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WO2014084008A1 - Film de revêtement dur et film conducteur transparent - Google Patents

Film de revêtement dur et film conducteur transparent Download PDF

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Publication number
WO2014084008A1
WO2014084008A1 PCT/JP2013/079968 JP2013079968W WO2014084008A1 WO 2014084008 A1 WO2014084008 A1 WO 2014084008A1 JP 2013079968 W JP2013079968 W JP 2013079968W WO 2014084008 A1 WO2014084008 A1 WO 2014084008A1
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WO
WIPO (PCT)
Prior art keywords
hard coat
coat layer
layer
particles
mass
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2013/079968
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English (en)
Japanese (ja)
Inventor
豊島裕
前田清成
土本達郎
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toray Advanced Film Co Ltd
Original Assignee
Toray Advanced Film Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toray Advanced Film Co Ltd filed Critical Toray Advanced Film Co Ltd
Priority to JP2013555666A priority Critical patent/JP5528645B1/ja
Priority to CN201380061679.9A priority patent/CN104822522B/zh
Priority to KR1020157010588A priority patent/KR101563564B1/ko
Publication of WO2014084008A1 publication Critical patent/WO2014084008A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/102—Oxide or hydroxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers

Definitions

  • the present invention relates to a hard coat film having high transparency and good slipperiness and blocking resistance, and more particularly to a hard coat film suitable for a transparent conductive film.
  • a hard coat film in which a hard coat layer is laminated on a base film is used as a surface film for a display or a touch panel, or as a base film for an electrode film for a touch panel (transparent conductive film for a touch panel).
  • the hard coat film used for these uses is required to have high transparency and good slipping and blocking resistance.
  • Patent Documents 1 and 2 It has been proposed to provide protrusions on the surface in order to improve the slipperiness and blocking resistance of the hard coat film or polyester film.
  • JP-A-7-314628 Japanese Patent Laid-Open No. 2000-211082
  • an object of the present invention is to provide a hard coat film having high transparency and good slipping and blocking resistance in view of the above-mentioned problems of the prior art.
  • Another object of the present invention is to provide a hard coat film suitable for a transparent conductive film.
  • a first hard coat layer containing particles is provided on at least one surface of the base film, and protrusions made of the particles are present on the surface of the first hard coat layer at a density of 300 to 4000 per 100 ⁇ m 2.
  • a resin layer is provided between the base film and the first hard coat layer, and the resin layer has a thickness of 0.005 to 0.3 ⁇ m and an average particle diameter of 1.
  • the hard coat film according to any one of 1) to 6), which contains particles that are three times or more.
  • the base film is a polyethylene terephthalate film, and has a resin layer having a refractive index of 1.55 to 1.61 between the base film and the first hard coat layer. Hard coat film according to crab.
  • Q represents an alkoxy group having 1 to 5 carbon atoms or a halogen atom.
  • II Treatment with a compound represented by the following general formula (2), and further surface treatment with a fluorine compound represented by the following general formula (3).
  • General formula (2) DR 7 -Rf 2 ...
  • B and D each independently represent a reactive site, and R 4 and R 7 are each independently derived from an alkylene group having 1 to 3 carbon atoms, or the alkylene group.
  • R 5 and R 6 each independently represent hydrogen or an alkyl group having 1 to 4 carbon atoms
  • Rf 2 represents a fluoroalkyl group
  • n represents an integer of 0 to 2.
  • the hydrophobic compound used in the hydrophobization treatment for obtaining inorganic particles having the surface of the particles hydrophobized is a fluorine compound having a fluoroalkyl group having 4 or more carbon atoms and a reactive site, carbon number 8 11)
  • Hard coat film is a fluorine compound having a fluoroalkyl group having 4 or more carbon atoms and a reactive site, carbon number 8 11
  • a second hard coat layer is provided on the surface of the base film opposite to the surface on which the first hard coat layer is provided, and the surface of the second hard coat layer is substantially free of protrusions made of particles.
  • the hard coat film according to any one of 1) to 14), wherein the center line average roughness (Ra2) of the surface of the second hard coat layer is 25 nm or less.
  • a transparent conductive film comprising a transparent conductive film on at least one surface of the hard coat film according to any one of 1) to 15) above.
  • the hard coat film of the present invention is suitable for a base film of a transparent conductive film.
  • FIG. 1 is an example of an observation view of the surface of the first hard coat layer observed with a scanning electron microscope.
  • FIG. 2 is a diagram schematically showing the planar shape of the protrusions on the surface of the first hard coat layer.
  • FIG. 3 is a schematic view schematically showing the surface of the first hard coat layer in FIG.
  • FIG. 4 is a schematic diagram in which a part of FIG. 3 is omitted.
