-cutting the surface of the printing layer, and / or several eyes formed are partially or completely formed It is peeled off.
  • the proportion of the portion that is clearly influenced by the cross cut portion is more than 35% and 65% or less of the whole.
  • E The ratio of the part judged to be clearly influenced by the cross-cut part is more than 65% of the whole.
  • ⁇ Ink repellency> The repelling of the ink when an ultraviolet curable ink (product name “UVPAL911 Black”, manufactured by Teikoku Ink Co., Ltd.) was applied to the surface of the resin layer was visually confirmed and evaluated according to the following criteria. A: No repelling is observed. B: A repellency is seen only at the end portion (no repellency is seen in other portions). C: Repelling is observed on the entire surface.
  • UVPAL911 Black product name “UVPAL911 Black”, manufactured by Teikoku Ink Co., Ltd.
  • optical films obtained in the Examples and Comparative Examples were manufactured using a double-sided tape (product name “TL-85S-12” manufactured by Lintec Corporation) and a glass plate (product name manufactured by NSG Precision Co., Ltd.). Attached to “Corning Glass Eagle XG” (size: 70 mm ⁇ 150 mm ⁇ 0.3 mm), an adherend having a resin layer exposed was prepared.
  • an adhesive sheet for evaluation of adhesive strength (product name “PET25 (A) P1069111LL” manufactured by Lintec Corporation) was cut into a size of 25 mm ⁇ 250 mm, and the release material of the adhesive sheet was peeled off, and then the resin layer of the adherend Affixed on the surface. After that, it is left for 24 hours in an environment of 23 ° C. and 50% RH (relative humidity), and in that environment, using a tensile testing machine (product name “Tensilon”) according to JIS Z0237.
  • the adhesive strength (N / 25 mm) was measured under the conditions of a peeling speed of 300 mm / min and a peeling angle of 180 °.
  • ⁇ Pencil hardness> According to JIS K 5600-5-4, the pencil hardness of the resin layer surface was measured using a pencil scratch hardness tester (manufactured by Yasuda Seiki Seisakusho, product name “No. 553-M”). The scratching speed was 1 mm / second.
  • ⁇ Durability test> an optical film having a printing layer produced by the same method as described in the above-mentioned “Adhesion with printing material” was used. After the optical film is allowed to stand for 240 hours in a 60 ° C., 90% RH (relative humidity) environment and promoted, 10 ⁇ 10 squares of 100 squares in total are formed on the surface of the printed layer. In addition, a cross cut of 10 mm ⁇ 10 ⁇ 10 squares having a width of 1 mm is applied to the grid pattern, and an adhesive tape (trade name “Cello Tape (registered trademark)” manufactured by Nichiban Co., Ltd.) is applied to the surface of the cross cut pattern of the grid pattern. )).
  • an adhesive tape trade name “Cello Tape (registered trademark)” manufactured by Nichiban Co., Ltd.
  • the optical films of the present invention of Examples 1 to 12 have high surface tension of the resin layer of the film, excellent adhesion to the printing material and adhesion to the adhesive, and high surface hardness. Therefore, it turns out that it is excellent in the damage prevention performance and is durable.
  • the optical films of Comparative Examples 1 to 13 are inferior in any of the following items: adhesion to the printing material, adhesion to the pressure-sensitive adhesive, surface strength of the resin layer of the film, and durability. As a result.
  • the optical film of the present invention is excellent in adhesion with a printing material and adhesiveness with a pressure-sensitive adhesive, and has a good anti-scratch property due to its high surface hardness, and has excellent durability. Since it has such characteristics, the optical film of the present invention is suitable as a member of a display device such as a liquid crystal display.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Surface Treatment Of Optical Elements (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Adhesives Or Adhesive Processes (AREA)
PCT/JP2013/052605 2012-02-06 2013-02-05 光学用フィルム、並びにディスプレイ装置 WO2013118720A1 (ja)

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JPWO2016006627A1 (ja) * 2014-07-11 2017-04-27 三菱レイヨン株式会社 微細凹凸構造体
KR101979200B1 (ko) * 2014-10-16 2019-05-17 주식회사 엘지화학 광학 필름 코팅용 조성물 및 이를 포함하는 광학 필름
KR102548098B1 (ko) * 2016-02-24 2023-06-27 도레이 카부시키가이샤 착색 수지 조성물
JP6291558B2 (ja) * 2016-11-08 2018-03-14 リンテック株式会社 光学用フィルム、並びにディスプレイ装置

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CN104115036B (zh) 2016-05-04
CN104115036A (zh) 2014-10-22
TW201343818A (zh) 2013-11-01

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