Hard coat film, optical display

Abstract

To provide a hard coat film to be laminated onto an optical display, the hard coat film capable of preventing slidability from deteriorating, when having washed a hard coat layer surface of the hard coat film with alcohol or for securing qualities such as excellent appearances at the time of shipping, and to provide an optical display having the hard coat film.SOLUTION: A hard coat film includes a base material layer and a hard coat layer. The hard coat layer is a layer including an active energy ray-curable resin (A) and a slipping agent (C) having a weight-average molecular weight (Mw) of 10,000 or more. After an alcohol wipe test in which a surface of the hard coat layer is reciprocally wiped by 50 times with a Kim towel wiper sufficiently impregnated with alcohol while applying a load of 0.4 kgf / cm2, a water contact angle on the surface of the hard coat layer is 92° or more. An optical display is equipped with the hard coat film.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a hard coat film having excellent slipperiness, which is suitable for use in touch panels and the like. [Background technology]

[0002] In recent years, touch panels that serve as both a display device and an input means have come into widespread use in various electronic devices. A hard coat film is used on the surface of a touch panel to prevent scratches on the screen caused by pressing with a finger or a pen.

[0003] As such a hard coat film, Patent Document 1 describes an antiglare hard coat film having a cured layer of an antiglare hard coat resin composition comprising an organic plastic film, a polyfunctional (meth)acrylate, organic fine particles, nanosilica, and a photopolymerization initiator, the organic fine particles including organic fine particles (B1) having an average particle diameter of 5 to 20 μm and organic fine particles (B2) having an average particle diameter of 50 to 300 nm.

[0004] The antiglare hard coat film described in this document is said to be able to suppress glare even in high-resolution images when used in applications such as touch panels, while at the same time causing very little wear to the nib of a touch pen and achieving a writing feel similar to that of writing with a pencil on paper. This document also describes that a slip agent or the like may be added to the hard coat resin composition as needed. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Patent Publication No. 2021-42288 Summary of the Invention [Problem to be solved by the invention]

[0006] Incidentally, touch panels provided with a hard coat film are required to have excellent quality in appearance etc. at the time of shipment. For this reason, the surface of the hard coat layer of the hard coat film is sometimes washed with alcohol such as ethanol to ensure that the surface of the hard coat layer is free of dirt etc. and to ensure excellent quality in appearance etc. at the time of shipment.

[0007] Furthermore, because touch panels are operated with fingers, the surface of the touch panel is usually stained with finger grease and the like. When fingerprints or other stains adhere to the surface of a touch panel, the appearance deteriorates and the displayed image often becomes difficult to see. To remove such stains, the touch panel may be cleaned with alcohol such as ethanol.

[0008] However, when the surface of the hard coat layer of a hard coat film is washed with alcohol, the slipperiness of the surface of the hard coat layer when inputting with a finger or a pen may be reduced.

[0009] The present invention has been made in consideration of the above-mentioned circumstances, and aims to provide a hard coat film whose slipperiness does not decrease even when the surface of the hard coat film is wiped and cleaned with ethanol in order to ensure quality such as excellent appearance at the time of shipment or to remove dirt such as finger grease adhering to the surface of the hard coat film, and an optical display equipped with the hard coat film. [Means for solving the problem]

[0010] In order to solve the above problems, the present inventors have conducted extensive research into hard coat films having a substrate layer and a hard coat layer, and have completed the present invention.

[0011] According to the present invention, the following hard coat films [1] to [7] and optical display [8] are provided. [1] A hard coat film having a material layer and a hard coat layer, the hard coat layer is a layer containing (A) component: an active energy ray-curable resin, and (C) component: a slip agent having a weight average molecular weight (Mw) of 10,000 or more, A Kimtowel soaked in alcohol was applied to the surface of the hard coat layer at a pressure of 0.4 kgf / cm. 2 the water contact angle of the surface of the hard coat layer after an alcohol wiping test in which the hard coat layer is wiped back and forth 50 times while applying a load of 1000 kJ / cm2 or more is 92° or more. Hard coat film. [2] The hard coat film according to [1], wherein the hard coat layer further contains component (B): a filler. [3] The hard coat film according to [1] or [2], wherein the difference between the water contact angle (°) of the hard coat layer surface after the alcohol wiping test and the water contact angle (°) of the hard coat layer surface before the alcohol wiping test is -10° or more.

[0012] [4] The hard coat film according to [1] or [2], wherein the water contact angle of the surface of the hard coat layer before the alcohol wiping test is 92° or more. [5] The hard coat film according to claim 1 or 2, [1] or [2], wherein the component (C): slip agent is at least one selected from the group consisting of silicone-based slip agents and fluorine-based slip agents. [6] The hard coat film according to [1] or [2], wherein the hard coat layer has a thickness of 0.1 to 30 μm. [7] The hard coat film according to [1] or [2], wherein the alcohol is ethanol. [8] An optical display comprising the hard coat film according to [1] or [2]. [Effects of the Invention]

[0013] According to the present invention, there are provided a hard coat film to be laminated on a display such as a touch panel, which can suppress a decrease in slipperiness even when the surface of the hard coat layer is washed with alcohol to ensure quality such as excellent appearance at the time of shipment or to remove dirt such as fingerprints adhering to the surface of the hard coat layer of the hard coat film, and an optical display including the hard coat film. [Brief explanation of the drawings]

[0014] [Figure 1] FIG. 1 is a cross-sectional view of one example (part) of an optical display provided with the hard coat film of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0015] The present invention will be described in detail below, divided into the sections of 1) hard coat film and 2) optical display.

[0016] 1) Hard coat film The hard coat film of the present invention is a laminated film having a substrate layer and a hard coat layer.

[0017] 1.Base material layer The substrate layer of the hard coat film of the present invention can be suitably selected from known resin films that have been conventionally used as optical films.

[0018] Examples of resin materials constituting the resin film include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene, polypropylene, viscose, diacetyl cellulose, triacetyl cellulose, acetyl cellulose butyrate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, polystyrene, polycarbonate, polymethylpentene, polysulfone, polyether ether ketone, polyether sulfone, polyetherimide, polyimide, fluororesin, polyamide, acrylic resin, norbornene-based resin, and cycloolefin resin. Among these, polyethylene terephthalate (PET), polycarbonate, triacetyl cellulose, and cycloolefin resin are preferred, with polyethylene terephthalate and triacetyl cellulose being more preferred, from the viewpoint of excellent transparency, adhesion, heat resistance, and mechanical strength, as well as the ease of satisfying the optical properties described below. Furthermore, from the viewpoint of the SDGs, the material constituting the resin film may be a material with a high biomass content, or a recyclable or reusable material, or a recycled or reused material.

[0019] When the substrate layer is used as a hard coat film, it preferably satisfies the optical properties described below and may be a single-layer or two or more-layer resin film. Furthermore, when forming a hard coat layer or the like on the substrate layer surface, physical treatments such as corona discharge treatment and oxidation treatment may be performed to improve adhesion.