  • the hard coat film which concerns on one embodiment of this invention has a 1st hard coat layer in the at least one surface of a base film.
  • the first hard coat layer contains particles, protrusions due to particles on the surface of the first hard coat layer (hereinafter, simply will be referred to as "projections") are perforated 300-4000 per 100 [mu] m 2 of.
  • the center line average roughness (Ra1) of the surface of the first hard coat layer is less than 30 nm.
  • Such a hard coat film of this embodiment has a haze value of less than 1.5%.
  • the slipping property and the blocking resistance are improved.
  • the range of the number density of protrusions is preferably in the range of 400 to 3,500 per 100 ⁇ m 2 , more preferably in the range of 500 to 3000, still more preferably in the range of 600 to 3000, and particularly preferably in the range of 700 to 2500.
  • the slipperiness and blocking resistance are lowered.
  • the number density of the particles exceeds 4000 per 100 ⁇ m 2 , the smoothness of the surface of the first hard coat layer is lowered, the haze value is increased, and the transparency of the hard coat film is lowered.
  • the hard coat film of this embodiment has a relatively large number of protrusions on the surface of the first hard coat layer as described above, while the surface of the first hard coat layer is relatively smooth and the haze value of the hard coat film is small. This is one of the features. Specifically, it is important that the center line average roughness (Ra1) on the surface of the first hard coat layer in this embodiment is less than 30 nm, and the haze value of the hard coat film is less than 1.5%. .
  • the center line average roughness (Ra1) of the first hard coat layer surface is preferably 25 nm or less, more preferably 20 nm or less, and particularly preferably 18 nm or less.
  • the lower limit center line average roughness (Ra1) is preferably 5 nm or more, more preferably 7 nm or more, and particularly preferably 9 nm or more from the viewpoint of ensuring slipperiness and blocking resistance.
  • the hard coat film of the present embodiment has a haze value of less than 1.5% from the viewpoint of realizing high transparency.
  • the haze value of the hard coat film of this embodiment is preferably 1.1% or less, more preferably 1.0% or less.
  • the lower haze value is preferably as small as possible, but practically about 0.01%.
  • the surface of the first hard coat layer has 300 to 4000 protrusions per 100 ⁇ m 2 , the center line average roughness (Ra1) of the first hard coat layer surface is less than 30 nm, and the haze value of the hard coat film is 1.
  • particles having an average particle diameter (r) of 0.05 to 0.5 ⁇ m are contained in the first hard coat layer, and these particles are relatively placed in the vicinity of the surface of the first hard coat layer. It is preferable that protrusions be formed on the surface of the first hard coat layer by making it exist in large quantities.
  • the ratio (r / d) of the average particle diameter (r) ( ⁇ m) of the particles contained in the first hard coat layer to the thickness (d) ( ⁇ m) of the first hard coat layer is 0.01 to 0.00. 30 is preferable. Thereby, the center line average roughness (Ra1) on the surface of the first hard coat layer is reduced, and the haze value of the hard coat film is also reduced.
  • a plastic film is preferably used for the base film.
  • the material constituting the base film include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyimide, polyphenylene sulfide, aramid, polypropylene, polyethylene, polylactic acid, polyvinyl chloride, polycarbonate, and polymethacrylic.
  • polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyimide, polyphenylene sulfide, aramid, polypropylene, polyethylene, polylactic acid, polyvinyl chloride, polycarbonate, and polymethacrylic.
  • Examples include methyl acid, alicyclic acrylic resin, cycloolefin resin, triacetyl cellulose, and those obtained by mixing and / or copolymerizing these resins.
  • a film obtained by unstretching these resins, or uniaxially stretching or biaxially stretching into a film can be applied
  • the polyester film is excellent in transparency, dimensional stability, mechanical properties, heat resistance, electrical properties, chemical resistance, and the like, and a polyethylene terephthalate film (PET film) is particularly preferably used.
  • PET film polyethylene terephthalate film
  • the range of the thickness of the base film is suitably 20 to 300 ⁇ m, preferably 30 to 200 ⁇ m, and more preferably 50 to 150 ⁇ m.
  • the base film preferably has at least a resin layer as shown below on the surface on which the first hard coat layer is laminated. That is, it is preferable to have the resin layer shown below between a base film and a 1st hard-coat layer.
  • the base film is preferably provided with a resin layer on at least the surface on which the first hard coat layer is laminated.
  • the resin layer is a layer containing a resin as a main component. Specifically, the resin layer is a layer containing 50% by mass or more of resin with respect to 100% by mass of the total solid content of the resin layer.
  • the resin forming the resin layer include polyester resin, acrylic resin, urethane resin, polycarbonate resin, epoxy resin, alkyd resin, urea resin, and the like. These resins can be used alone or in combination.