[0020] The thickness of the substrate layer is not particularly limited, but in consideration of use in touch panels, it is preferably 25 to 500 μm, more preferably 40 to 400 μm, particularly preferably 60 to 300 μm, and even more preferably 80 to 200 μm, which tends to increase the scratch resistance and hardness of the hard coat film.

[0021] 2.Hard coat layer The hard coat layer of the hard coat film of the present invention (sometimes referred to herein as the "HC layer of the present invention") is preferably a layer formed from a hard coat layer-forming composition (sometimes referred to herein as the "HC layer-forming composition of the present invention") containing component (A): an active energy ray-curable resin, and component (C): a slip agent having a weight-average molecular weight (Mw) of 10,000 or more, and preferably further contains component (B): a filler. Furthermore, from the perspective of the SDGs, the material constituting the hard coat layer may be a material with a high biomass content, a material that can be recycled or reused, or a recycled or reused material.

[0022] (1) (A) Component: Main ingredient The HC layer-forming composition according to the present invention preferably contains a curable component as component (A) (in this specification, the "curable component" may be referred to as "component (A)"). The component (A) is a component that has the property of being crosslinked or cured by a trigger such as an active energy ray such as ultraviolet light or an electron beam, or heat, and examples of the component (A) include an active energy ray-curable component and a thermosetting component. From the viewpoint of easily designing the resulting hard coat layer to have a desired hardness, etc., the HC layer-forming composition according to the present invention preferably contains an active energy ray-curable component.

[0023] Examples of thermosetting components include urethane resins, epoxy resins, polyimide resins, phenolic resins, silicone resins, cyanate resins, bismaleimide triazine resins, allylated polyphenylene ether resins (thermosetting PPE), formaldehyde resins, unsaturated polyesters, and copolymers thereof. Among these, urethane resins are preferred. These resins may also have functional groups, such as hydroxyl groups and carboxyl groups, that can react with crosslinkers.

[0024] The active energy ray-curable component can be selected from conventionally known components, and an active energy ray-curable monomer, prepolymer, resin, or a mixture of two or more thereof can be used. Among them, from the viewpoint of kneadability with component (B) and ease of adjusting optical properties to a desired range, polyfunctional (meth)acrylic monomers, (meth)acrylate prepolymers, organic-inorganic hybrid resins, etc. are preferred.

[0025] Here, the term "(meth)acrylic monomer" refers to an acrylic monomer or a methacrylic monomer, the term "(meth)acrylate prepolymer" refers to an acrylate prepolymer or a methacrylate prepolymer, and the term "(meth)acrylic acid" refers to acrylic acid or methacrylic acid, as well as other similar terms.

[0026] Examples of polyfunctional (meth)acrylic monomers include 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, hydroxypivalic acid neopentyl glycol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, caprolactone-modified dicyclopentenyl di(meth)acrylate, ethylene oxide-modified phosphate di(meth)acrylate, allylated cyclohexyl di(meth)acrylate, isocyanurate di(meth)acrylate, trimethylsilyl acrylate, and the like. Examples of suitable monomers include polyfunctional (meth)acrylates such as trimethylolpropane tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, propionic acid-modified dipentaerythritol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, propylene oxide-modified trimethylolpropane tri(meth)acrylate, tris(acryloxyethyl)isocyanurate, propionic acid-modified dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and caprolactone-modified dipentaerythritol hexa(meth)acrylate. These monomers can be used alone or in combination of two or more.

[0027] Examples of the (meth)acrylate prepolymer include polyester acrylate prepolymer, epoxy acrylate prepolymer, urethane acrylate prepolymer, and polyol acrylate prepolymer.

[0028] Here, polyester acrylate prepolymers can be obtained by esterifying the hydroxyl groups of a polyester oligomer having hydroxyl groups at both ends, obtained by condensation of a polycarboxylic acid and a polyhydric alcohol, with (meth)acrylic acid, or by esterifying the terminal hydroxyl groups of an oligomer obtained by adding an alkylene oxide to a polycarboxylic acid with (meth)acrylic acid. Epoxy acrylate prepolymers can be obtained by esterifying the oxirane ring of a relatively low-molecular-weight bisphenol epoxy resin or novolac epoxy resin with (meth)acrylic acid. Urethane acrylate prepolymers can be obtained by esterifying a polyurethane oligomer obtained by reacting a polyether polyol or polyester polyol with a polyisocyanate with (meth)acrylic acid. Polyol acrylate prepolymers can be obtained by esterifying the hydroxyl groups of a polyether polyol with (meth)acrylic acid. These prepolymers can be used alone or in combination of two or more. They may also be used in combination with the above-mentioned polyfunctional (meth)acrylic monomers.

[0029] Organic-inorganic hybrid resins are functional materials that contain both inorganic and organic components within the same molecule. They combine the excellent properties of inorganic components, such as hardness, heat resistance, and weather resistance, with the flexibility, light weight, and processability of organic components. Examples of organic-inorganic hybrid resins include compounds obtained by bonding organic compounds having polymerizable unsaturated groups, such as (meth)acryloyl, silanol, vinyl, or allyl groups, to inorganic particles such as silica via a silane coupling agent; silsesquioxane compounds obtained by hydrolysis and polycondensation of trifunctional silane compounds; and so on. Among these, compounds obtained by bonding organic compounds having polymerizable unsaturated groups to inorganic particles are preferred, with compounds obtained by bonding organic compounds having polymerizable unsaturated groups to silica inorganic particles being more preferred, and compounds obtained by bonding organic compounds having (meth)acryloyl groups to silica inorganic particles being even more preferred, from the perspective of achieving high hardness in the cured hard coat layer.

[0030] The inorganic fine particles contained in the organic-inorganic hybrid resin do not correspond to the filler described below, but function as a binder, improving the hardness of the formed hard coat layer and ensuring the transparency of the resulting hard coat layer. The average particle size of the inorganic fine particles is preferably 5 to 500 nm, more preferably 10 to 250 nm, particularly preferably 15 to 100 nm, and even more preferably 20 to 70 nm. This makes it easier to maintain the strength of the hard coat layer after curing. The average particle size of the inorganic fine particles is measured by dynamic light scattering.

[0031] The organic-inorganic hybrid resin is also preferably used in combination with other active energy ray-curable components such as the aforementioned polyfunctional (meth)acrylate monomers. When the organic-inorganic hybrid resin is used in combination with the aforementioned other active energy ray-curable components, the content of the organic-inorganic hybrid resin per 100 parts by mass of the active energy ray-curable components is preferably 10 to 200 parts by mass, more preferably 50 to 150 parts by mass, and particularly preferably 75 to 125 parts by mass. The organic-inorganic hybrid resin is also preferably in the form of an organosol (colloidal).

[0032] (2) (B) Component: Filler The composition for forming an HC layer according to the present invention preferably contains a filler as component (B) (in this specification, the "filler" may be referred to as "component (B)"). This allows the desired unevenness to be formed on the surface of the hard coat layer, and optical properties such as haze to be adjusted to desired values.

[0033] The filler is not particularly limited and examples thereof include inorganic fillers such as silica, calcium carbonate, aluminum hydroxide, magnesium hydroxide, clay, talc, and titanium dioxide; organic fillers such as acrylic resins, acrylic-styrene copolymers, melamine resins, polycarbonate resins, polyethylene resins, polystyrene resins, benzoguanamine resins, and epoxy resins; and organic-inorganic fillers made of silicon-containing compounds having an intermediate structure between inorganic and organic. These fillers may be used alone or in combination of two or more.

[0034] Among these, the filler used in the present invention is preferably an organic filler, and more preferably an organic filler made of an acrylic resin, from the viewpoint that it is likely to be unevenly distributed on the surface of the hard coat layer and to exhibit good optical properties.

[0035] The shape of the filler may be a regular shape such as a sphere, or an indefinite shape with no specific shape. From the viewpoint of more easily achieving the effects of the present invention, a regular shape is preferable, a spherical shape is more preferable, and a true sphere is even more preferable.

[0036] From the viewpoint of more easily achieving the effects of the present invention, the average particle size of the filler is preferably 0.1 to 10 μm, more preferably 0.4 to 7 μm, particularly preferably 0.8 to 4 μm, and even more preferably 1.2 to 2 μm. The average particle size of the filler can be measured using a laser diffraction / scattering particle size distribution analyzer.

[0037] The refractive index of the filler is preferably 1.2 to 1.7, more preferably 1.3 to 1.6, and particularly preferably 1.35 to 1.5, which makes it easier to obtain the desired optical properties.

[0038] The content of component (B) is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, even more preferably 0.1 to 3 parts by mass, and particularly preferably 0.3 to 1 part by mass, relative to 100 parts by mass of component (A), which makes it easier to achieve the effects of the present invention.

[0039] (3) (C) Component: Slip agent The composition for forming an HC layer according to the present invention preferably contains, as component (C), a slip agent having a weight-average molecular weight (Mw) of 10,000 or more, which allows the hard coat layer to exhibit excellent slip properties even after being washed with an alcohol such as ethanol.

[0040] Furthermore, the component (C) used in the present invention preferably has a photoreactive group, such as a group having a photopolymerizable unsaturated bond, such as a vinyl group, an allyl group, an acryloyl group, or a methacryloyl group.

[0041] Slip agents containing photoreactive groups produce a cured product through a crosslinking reaction upon irradiation with active energy rays. The photoreactive groups then become crosslinking points. The higher the weight-average molecular weight of component (C), the more reactive groups it contains. This increases the number of crosslinking sites between component (C) and component (A), resulting in more complex molecular entanglements. This makes the slip agent less likely to fall off the hard coat layer surface, and it is believed that the excellent slip properties are likely to be maintained even after the hard coat layer surface is washed with alcohol such as ethanol.

[0042] Examples of slip agents include silicone-based slip agents, fluorine-based slip agents, acrylic-based slip agents, vinyl-based slip agents, etc. Among these, silicone-based slip agents and fluorine-based slip agents are preferred, and fluorine-based slip agents are particularly preferred, from the viewpoints of imparting excellent slip properties and improving compatibility with other components used and scratch resistance.

[0043] Preferred examples of the silicone-based slip agent include a mixture of silicone urethane acrylate and urethane acrylate, polydimethylsiloxane, and modified polydimethylsiloxane.

[0044] Preferred examples of the fluorine-based slip agent include compounds having a perfluoroalkyl group or a fluorinated alkenyl group in the main chain or side chain. The slip agents can be used alone or in combination of two or more.

[0045] The weight-average molecular weight (Mw) of the slip agent is preferably 12,000 or more, and particularly preferably 14,000 or more, from the viewpoints of imparting excellent slip properties and improving compatibility with other components used and scratch resistance. There are no particular restrictions on the upper limit of the weight-average molecular weight (Mw) of component (C), but from the viewpoints of compatibility with other components and the hardness of the resulting hard coat layer, it is preferably 200,000 or less, more preferably 150,000 or less, particularly preferably 100,000 or less, and even more preferably 80,000 or less.

[0046] When the slip agent is a silicone-based slip agent, the weight average molecular weight (Mw) of the slip agent is preferably 17,000 to 60,000, particularly preferably 20,000 to 40,000, further preferably 24,000 to 35,000, and of these, preferably 28,000 to 32,000.

[0047] When the slip agent is a fluorine-based slip agent, the weight average molecular weight (Mw) of the slip agent is preferably 15,000 to 60,000, more preferably 25,000 to 50,000, particularly preferably 30,000 to 55,000, even more preferably 33,000 to 50,000, and of these, preferably 36,000 to 45,000.

[0048] The weight average molecular weight (Mw) of the slip agent can be determined, for example, as a value converted into standard polystyrene by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent.

[0049] The content of component (C) is preferably 0.01 to 20 parts by mass, more preferably 0.05 to 16 parts by mass, and even more preferably 0.1 to 12 parts by mass, relative to 100 parts by mass of component (A). When the slip agent is a silicone-based slip agent, the content is preferably 1 to 10 parts by mass, more preferably 2 to 8 parts by mass, particularly preferably 3 to 7 parts by mass, and even more preferably 4 to 6 parts by mass. When the slip agent is a fluorine-based slip agent, the content is preferably 0.2 to 8 parts by mass, more preferably 0.4 to 4 parts by mass, particularly preferably 0.5 to 2 parts by mass, and even more preferably 0.6 to 1 part by mass. This allows the effect of imparting and maintaining excellent slip properties to be fully obtained, and the scratch resistance of the formed hard coat layer to be further improved.

[0050] (4) Other ingredients The HC layer-forming composition according to the present invention may contain other components in addition to the components (A), (B), and (C). Preferred examples of the other components include a dispersant as component (D) and a photopolymerization initiator as component (E).

[0051] D) Ingredient: Dispersant The HC layer-forming composition according to the present invention preferably contains a dispersant as component (D) (sometimes referred to as "component (D)" in this specification). This makes it possible to adjust the optical properties within the desired ranges and also makes it easier to obtain suitable physical properties related to the hard coat layer surface.

[0052] Component (D) includes organic dispersants and inorganic dispersants.

[0053] The organic dispersant is preferably a compound having at least one polar group in the molecule. Here, the polar group refers to a polar functional group (or atomic group), such as a carboxyl group, a hydroxyl group, a sulfo group, a primary amino group, a secondary amino group, a tertiary amino group, an amide group, a quaternary ammonium base, a pyridinium base, a sulfonium base, and a phosphonium base. The use of an organic dispersant having such a polar group can more effectively control the degree of filler settling in the coating film of the HC layer-forming composition according to the present invention, thereby achieving the desired surface properties. This is because the organic dispersant having such a polar group can be more effectively coordinated to the surface of the inorganic component-containing filler.