  • the resin layer is interposed between the base film and the first hard coat layer, and from the viewpoint of improving the adhesion between the base film and the first hard coat layer, the resin is a polyester resin, an acrylic resin, and a polyurethane resin. It is preferable to contain at least one selected from the group consisting of In particular, the resin layer preferably contains at least a polyester resin as a resin.
  • the resin content in the resin layer is preferably 60% by mass or more, more preferably 70% by mass or more, and particularly preferably 80% by mass or more with respect to 100% by mass of the total solid content of the resin layer.
  • the resin content in the resin layer is preferably 95% by mass or less, and more preferably 90% by mass or less.
  • the resin layer may be formed in a two-layer configuration.
  • a first resin layer mainly composed of a polyester resin and a second resin layer mainly composed of an acrylic resin are sequentially formed from the base film side. Details of the two-layer configuration will be described later.
  • the resin layer preferably contains particles from the viewpoint of ensuring appropriate slipping and winding properties in the manufacturing process of the hard coat film.
  • the particles contained in the resin layer are not particularly limited, but inorganic particles such as silica particles, titanium oxide, aluminum oxide, zirconium oxide, calcium carbonate, zeolite particles, acrylic particles, silicone particles, polyimide particles, Teflon (registered trademark) ) Organic particles such as particles, crosslinked polyester particles, crosslinked polystyrene particles, crosslinked polymer particles, and core-shell particles.
  • silica particles are preferable, and colloidal silica is particularly preferable.
  • the particles contained in the resin layer preferably have an average particle size larger than the thickness of the resin layer.
  • the average particle diameter is preferably 1.3 times or more of the thickness of the resin layer, more preferably 1.5 times or more, and particularly preferably 2.0 times or more.
  • the upper limit is preferably 20 times or less, more preferably 15 times or less, and particularly preferably 10 times or less.
  • the slip property and the blocking resistance are further improved by directly laminating the first hard coat layer on the resin layer containing particles having an average particle diameter larger than the thickness of the resin layer.
  • the average particle size of the particles contained in the resin layer is appropriately selected according to the thickness design of the resin layer. Specifically, the range of the average particle size is preferably in the range of 0.02 to 1 ⁇ m. A range of 0.05 to 0.7 ⁇ m is more preferable, and a range of 0.1 to 0.5 ⁇ m is particularly preferable. If the average particle size is less than 0.02 ⁇ m, the slipperiness and blocking resistance may be lowered. If the average particle diameter exceeds 1 ⁇ m, the particles may fall off, the transparency may be lowered, or the appearance may be deteriorated.
  • the thickness range of the resin layer is preferably in the range of 0.005 to 0.3 ⁇ m.
  • the thickness of the resin layer is further preferably 0.01 ⁇ m or more, more preferably 0.015 ⁇ m or more, and particularly preferably 0.02 ⁇ m or more.
  • the thickness of the resin layer is preferably 0.25 ⁇ m or less, preferably 0.2 ⁇ m or less, particularly preferably 0.15 ⁇ m or less.
  • the range of the content of the particles in the resin layer is preferably in the range of 0.05 to 10% by mass, more preferably in the range of 0.1 to 8% by mass, particularly 0% to 100% by mass of the total solid content of the resin layer.
  • the range of 5 to 5% by mass is preferable.
  • the content of the particles in the resin layer is less than 0.05% by mass, good slipping property and blocking resistance may not be obtained.
  • the content of the particles exceeds 10% by mass, the transparency is lowered. Or the applicability of the first hard coat layer may deteriorate, or the adhesion between the base film and the first hard coat layer may be reduced.
  • the resin layer preferably further contains a crosslinking agent.
  • the resin layer is preferably a thermosetting layer containing the above-described resin and a crosslinking agent.
  • the conditions (heating temperature, time) for thermosetting the resin layer are not particularly limited, but the heating temperature is preferably 70 ° C or higher, more preferably 100 ° C or higher, particularly preferably 150 ° C or higher, and most preferably 200 ° C or higher. .
  • the heating temperature is preferably 300 ° C. or lower.
  • the range of the heating time is preferably 5 to 300 seconds, and more preferably 10 to 200 seconds.
  • crosslinking agent examples include melamine crosslinking agent, oxazoline crosslinking agent, carbodiimide crosslinking agent, isocyanate crosslinking agent, aziridine crosslinking agent, epoxy crosslinking agent, methylolated or alkylolized urea crosslinking agent, acrylamide
  • examples thereof include system crosslinking agents, polyamide resins, amide epoxy compounds, various silane coupling agents, and various titanate coupling agents.
  • laminic crosslinking agents, oxazoline crosslinking agents, carbodiimide crosslinking agents, isocyanate crosslinking agents, and aziridine crosslinking agents are preferable, and melamine crosslinking agents are particularly preferable.