[0054] The polar groups may be randomly arranged in the resin molecule, but are preferably arranged at the terminals of the molecule in a block structure or a graft structure, which enhances the adsorption performance to the filler.

[0055] The polar group of the organic dispersant may be introduced into one molecule or multiple polar groups. When multiple polar groups are present in the molecule, a basic skeleton is required to bond the organic compounds having the respective polar groups together. Such a basic skeleton is preferably composed of an ester chain, a vinyl chain, an acrylic chain, an ether chain, a urethane chain, or the like. Furthermore, some of the hydrogen atoms in these molecules may be substituted with halogen atoms.

[0056] Among these, preferred organic dispersants are olefin-based resins, acrylic-based resins, urethane-based resins, polyester-based resins, and alkyd-based resins. Olefin-based resins, acrylic-based resins, urethane-based resins, and polyester-based resins are particularly preferred because they allow optical properties such as the rate of change in haze value to be adjusted to the desired range and provide a surface roughness suitable for high-definition displays. The molecular weight of the organic dispersant is not particularly limited and can be selected from a wide range of molecular weights from 100 to 900,000. The organic dispersants can be used singly or in combination of two or more.

[0057] Specific examples of organic dispersants include formalin condensates of naphthalenesulfonates [alkali metal (Li, Na, K, etc.) salts, ammonium salts, etc.], polystyrenesulfonates (same as above), polyacrylates (same as above), poly(2-4)carboxylic acid (maleic acid / glycerin / monoallyl ether copolymer, etc.) salts (same as above), partial esters of α-olefin / maleic anhydride copolymers, carboxymethyl cellulose and polyvinyl alcohol, polyoxyalkylenes, polyhydric alcohols, carboxylates, sulfates, sulfonates, phosphates, primary to tertiary amine salts, and quaternary ammonium salts.

[0058] Examples of inorganic dispersants include alkali metal (as above) salts of polyphosphates and phosphate-based dispersants (phosphoric acid, monoalkyl (C8-20) phosphate esters, dialkyl phosphate esters, etc.).

[0059] The blending amount of component (D) is preferably more than 0 part by mass and not more than 2 parts by mass, more preferably 0.01 to 1.5 parts by mass, even more preferably 0.1 to 1 part by mass, and particularly preferably 0.2 to 0.5 parts by mass, per 100 parts by mass of component (A). This allows the optical properties to be adjusted within the desired range, and also provides more suitable surface characteristics.

[0060] Component (E): Photopolymerization initiator By using a photopolymerization initiator, the amount of light irradiation can be reduced and the polymerization and curing time can be shortened when forming a hard coat layer. In particular, when crosslinking is carried out by irradiation with active light such as ultraviolet light as the active energy ray, the presence of a photopolymerization initiator is preferred.

[0061] The photopolymerization initiator is not particularly limited, and conventionally known ones can be used. For example, photoradical polymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, benzophenone, p-phenylbenzophenone, 2-methylanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, benzyl dimethyl ketal, p-dimethylaminobenzoic acid ester, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one; triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrakis(pentafluorophenyl)borate, 4,4'-bis[diphenylsulfonio]diphenylsulfide-bishexafluorophosphate, 4,4'-Bis[di(β-hydroxyethoxy)phenylsulfonio]diphenylsulfide-bishexafluoroantimonate, 7-[di(p-toluyl)sulfonio]-2-isopropylthioxanthone hexafluorophosphate, 7-[di(p-toluyl)sulfonio]-2-isopropylthioxanthone hexafluoroantimonate, 7-[di(p-toluyl)sulfonio]-2-isopropyltetrakis(pentafluorophenyl)borate, phenylcarbonyl-4'-diphenylsulfonio-diphenylsulfide-hexafluorophosphate, phenylcarbonyl-4'-diphenylsulfonio-diphenylsulfide-hexafluoroantimonate, 4-tert-butylphenylcarbonyl-4'-diphenylsulfonio-diphenylsulfide-hexafluoro 4-tert-butylphenylcarbonyl-4'-diphenylsulfonio-diphenylsulfide-hexafluoroantimonate, 4-tert-butylphenylcarbonyl-4'-diphenylsulfonio-diphenylsulfide-tetrakis(pentafluorophenyl)borate, thiophenyldiphenylsulfonium hexafluoroantimonate, thiophenyldiphenylsulfonium hexafluorophosphate, 4-{4-(2-chlorobenzoyl)phenylthio}phenylbis(4-fluorophenyl)sulfonium hexafluoroantimonate, thiophenyldiphenylsulfonium hexafluoroantimonate halide, 4,4',4''-tri(β-hydroxyethoxyphenyl)sulfonium hexafluoroantimonate, 4,Sulfonium salt compounds such as 4'-bis[diphenylsulfonio]diphenylsulfide-bishexafluoroantimonate, diphenyl[4-(phenylthio)phenyl]sulfonium trifluorotrispentafluoroethylphosphate, tris[4-(4-acetylphenylsulfanyl)phenyl]sulfonium tris[(trifluoromethyl)sulfonyl]methanide; diphenyliodonium tetrakis(pentafluorophenyl)borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonide Examples of photo-polymerization initiators include iodonium salt compounds such as iodonium tetrakis(pentafluorophenyl)borate, di(4-nonylphenyl)iodonium hexafluorophosphate, and (tricumyl)iodonium tetrakis(pentafluorophenyl)borate; phosphonium salt compounds such as tri-n-butyl(2,5-dihydroxyphenyl)phosphonium bromide and hexadecyltributylphosphonium chloride; and ammonium salt compounds such as benzyltrimethylammonium chloride, phenyltributylammonium chloride, and benzyltrimethylammonium bromide. These photo-polymerization initiators can be used alone or in combination of two or more.

[0062] When a photopolymerization initiator is used, the blending ratio thereof is preferably 0.1 to 20 parts by mass, more preferably 0.2 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, per 100 parts by mass of component (A), which makes it easier for the hard coat layer to exhibit the desired abrasion resistance and hardness.

[0063] (F) Other additives The coating layer-forming composition according to the present invention may further contain other additives such as antioxidants, ultraviolet absorbers, silane coupling agents, light stabilizers, antifoaming agents, infrared absorbers, oxygen absorbers, refractive index adjusters, plasticizers, antistatic agents, and colorants, as long as they do not affect the effects of the present invention.

[0064] (4) Formation of hard coat layer The HC layer according to the present invention is preferably formed by applying the composition for forming an HC layer according to the present invention to the surface of the substrate layer or another layer laminated on the substrate layer, and irradiating the resulting coating film with active energy rays to cure the coating film.