  • Examples of the melamine-based crosslinking agent include imino group type methylated melamine resin, methylol group type melamine resin, methylol group type methylated melamine resin, and fully alkyl type methylated melamine resin. Among these, imino group type melamine resins and methylolated melamine resins are preferably used.
  • the range of the content of the crosslinking agent in the resin layer is preferably in the range of 0.5 to 40% by mass, more preferably in the range of 1 to 30% by mass, especially 2 to 2% with respect to 100% by mass of the total solid content of the resin layer. A range of 20% by weight is preferred.
  • the reflection color of the hard coat film obtained by laminating the first hard coat layer on the base film via the resin layer is preferably a neutral colorless hue.
  • the range of the refractive index of the resin layer is preferably 1.55 to 1.61, and more preferably 1.56 to 1.60. A range of 1.57 to 1.59 is more preferable.
  • the refractive index of a polyethylene terephthalate film is generally about 1.62 to 1.70, and by adjusting the refractive index of the resin layer to the above range (1.55 to 1.61), The reflected color can be close to neutral and colorless. That is, the difference (np ⁇ nr) between the refractive index (np) of the PET film and the refractive index (nr) of the resin layer is preferably in the range of 0.02 to 0.1, preferably 0.03 to 0.00. The range of 09 is more preferable, and the range of 0.04 to 0.08 is particularly preferable.
  • a polyester resin containing a naphthalene ring in the molecule is preferable to use as the resin.
  • a polyester resin containing a naphthalene ring can be synthesized, for example, by using a polyvalent carboxylic acid such as 1,4-naphthalenedicarboxylic acid or 2,6-naphthalenedicarboxylic acid as a copolymerization component.
  • the range of the content of the polyester resin containing a naphthalene ring in the molecule in the resin layer is preferably 5 to 70% by mass, more preferably 10 to 60% by mass with respect to 100% by mass of the total resin.
  • the resin layer is applied on the base film by a wet coating method, and is thermoset and laminated. Furthermore, it is preferable that the resin layer is applied by a wet coating method in the manufacturing process of the base film, which is applied by a so-called in-line coating method, and is thermally cured and laminated. Examples of the wet coating method include a reverse coating method, a spray coating method, a bar coating method, a gravure coating method, a rod coating method, and a die coating method.
  • a resin layer having a two-layer structure can be adopted.
  • Such a two-layered resin layer is preferably formed by applying one coating solution once and causing self-phase separation in the drying process. That is, a coating liquid containing the main component (polyester resin) of the first resin layer and the main component (acrylic resin) of the second resin layer is applied, and self-phase separation of each component is utilized in the drying process. It is preferable to employ a method of forming the first resin layer and the second resin layer.
  • the surface energy difference between the main component (polyester resin) of the first resin layer and the main component (acrylic resin) of the second resin layer it is preferable to increase the surface energy difference between the main component (polyester resin) of the first resin layer and the main component (acrylic resin) of the second resin layer. That is, it is preferable to use a polyester resin having a high surface energy and an acrylic resin having a low surface energy. In particular, it is preferable to use a polyester resin having a sulfonic acid group in order to increase the surface energy of the polyester resin.
  • the thickness of the first resin layer is set from the viewpoint of enhancing the adhesion between the base film and the first hard coat layer and making the reflected color of the hard coat film close to neutral and colorless. It is preferable to be larger than the thickness of the two resin layers.
  • the thickness of the first resin layer is preferably 1.5 times or more, more preferably 2.0 times or more, and particularly preferably 3.0 times or more the thickness of the second resin layer.
  • the thickness range of the first resin layer is preferably 0.02 to 0.2 ⁇ m, more preferably 0.03 to 0.15 ⁇ m, and particularly preferably 0.05 to 0.12 ⁇ m. preferable.
  • the thickness of the second resin layer is preferably in the range of 0.005 to 0.1 ⁇ m, more preferably in the range of 0.01 to 0.07 ⁇ m, and particularly preferably in the range of 0.01 to 0.05 ⁇ m.
  • the resin layer provided between the base film and the first hard coat layer preferably has a surface wetting tension of 52 mN / m or less. That is, in the present invention, it is preferable that the wetting tension on the surface of the resin layer to which the first hard coat layer is applied is 52 mN / m or less.
  • the wetting tension is a physical property value defined in JIS-K-6768.
  • a mode in which a resin layer having a wetting tension of 52 mN / m or less is provided between the base film and the first hard coat layer is effective when the thickness of the first hard coat layer is relatively small.
  • the absolute amount of particles contained in the first hard coat layer is also reduced.
  • the particles contained in the first hard coat layer are likely to be unevenly distributed near the surface. Can be formed.
  • This aspect is effective when the thickness of the first hard coat layer is less than 2 ⁇ m, and is particularly effective when the thickness of the first hard coat layer is 1.7 ⁇ m or less.