[0065] The composition for forming a hard coat layer according to the present invention is preferably prepared by adding the above-described essential components (A) to (C) and, if desired, other components to an appropriate solvent and dissolving or dispersing these components.

[0066] Examples of the solvent to be used include aliphatic hydrocarbons such as hexane and heptane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as methylene chloride and ethylene chloride; alcohols such as methanol, ethanol, 2-propanol, n-butanol, isobutyl alcohol (IBA), and n-octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-pentanone, diisobutyl ketone, cyclohexanone, isophorone, and cyclohexanone; ethyl acetate, butyl acetate, ethyl lactate, and γ-butyrolactone. cellosolves such as methyl cellosolve, ethyl cellosolve, ethylene glycol mono-n-butyl ether, ethylene glycol mono-t-butyl ether, and propylene glycol monomethyl ether (PGM); glycol ethers such as 3-methoxy-3-methylbutanol, 3-methoxy-3-methylbutyl acetate, diethylene glycol monobutyl ether, and 1-ethoxy-2-propanol; amides such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; etc. These solvents can be used alone or in combination of two or more.

[0067] The amount of solvent used can be determined appropriately so that the composition for forming a hard coat layer according to the present invention has a state (concentration, viscosity) suitable for forming a coating film. When a solvent is used, the amount used is preferably 10 to 500 parts by mass, more preferably 30 to 300 parts by mass, and even more preferably 50 to 200 parts by mass, per 100 parts by mass of component (A).

[0068] There are no particular limitations on the method for applying the HC layer-forming composition according to the present invention to the surface of the substrate layer or another layer laminated on the substrate layer, and any conventionally known method can be used, such as bar coating, knife coating, roll coating, blade coating, die coating, curtain coating, gravure coating, etc. The coating film is preferably dried at 40 to 120°C for about 30 seconds to 5 minutes.

[0069] The coating film is then cured by irradiating it with active energy rays, thereby forming a hard coat layer. Examples of active energy rays used to cure the coating film include ultraviolet rays; electron beams; laser light such as semiconductor lasers, argon lasers, and He-Cd lasers; and ionizing radiation such as α-rays, β-rays, γ-rays, neutron beams, X-rays, and accelerated electron beams. Among these, ultraviolet rays and electron beams are preferred as active energy rays, as they can be generated using a relatively simple device, and ultraviolet rays are more preferred.

[0070] When ultraviolet rays are used as the active energy rays, the ultraviolet light source may be an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a black light lamp, a metal halide lamp, or the like.

[0071] The UV light intensity is 50 to 1,000 mJ / cm 2 is preferably 100 to 700 mJ / cm 2 The irradiance of the ultraviolet light is usually 100 to 1000 mW / cm. 2 It is preferable that the intensity is 200 to 700 mW / cm 2The irradiation time is usually from 1 second to 1 hour, and the irradiation temperature is usually from 20 to 100°C.

[0072] The electron beam irradiation can be carried out using an electron beam accelerator, etc. The irradiation dose of the electron beam is preferably 10 to 1000 krad.

[0073] The irradiation with active energy rays can be carried out in an air atmosphere or an inert gas atmosphere, such as nitrogen, argon, or helium.

[0074] The thickness of the obtained hard coat layer is preferably 0.1 to 30 μm, more preferably 0.2 to 20 μm, particularly preferably 0.5 to 10 μm, even more preferably 1 to 7 μm, and most preferably 2 to 5 μm. This makes it easier to form a hard coat layer with the desired surface properties, and the obtained hard coat layer more easily exhibits the effects of the present invention. Note that if the thickness of the hard coat layer is less than 0.1 μm, it may be difficult to obtain the hardness required for practical use.

[0075] (5) Other layers The hard-coated film of the present invention may be provided with other layers, such as a hard-coat layer, an optical adjustment layer, a primer layer, or a pressure-sensitive adhesive layer, depending on the purpose. Among these, the hard-coat layer is preferred as the other layer, and in the hard-coated film of the present invention, it is preferably provided on the side of the substrate layer opposite to the side having the hard-coat layer. The hard-coat layer is preferably provided on the outermost surface of the touch panel, i.e., the surface that comes into direct contact with fingers, a touch pen, or the like. This improves the durability of the touch panel provided with the hard-coated film of the present invention.

[0076] In the hard coat film of the present invention, a primer layer may be provided between the substrate layer and the hard coat layer. This serves to enhance the adhesion between the substrate layer and the hard coat layer. The primer layer is formed, for example, by applying a reactive coating liquid containing a polyester polyol or polyether polyol and a polyisocyanate to the surface of the substrate layer in an amount of 0.5 to 2 g / m. 2 It can be formed by coating.

[0077] In the hard-coated film of the present invention, the pressure-sensitive adhesive layer may be provided on the surface of the substrate layer opposite to the surface having the hard-coated layer. This allows for good adhesion to other substrates (for example, transparent conductive films such as ITO films, front panels of displays, etc.). The pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is not particularly limited, and known pressure-sensitive adhesives having a predetermined transparency, such as acrylic pressure-sensitive adhesives, rubber pressure-sensitive adhesives, silicone pressure-sensitive adhesives, and urethane pressure-sensitive adhesives, may be used. When the hard-coated film of the present invention comprises a pressure-sensitive adhesive layer, a release film may be laminated on the surface of the pressure-sensitive adhesive layer. The release film serves to protect the surface of the pressure-sensitive adhesive layer and is peeled and removed during use. The release film is not particularly limited as long as its release surface (the surface in contact with the pressure-sensitive adhesive layer) has the desired releasability, and known release films may be used.

[0078] (6) Surface protection sheet The hard coat film of the present invention may have a surface protective sheet on the hard coat layer for the purpose of protecting the surface of the hard coat layer until use. The surface protective sheet is peeled off and removed when used. As the surface protective sheet, it is preferable to use a conventionally known resin film.

[0079] (7) Layer composition Examples of the layer structure of the hard coat film of the present invention include, but are not limited to, the following: In the following, the following symbols are used: BL: Base material layer Coat: Hard coat layer PL: Primer layer HC: Hard coat layer RF: Release film AL: Adhesive layer SP: Surface protection sheet

[0080] BL / Coat, BL / Coat / SP, HC / BL / Coat, HC / BL / Coat / SP, BL / PL / Coat, BL / PL / Coat / SP, HC / BL / PL / Coat, HC / BL / PL / Coat / SP, RF / AL / BL / Coat, RF / AL / BL / Coat / SP, RF / AL / BL / PL / Coat, RF / AL / BL / PL / Coat / SP

[0081] 3. Characteristics of hard coat film (1) Water contact angle (i) In the HC layer according to the present invention, the change in water contact angle on the surface of the hard coat layer before and after the alcohol wiping test described below is preferably -10° or more, more preferably -8.5° or more, even more preferably -6° or more, particularly preferably -4.5° or more, and particularly preferably -3° or more, and most preferably -1° or more. The upper limit of the change in water contact angle is usually preferably 0° or less, more preferably 0.01° or less, and preferably 0.1° or less. The HC layer surface according to the present invention exhibits a small change in water contact angle Δ, even after cleaning with an alcohol such as ethanol, and maintains excellent slip properties on the layer surface. Here, the change in water contact angle is a value calculated from the following formula:

[0082]

number

[0083] The alcohol wipe test is carried out as follows. [Alcohol wipe test] A Kimtowel soaked in alcohol was wiped at 0.4kgf / cm 2 The surface of the hard coat layer of the hard coat film is reciprocated 50 times under a load of 1000 kJ / min. The water contact angle of the hard coat layer surface can be measured by the method described in the examples.

[0084] The water contact angle of the hard coat layer surface before an alcohol wipe test using ethanol as the alcohol (hereinafter sometimes referred to as an "ethanol wipe test") is preferably 80° to 150°, more preferably 90° to 140°, particularly preferably 95° to 130°, still more preferably 100° to 120°, and of these, preferably 105° to 115°, most preferably 107° to 110°. This makes it easy to exhibit good slip properties before the ethanol wipe test, and also makes it easy to adjust the water contact angle to one that easily exhibits good slip properties even after the ethanol wipe test.

[0085] The water contact angle of the hard coat layer surface after the alcohol wiping test is preferably 80° to 150°, more preferably 88° to 140°, particularly preferably 92° to 130°, even more preferably 96° to 120°, and of these, preferably 100° to 115°, most preferably 105° to 110°. This makes it easy to exhibit good slip properties even after the alcohol wiping test, and to easily satisfy the difference in water contact angle before and after washing.

[0086] (2) Total light transmittance The total light transmittance of the hard coat film of the present invention is preferably 80% or more, more preferably 85% or more, and even more preferably 90% or more. The upper limit of the total light transmittance is usually preferably 100% or less. This ensures that the image displayed on the resulting display has excellent visibility. The total light transmittance can be measured using a haze meter in accordance with JIS K 7361-1:1997.

[0087] (3) Haze value The haze value of the hard coat layer surface of the hard coat film of the present invention is preferably 10% or less, more preferably 7% or less, even more preferably 4% or less, and particularly preferably 3% or less. The lower limit of the haze value is usually preferably 0% or more. This ensures excellent visibility of the displayed image on the resulting display. The haze value can be measured using a haze meter in accordance with JIS K 7136:2000.

[0088] (4) Transparency The transmission clarity of the hard coat film of the present invention is preferably 460 or more, more preferably 465 or more, particularly preferably 470 or more, and even more preferably 475 or more. The upper limit of the transmission clarity is not particularly limited, but is usually preferably 500 or less. This makes it easier to obtain good display image quality (visibility). The transmission clarity can be determined in accordance with JIS K 7374 by using an image clarity tester in transmission mode, irradiating light from the hard coat layer side, and calculating the total image clarity value of five combs (comb widths: 0.125 mm, 0.25 mm, 0.5 mm, 1.0 mm, 2.0 mm).

[0089] (5) Pencil hardness In the hard-coated film of the present invention, the pencil hardness of the hard-coat layer surface is preferably B or higher, more preferably HB or higher, particularly preferably F or higher, even more preferably H or higher, and especially preferably 2H or higher. The upper limit of the pencil hardness is not particularly limited, but from the viewpoint of optimizing the touch feeling and smoothness of the touch panel, it is usually preferably 9H or lower, more preferably 7H or lower, particularly preferably 5H or lower, and particularly preferably 4H or lower. This makes it easier to obtain a display with excellent scratch resistance and high appearance quality. The pencil hardness can be measured in accordance with JIS K 5600 by the method described in the Examples.

[0090] (8) Scratch resistance In the hard coat film of the present invention, the surface of the hard coat layer has hard coat properties in terms of excellent scratch resistance. This makes it easier to maintain the appearance quality of the display when used in a display, and also makes it easier to provide a good touch feeling and smoothness of the touch panel. Excellent scratch resistance can be confirmed by the absence of any change in appearance in a scratch resistance test using steel wool. Specifically, the surface of the hard coat layer is subjected to a scratch test using #0000 steel wool at 250 g / cm in accordance with JIS K5600-5-10. 2 The scratch resistance can be confirmed by the number of scratches that appear on the surface after rubbing 10 times back and forth over a distance of 10 cm under a load of 1000 psi. In the scratch resistance test, the number of scratches that appear on the surface of the hard coat layer is preferably 10 or less, more preferably 3 or less, and particularly preferably 0.

[0091] 4. Use of hard-coated film As described above, the hard coat film of the present invention can suppress a decrease in the slipperiness of the hard coat layer surface even when washed with alcohol such as ethanol. Therefore, the hard coat film is suitable for use in various optical displays such as liquid crystal displays, organic electroluminescence (EL) displays, and LED displays (including mini LEDs and micro LEDs), particularly touch panels (displays).

[0092] 2) Optical Display The optical display of the present invention comprises the hard coat film of the present invention. For example, the hard coat film of the present invention is preferably laminated on a transparent conductive film [ITO (indium tin oxide) film] of a resistive touch panel component. A cross-sectional view of an example of a touch panel (a part of a touch panel) using the hard coat film of the present invention is shown in FIG. 1. In FIG. 1, 10 denotes the hard coat film of the present invention, 10a denotes a hard coat layer, 10b denotes a substrate layer, 11a and 11b denote ITO films, 12 denotes dot spacers, 13 denotes a transparent substrate, and 14 denotes a liquid crystal display (LCD). The arrow indicates the direction of pressure applied to the touch panel surface with a finger, pen, or the like. A hard coat layer is preferably laminated on the surface of the hard coat film 10 of the present invention (the surface that is pressed with a finger, pen, or the like). By laminating the hard coat film of the present invention in this manner, the resulting touch panel can be cleaned with alcohol such as ethanol to maintain excellent image quality even if it becomes soiled with fingerprints or other contaminants, and the deterioration of slipperiness due to cleaning is suppressed, so that the comfortable operability of the touch panel can be maintained for a long time.

[0093] The above-described embodiments have been described to facilitate understanding of the present invention, and are not intended to limit the present invention. Therefore, each element disclosed in the above embodiments is intended to include all design modifications and equivalents that fall within the technical scope of the present invention.

[0094] In this specification, when it is written "α to β" (α and β are any numerical values), it means "not less than α and not more than β" unless otherwise specified, and also includes the meaning "preferably greater than α" or "preferably smaller than β." Furthermore, when it is written "not less than α" (α is any numerical value), it also includes the meaning "preferably greater than α" unless otherwise specified, and when it is written "not more than β" (β is any numerical value), it also includes the meaning "preferably smaller than β" unless otherwise specified. [Example]

[0095] The present invention will be explained in more detail below with reference to examples, but the scope of the present invention is not limited to these examples.