  • the wetting tension on the surface of the resin layer is preferably 50 mN / m or less.
  • the lower limit of the wetting tension on the surface of the resin layer is preferably 35 mN / m or more, more preferably 37 mN / m or more, and 40 mN / m. The above is particularly preferable. If the wetting tension on the surface of the resin layer is less than 35 mN / m, the adhesion of the first hard coat layer may be lowered.
  • the resin to be contained in the resin layer is a polyester resin or an acrylic resin. It is preferable to use at least one selected from the group consisting of polyurethane resins. Among these resins, it is preferable to use a polyester resin and / or an acrylic resin, and it is particularly preferable to use at least a polyester resin as the resin.
  • the wetting tension on the surface of the resin layer can be controlled by adjusting the type and content of the crosslinking agent described above. For example, when the content of the crosslinking agent increases, the wetting tension on the surface of the resin layer tends to decrease. Conversely, when the content of the crosslinking agent decreases, the wetting tension on the surface of the resin layer tends to increase.
  • the first hard coat layer contains particles, and protrusions due to the particles are formed on the surface of the first hard coat layer.
  • the number density of protrusions on the surface of the first hard coat layer is 300 to 4000 per unit area (100 ⁇ m 2 ) of the surface of the first hard coat layer.
  • the range of the number density of the protrusions is preferably in the range of 400 to 3,500 per 100 ⁇ m 2 , more preferably in the range of 500 to 3000, further preferably in the range of 600 to 3000, and particularly preferably in the range of 700 to 2500. .
  • the range of the average particle diameter (r) of the particles contained in the first hard coat layer is preferably in the range of 0.05 to 0.5 ⁇ m, more preferably in the range of 0.06 to 0.4 ⁇ m, particularly 0.07. A range of ⁇ 0.3 ⁇ m is preferred.
  • the average particle diameter (r) of the particles contained in the first hard coat layer is less than 0.05 ⁇ m, a sufficiently large protrusion is not formed on the surface of the first hard coat layer, and slipping and blocking resistance are prevented. May not be improved sufficiently.
  • the average particle diameter (r) exceeds 0.5 ⁇ m, the smoothness of the surface of the first hard coat layer is lowered, the center line average roughness (Ra1) is 30 nm or more, or the haze value of the hard coat film is 1. .5% or more may cause inconvenience such as a decrease in transparency.
  • the average particle diameter (r) of the particles contained in the first hard coat layer is sufficiently smaller than the thickness (d) of the first hard coat layer. That is, the ratio between the average particle diameter (r) of the particles and the thickness (d) of the first hard coat layer is preferably in the range of 0.01 to 0.30. It is preferable that a relatively large amount of such particles be present near the surface of the first hard coat layer to form a relatively large number of protrusions on the surface of the first hard coat layer as described above. This can improve slipperiness and blocking resistance without reducing the smoothness of the surface of the first hard coat layer.
  • the range of the ratio (r / d) of the average particle diameter (r) of the particles contained in the first hard coat layer to the thickness (d) of the first hard coat layer is further in the range of 0.01 to 0.20.
  • the range of 0.01 to 0.15 is more preferable, the range of 0.02 to 0.10 is particularly preferable, and the range of 0.02 to 0.08 is most preferable.
  • the range of the average diameter of the protrusions formed on the surface of the first hard coat layer by the particles as described above is preferably in the range of 0.03 to 0.3 ⁇ m. Further, the range of the average diameter of the protrusions is preferably in the range of 0.04 to 0.25 ⁇ m, and more preferably in the range of 0.05 to 0.2 ⁇ m. Thereby, slipperiness and blocking resistance can be improved without reducing transparency.
  • the average height of the protrusions is preferably in the range of 0.03 to 0.3 ⁇ m. Further, the range of the average height of the protrusions is preferably in the range of 0.04 to 0.25 ⁇ m, and more preferably in the range of 0.05 to 0.2 ⁇ m. Thereby, slipperiness and blocking resistance can be improved without reducing transparency.
  • the shape of the protrusion formed on the surface of the first hard coat layer is not particularly limited, but preferably has a circular shape or a planar shape close to a circular shape.
  • the planar shape of the protrusion refers to the planar shape when the surface of the first hard coat layer is observed with a scanning electron microscope (SEM).
  • FIG. 1 is an example of a surface photograph of the first hard coat layer by a scanning electron microscope. Projections 11 made of particles are formed on the surface of the first hard coat layer.
  • FIG. 2 is a diagram schematically showing the planar shape of the protrusions on the surface of the first hard coat layer.