[0096] (Materials used) The following materials were used: [Component (A): Main ingredient] (A1): Organic-inorganic hybrid resin [product name: Opstar Z7530, manufactured by Arakawa Chemical Industries, Ltd., active energy ray curable, contains photopolymerization initiator] [Component (B): Filler] (B1): Organic fine particles [product name: SSX-101, manufactured by Sekisui Chemical Co., Ltd., material: cross-linked polymethyl methacrylate, particle shape: spherical, average particle size 1.5 μm, refractive index: 1.49] [Component (C): Slip agent] (C1): Silicone-based slip agent (weight average molecular weight (Mw) = 29,000, manufactured by Shin-Etsu Silicones Co., Ltd., having a photoreactive group) (C2): Fluorine-based slip agent (weight average molecular weight (Mw) = 15,000, manufactured by DIC Corporation, having a photoreactive group) (C3): Fluorine-based slip agent (weight average molecular weight (Mw) = 36,000, manufactured by Fluoro Technology, Inc., having a photoreactive group) (C4): Silicone slip agent (weight average molecular weight (Mw) = 21,000, manufactured by Mitsubishi Chemical Corporation, having a photoreactive group) [Component (D): Dispersant] (D1): Partial hydrolysis product of α-olefin-maleic anhydride copolymer (trade name: FLOLENE G-700, manufactured by Kyoeisha Chemical Co., Ltd.) [Component (E): Photoacid Generator] (E1): Photoacid generator (product name: CAT-7605, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0097] Example 1 A composition for forming a hard coat layer was prepared by uniformly mixing 100 parts by mass of the (A1) component (solid content equivalent; the same applies below), 0.5 parts by mass of the (B1) component, 4 parts by mass of the (C1) component, 0.3 parts by mass of the (D1) component, and 0.03 parts by mass of the (E1) component using a solvent.

[0098] The composition for forming a hard coat layer was applied with a Mayer bar onto a PET film (trade name: Lumirror PET125U403, thickness: 125 μm, manufactured by Toray Industries, Inc.) as a substrate layer to form a coating film. The coating film was then placed in an oven maintained at 70°C for 1 minute to dry. Next, under a nitrogen atmosphere, an ultraviolet irradiation device (Eigrantage ECS-401GX, manufactured by Eye Graphics Co., Ltd.) was used, and a high-pressure mercury lamp was used as a light source, with an illuminance of 200 mW / cm. 2 , Light intensity: 250mJ / cm 2 The coating film was cured by ultraviolet irradiation under the irradiation conditions above, to prepare a hard coat film (Hard Coat Film 1) having a hard coat layer with a thickness of 1.5 μm.

[0099] (Examples 2 and 3, Comparative Examples 1 and 2) Hard coat films of Examples 2 and 3 and Comparative Examples 1 and 2 were produced in the same manner as in Example 1, except that the types and blending amounts of the (A1), (B1), (C), and (D) photopolymerization initiators in Example 1 were changed to those shown in Table 1 below.

[0100] [Table 1]

[0101] The following tests were carried out on the obtained hard-coated film. In Table 2, "before washing" means "before the ethanol wiping test" and "after washing" means "after the ethanol wiping test." Furthermore, "change (after - before)" represents the difference between the value after the ethanol wiping test and the value before the ethanol wiping test.

[0102] [Total light transmittance] For the hard coat films produced in Examples 1 to 3 and Comparative Examples 1 and 2, the total light transmittance (%) was measured in accordance with JIS K 7361-1:1997 using a haze meter ("NDH-5000", manufactured by Nippon Denshoku Industries Co., Ltd.) by irradiating the film with light from the hard coat layer side after blank correction. The results are shown in Table 2.

[0103] [Haze value] The haze values ​​(%) of the hard coat films produced in Examples 1 to 3 and Comparative Examples 1 and 2 were measured in accordance with JIS K 7136:2000 using a haze meter ("NDH-5000", manufactured by Nippon Denshoku Industries Co., Ltd.) by irradiating the film with light from the hard coat layer side after blank correction. The results are shown in Table 2.

[0104] [Pencil hardness] The pencil hardness of the hard coat layer surface of the hard coat films produced in Examples 1 to 3 and Comparative Examples 1 and 2 was measured in accordance with JIS K 5600. Specifically, pencils with different lead hardnesses ("Mitsubishi Pencil UNI," manufactured by Mitsubishi Pencil Co., Ltd.) were moved 7 mm at a 45° angle under a 750 g load, and the degree of scratching on the hard coat layer surface was visually observed. This was repeated five times, and the hardness of the hardest pencil lead that did not scratch the hard coat layer surface four or more times was recorded as the pencil hardness. The results are shown in Table 2.

[0105] [Scratch resistance] The hard coat films produced in Examples 1 to 3 and Comparative Examples 1 and 2 were evaluated for scratch resistance on the hard coat layer surface. That is, the hard coat layer surface was subjected to abrasion resistance of 250 g / cm using #0000 steel wool in accordance with JIS K5600-5-10. 2 The hard coat layer was rubbed back and forth 10 times at a load of 0.05g over a sliding distance of 10cm. The hard coat layer surface was then visually inspected under a three-band fluorescent lamp for scratches and evaluated according to the following criteria. The results are shown in Table 2. ◎: 0 scratches confirmed ○: 1 to 3 scratches confirmed △: 4 to 10 scratches confirmed ×: 11 or more scratches confirmed

[0106] [Transmission clarity] For the hard-coated films produced in Examples 1 to 3 and Comparative Examples 1 and 2, light was irradiated from the hard-coat layer side in transmission mode using an image clarity tester ("ICM-1T", manufactured by Suga Test Instruments Co., Ltd.) in accordance with JIS K 7374, and the total image clarity value for five combs (comb widths: 0.125 mm, 0.25 mm, 0.5 mm, 1.0 mm, 2.0 mm) was calculated, and this calculated value was taken as the transmission clarity. The results are shown in Table 2.

[0107] [XPS element concentration] The amounts (XPS counts) of carbon atoms (C), nitrogen atoms (N), oxygen atoms (O), silicon atoms (Si), and fluorine atoms (F) on the surface of the hard coat layer in the hard coat films produced in Examples 1 to 3 and Comparative Example 2 were measured by X-ray photoelectron spectroscopy (XPS) under the following conditions. [XPS conditions] Measurement equipment: ULVAC, product name "PHI Quantera SXM" X-ray: AlKα (1486.6eV) Measurement elements: carbon (C), nitrogen (N), oxygen (O), silicon (Si), fluorine (F)

[0108] Then, for Example 1 and Comparative Example 2, the silicon atomic ratio (atomic %) was calculated according to the following formula (1), and this was taken as the initial silicon atomic ratio (atomic %) (before wiping with ethanol). Formula (1): Silicon atom ratio (atomic %) = {Si element amount / (C element amount + N element amount + O element amount + Si element amount + F element amount)} × 100

[0109] For Examples 2 and 3, the fluorine atom ratio (atomic %) was calculated according to the following formula (2), and this was taken as the initial fluorine atom ratio (atomic %) (before wiping with ethanol). The results are shown in Table 2. Equation (2): Fluorine atom ratio (atomic %) = {F element amount / (C element amount + N element amount + O element amount + Si element amount + F element amount)} × 100

[0110] Next, the surfaces of the hard coat layers of the hard coat films produced in Examples 1 to 3 and Comparative Examples 1 and 2 were coated with a Kimtowel sufficiently saturated with ethanol at a pressure of 0.4 kgf / cm. 2 The hard coat layer surface was wiped back and forth 50 times while applying a load of 1000 kJ / min. The amounts of carbon atoms (C), nitrogen atoms (N), oxygen atoms (O), silicon atoms (Si), and fluorine atoms (F) (XPS count numbers) were then measured for the surface of the hard coat layer under the same conditions as those for the X-ray photoelectron spectroscopy (XPS) described above.

[0111] For Example 1 and Comparative Example 2, the silicon atomic ratio (atomic %) was calculated according to the above formula (1), and this was designated as the silicon atomic ratio (atomic %) after wiping with ethanol. Furthermore, the "change (after - before)" was calculated by subtracting the initial (before wiping with ethanol) silicon atomic ratio (atomic %) from the silicon atomic ratio (atomic %) after wiping with ethanol. The results are shown in Table 2. The smaller the "change (after - before)" calculated from the silicon atomic ratio (atomic %) before and after wiping with ethanol, the smaller the change in silicon atoms on the hard coat layer surface before and after wiping with ethanol. This serves as an indicator for estimating the resistance of the silicone-based slip agent to removal by wiping with ethanol. The "change (after - before)" value is preferably -10 or greater, more preferably -7 or greater, particularly preferably -5 or greater, and even more preferably -2 or greater. The upper limit of the "change (after - before)" value is preferably 0% or less.

[0112] For Examples 2 and 3, the fluorine atomic ratio (atomic %) was calculated according to the above formula (2), and this was designated as the fluorine atomic ratio (atomic %) after wiping with ethanol. Furthermore, the "change (after - before)" was calculated by subtracting the initial fluorine atomic ratio (atomic %) (before wiping with ethanol) from the fluorine atomic ratio (atomic %) after wiping with ethanol. The results are shown in Table 2. The smaller the "change (after - before)" value calculated from the fluorine atomic ratio (atomic %) before and after wiping with ethanol, the smaller the change in fluorine atoms on the hard coat layer surface before and after wiping with ethanol. This serves as an indicator for estimating the resistance of the fluorine-based slip agent to removal by wiping with ethanol in the present invention. The "change (after - before)" value is preferably -10 or greater, more preferably -6 or greater, particularly preferably -3 or greater, and even more preferably -1 or greater. The upper limit of the "change (after - before)" value is preferably 0% or less.

[0113] [Water contact angle] A glass plate was attached to the substrate layer side surface of the hard-coated films produced in Examples 1 to 3 and Comparative Examples 1 and 2, and then the hard-coated film with the glass plate attached was placed on the test stand of a contact angle meter (DH350 test stand, manufactured by Kyowa Corporation) with the glass plate side facing down. Next, 2 μL of water was dropped onto the hard-coat layer surface of the hard-coated film with the glass plate attached, and the contact angle (°) immediately after the drop was measured with the contact angle meter, and this was taken as the initial water contact angle (°) (before wiping with ethanol). The results are shown in Table 2.

[0114] Next, the surfaces of the hard coat layers of the hard coat films produced in Examples 1 to 3 and Comparative Examples 1 and 2 were coated with a Kimtowel sufficiently saturated with ethanol at a pressure of 0.4 kgf / cm. 2 The hard coat layer surface was wiped back and forth 50 times while applying a load of 1000 kJ / min. The water contact angle was then measured under the same measurement conditions as above, and this was taken as the value of the water contact angle after wiping with ethanol. The "change (after - before)" was calculated by subtracting the initial water contact angle (before wiping with ethanol) from the water contact angle after wiping with ethanol. The results are shown in Table 2.

[0115] [Sensory evaluation of slipperiness] The initial slipperiness (before wiping with ethanol) of the hard coat layer surfaces of the hard coat films produced in Examples 1 to 3 and Comparative Examples 1 and 2 was evaluated by sliding a finger over them according to the following criteria. The results are shown in Table 2. ◎...My fingers were very slippery. 〇...My finger slipped. △...It was difficult for my fingers to slide. ×...My fingers didn't slip.

[0116] Next, the surfaces of the hard coat layers of the hard coat films produced in Examples 1 to 3 and Comparative Examples 1 and 2 were coated with a Kimtowel sufficiently saturated with ethanol at a pressure of 0.4 kgf / cm. 2 The surface of the hard coat layer was wiped back and forth 50 times while applying a load of 1000 kJ / min. The surface was then evaluated for slipperiness in the same manner as above, and this was taken as the slipperiness after wiping with ethanol. The results are shown in Table 2.

[0117] [Table 2]

[0118] As can be seen from Table 2, the hard coat film of the present invention had excellent slipperiness even after wiping with ethanol. [Explanation of symbols]

[0119] 10. Hard coated film 10a: Hard coat layer 10b...Base material layer 11a, 11b...ITO film 12 dot spacer 13. Transparent substrate 14 LCD

Claims

1. A hard coat film having a substrate layer and a hard coat layer, the hard coat layer is a layer containing (A) a component: an active energy ray-curable resin, and (C) a component: a slip agent having a weight average molecular weight (Mw) of 10,000 or more, A Kimtowel sufficiently soaked in alcohol was applied to the surface of the hard coat layer at a pressure of 0.4 kgf / cm ２ the water contact angle of the surface of the hard coat layer after an alcohol wiping test in which the hard coat layer is wiped back and forth 50 times while applying a load of 1000 kJ / cm2 or more is 92° or more. Hard coat film.

2. 2. The hard coat film according to claim 1, wherein the hard coat layer further contains component (B): a filler.

3. 3. The hard coat film according to claim 1, wherein a difference between the water contact angle (°) of the surface of the hard coat layer after the alcohol wiping test and the water contact angle (°) of the surface of the hard coat layer before the alcohol wiping test is −10° or more.

4. 3. The hard coat film according to claim 1, wherein the water contact angle of the surface of the hard coat layer before the alcohol wiping test is 92° or more.

5. 3. The hard coat film according to claim 1, wherein the component (C): slip agent is at least one selected from the group consisting of silicone-based slip agents and fluorine-based slip agents.

6. 3. The hard coat film according to claim 1, wherein the hard coat layer has a thickness of 0.1 to 30 μm.

7. 3. The hard coat film according to claim 1, wherein the alcohol is ethanol.

8. An optical display comprising the hard coat film according to claim 1 or 2.

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