  • the planar shape of the protrusion means that the diameter (Lmin) of the protrusion 11 orthogonal to the line segment representing the maximum diameter (Lmax) of the protrusion 11 and the center Lc, and the maximum of the protrusion 11. It means that the ratio (Lmin / Lmax) to the diameter (Lmax) is 0.65 or more.
  • the ratio (Lmin / Lmax) is preferably 0.70 or more, more preferably 0.80 or more, and particularly preferably 0.85 or more.
  • the upper limit is 1.0.
  • the diameter of the protrusion means the maximum diameter (Lmax) shown in FIG.
  • the average diameter of the protrusions can be obtained from a surface photograph of the first hard coat layer as shown in FIG. 1 using a scanning electron microscope.
  • the height of the protrusion means the length from the top of the protrusion to the surface of the first hard coat layer.
  • the average height of the protrusions can be measured from a cross-sectional photograph taken with a transmission electron microscope (TEM) of the first hard coat layer.
  • TEM transmission electron microscope
  • the range of the average spacing of the protrusions on the surface of the first hard coat layer is preferably in the range of 0.10 to 0.70 ⁇ m, more preferably in the range of 0.15 to 0.50 ⁇ m, particularly 0.20 to 0.40 ⁇ m. A range is preferred. Thereby, slipperiness and blocking resistance can be improved without reducing transparency.
  • the average interval between the protrusions can be obtained from a surface photograph of the first hard coat layer by a scanning electron microscope.
  • FIG. 3 is a diagram schematically showing a surface photograph of the first hard coat layer by a scanning electron microscope. A method for measuring the average interval between the protrusions will be described with reference to FIG.
  • a single straight line 20 is drawn in the horizontal direction, and a vertical straight line 30 orthogonal to the horizontal straight line 20 is drawn.
  • the distance between the adjacent protrusions is measured.
  • a similar operation is performed on the vertical straight line 30. The intervals (distances) of all the protrusions thus obtained are averaged.
  • FIG. 4 is a diagram in which only the projections on the horizontal straight line 20 or the vertical straight line 30 in FIG. 3 are selected and edited.
  • the number of protrusions riding on the horizontal straight line 20 is five as indicated by reference numerals 1 to 5.
  • the interval between adjacent protrusions is, for example, the distance P between the protrusion 1 and the protrusion 2 adjacent to the protrusion 1.
  • the distance between the protrusion 2 and the protrusion 3 and the protrusion 4 and the protrusion 5 the distance between adjacent protrusions for all particles on the horizontal straight line 20 is measured. Measure.
  • the above operation is performed by changing the position of the straight line in the horizontal direction and the position of the straight line in the vertical direction three times, and the average of all the obtained protrusion intervals is taken as the average interval of the protrusions.
  • each protrusion on the surface of the first hard coat layer is preferably formed by one particle. This makes it easy to adjust the center line average roughness (Ra1) of the first hard coat layer surface to less than 30 nm and to adjust the haze value of the hard coat film to less than 1.5%. If protrusions are formed in a state where a plurality of particles are aggregated, the center line average roughness (Ra1) on the surface of the first hard coat layer and the haze value of the hard coat film tend to increase, such being undesirable.
  • the range of the content of the particles in the first hard coat layer is preferably 2.5 to 17% by mass, more preferably 3 to 15% by mass with respect to 100% by mass of the total solid content of the first hard coat layer.
  • the range of 4 to 12% by mass is particularly preferable.
  • particles having an average particle diameter (r) sufficiently smaller than the thickness (d) of the first hard coat layer are contained in the first hard coat layer, and the particles are in the vicinity of the surface of the first hard coat layer. It is preferable that a relatively large number of protrusions be formed on the surface of the first hard coat layer.
  • the particles In order for the particles to be present in the vicinity of the surface of the first hard coat layer, it is necessary to move (float) the particles in the vicinity of the surface in the process of forming the first hard coat layer. This can be achieved, for example, by using particles that have been subjected to a surface treatment for reducing the surface free energy of the particles, or particles that have been subjected to a hydrophobic treatment for hydrophobizing the surface of the particles. As the particles to be subjected to these treatments, inorganic particles are preferable, and silica particles are particularly preferable.
  • inorganic particles are preferably used.
  • Inorganic particles are preferably inorganic particles containing an element selected from Si, Na, K, Ca, and Mg. More preferably, inorganic particles containing a compound selected from silica particles (SiO 2 ), alkali metal fluorides (NaF, KF, etc.), and alkaline earth metal fluorides (CaF 2 , MgF 2, etc.) can be mentioned, Silica particles are particularly preferable from the viewpoint of durability.
  • the surface treatment for reducing the surface free energy of the particles includes an organosilane compound having a fluorine atom represented by the following general formula (1), a hydrolyzate of the organosilane, and a hydrolysis of the organosilane. And a surface treatment with at least one compound selected from the group consisting of partial condensates.
  • n represents an integer of 1 to 10
  • m represents an integer of 1 to 5.
  • Q represents an alkoxy group having 1 to 5 carbon atoms or a halogen atom.
  • Specific examples of the compound of the general formula (1) include the following compounds. C 4 F 9 CH 2 CH 2 Si (OCH 3) 3 C 6 F 13 CH 2 CH 2 Si (OCH 3 ) 3 C 8 F 17 CH 2 CH 2 Si (OCH 3) 3 C 6 F 13 CH 2 CH 2 CH 2 Si (OCH 3) 3 C 6 F 13 CH 2 CH 2 CH 2 Si (OCH 3) 3 C 6 F 13 CH 2 CH 2 Si (OC 2 H 5) 3 C 8 F 17 CH 2 CH 2 CH 2 Si (OC 2 H 5) 3 C 6 F 13 CH 2 CH 2 CH 2 CH 2 Si (OC 2 H 5 ) 3 C 6 F 13 CH 2 CH 2 SiCl 3 C 6 F 13 CH 2 CH 2 SiBr 3 C 6 F 13 CH 2 CH 2 CH 2 SiCl 3 C 6 F 13 CH 2 CH 2 Si (OCH 3 ) Cl 2
  • B and D each independently represent a reactive site
  • R 4 and R 7 are each independently derived from an alkylene group having 1 to 3 carbon atoms, or the alkylene group.
  • R 5 and R 6 each independently represent hydrogen or an alkyl group having 1 to 4 carbon atoms
  • Rf 2 represents a fluoroalkyl group
  • n represents an integer of 0 to 2.
  • Examples of the reactive site represented by B and D include a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, an acryloyloxy group, a methacryloyloxy group, an epoxy group, a carboxyl group, and a hydroxyl group.
  • Specific examples of the general formula (2) include acryloxyethyltrimethoxysilane, acryloxypropyltrimethoxysilane, acryloxybutyltrimethoxysilane, acryloxypentyltrimethoxysilane, acryloxyhexyltrimethoxysilane, acryloxyheptyltri Methoxysilane, methacryloxyethyltrimethoxysilane, methacryloxypropyltrimethoxysilane, methacryloxybutyltrimethoxysilane, methacryloxyhexyltrimethoxysilane, methacryloxyheptyltrimethoxysilane, methacryloxypropylmethyldimethoxysilane, methacryloxypropylmethyldimethoxy Examples include silane and compounds in which the methoxy group in these compounds is substituted with other alkoxyl groups or hydroxyl groups. It is.
  • Specific examples of the general formula (3) include 2,2,2-trifluoroethyl acrylate, 2,2,3,3,3-pentafluoropropyl acrylate, 2-perfluorobutylethyl acrylate, 3-perfluoro Butyl-2-hydroxypropyl acrylate, 2-perfluorohexylethyl acrylate, 3-perfluorohexyl-2-hydroxypropyl acrylate, perfluorooctylmethyl acrylate, 2-perfluorooctylethyl acrylate, 3-perfluorooctyl-2- Hydroxypropyl acrylate, 2-perfluorodecylethyl acrylate, 2-perfluoro-3-methylbutylethyl acrylate, 3-perfluoro-3-methoxybutyl-2-hydroxypropyl acrylate, 2-perf Oro-5-methylhexyl ethyl acrylate, 3-perfluoro-5-methylhexyl-2-
  • hydrophobic compound for subjecting the particle surface to a hydrophobic treatment examples include compounds having a hydrophobic group and a reactive site in the molecule.
  • the hydrophobic group of the hydrophobic compound is not particularly limited as long as it generally has a hydrophobic function, but specific examples of the hydrophobic group include, for example, a fluoroalkyl group having 4 or more carbon atoms, a hydrocarbon group having 8 or more carbon atoms, and Examples include at least one functional group selected from the group consisting of siloxane groups.
  • the reactive site is a site that chemically reacts with radicals generated by receiving energy such as light or heat.
  • Specific examples include vinyl group, allyl group, acryloyl group, methacryloyl group, acryloyloxy group, It is more preferable to have a reactive site that undergoes a chemical reaction upon receiving energy such as light or heat, such as a methacryloyloxy group, an epoxy group, a carboxyl group, or a hydroxyl group.
  • a hydrophobic compound for subjecting the particle surface to a hydrophobization treatment a compound having a fluoroalkyl group having 4 or more carbon atoms and a reactive site (fluorine compound), a hydrocarbon group having 8 or more carbon atoms and reactivity. It is preferable to use at least one selected from the group consisting of a compound having a moiety (long chain hydrocarbon compound) and a compound having a siloxane group and a reactive moiety (silicone compound).
  • the long-chain hydrocarbon compound represents a compound having a hydrocarbon group having 8 or more carbon atoms which is a hydrophobic group in the molecule and a reactive site.
  • the hydrocarbon group having 8 or more carbon atoms preferably has 8 to 30 carbon atoms.
  • the hydrocarbon group having 8 or more carbon atoms can be selected regardless of a linear structure, a branched structure, or an alicyclic structure. More preferably, a linear alkyl alcohol having 10 to 22 carbon atoms, an alkyl epoxide, an alkyl acrylate, an alkyl methacrylate, an alkyl carboxylate (including acid anhydrides and esters), etc. are used as the long-chain hydrocarbon compound. be able to.
  • long-chain hydrocarbon compound examples include polyhydric alcohols such as octanol, hexanediol, heptanediol, octanediol, stearyl alcohol, octyl acrylate, octyl methacrylate, 2-hydroxyoctyl acrylate, 2-hydroxyoctyl methacrylate, etc.
  • Acrylate (methacrylate) acrylic silane such as octyltrimethoxysilane, and the like.
  • silicone compound examples include compounds having a siloxane group that is a hydrophobic group in the molecule and a reactive site.
  • a reactive site of the silicone compound an acryloyloxy group or a methacryloyloxy group is preferably used.
  • siloxane group a polysiloxane group represented by the following general formula (4) is preferably used.
  • R 8 and R 9 are each independently an alkyl group having 1 to 6 carbon atoms, a phenyl group, a 3-acryloxy-2-hydroxypropyl-oxypropyl group, a 2-acryloxy-3-hydroxypropyl group.
  • silicone compound having a polysiloxane group represented by the general formula (4) as a hydrophobic group include compounds having a dimethylsiloxane group represented by the following general formula (5) and a reactive site.
  • Specific examples of the silicone compound having a dimethylsiloxane group of the general formula (5) and a reactive site include X-22-164B, X-22-164C, X-22-5002, X-22-174D, X -22-167B (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.).
  • R represents alkyl having 1 to 7 carbon atoms
  • k represents an integer of 0 or 1
  • m represents an integer of 10 to 200.
  • silicone compound having a polysiloxane group represented by the general formula (4) as a hydrophobic group and a reactive site is 3-acryloxy-2-hydroxy represented by the general formula (6).
  • examples thereof include compounds having a propyl-oxypropyl group and a methyl group, and compounds having a 2-acryloxy-3-hydroxypropyl-oxypropyl group and a methyl group represented by the general formula (7).
  • R represents an alkyl having 1 to 7 carbon atoms
  • k represents an integer of 0 or 1
  • m represents an integer of 10 to 200.
  • silicone compound having a polysiloxane group represented by the general formula (4) and a reactive site as a hydrophobic group is an acryloyloxy group or methacryloyloxy at the terminal represented by the general formula (8).
  • examples thereof include a compound having a polyethylene glycol propyl ether group having a group and a methyl group, and a compound having a polyethylene glycol propyl ether group having a hydroxy group at the terminal and a methyl group, represented by the general formula (9).
  • R represents alkyl having 1 to 7 carbon atoms
  • k represents an integer of 0 or 1
  • x represents an integer of 1 to 10
  • m represents 10 to 200. Represents an integer.
  • the fluorine compound having a fluoroalkyl group having 4 or more carbon atoms and a reactive site will be described.
  • the fluoroalkyl group may have a linear structure or a branched structure.
  • the fluoroalkyl group preferably has 4 to 8 carbon atoms.
  • fluorine compound fluoroalkyl alcohol, fluoroalkyl epoxide, fluoroalkyl halide, fluoroalkyl acrylate, fluoroalkyl methacrylate, fluoroalkyl carboxylate (including acid anhydrides and esters), and the like can be used.
  • fluoroalkyl acrylate and fluoroalkyl methacrylate are preferable.
  • a compound having a fluoroalkyl group having 4 or more carbon atoms can be used from the compounds exemplified in the general formula (3).
  • the number of fluoroalkyl groups in the fluorine compound is not necessarily one, and the fluorine compound may have a plurality of fluoroalkyl groups.
  • the first hard coat layer preferably has a high hardness in order to suppress the occurrence of scratches on the hard coat film surface, and the pencil hardness defined by JIS K5600-5-4 (1999) is H or more. Those are preferred. The upper limit of pencil hardness is about 9H.
  • the first hard coat layer preferably contains a thermosetting resin or an active energy ray curable resin as a resin, and particularly preferably contains an active energy ray curable resin.
  • the active energy ray-curable resin means a resin that is polymerized and cured by active energy rays such as ultraviolet rays and electron beams.
  • a compound (monomer or oligomer) having a polymerizable functional group such as acryloyl group, methacryloyl group, acryloyloxy group, methacryloyloxy group, vinyl group, and allyl group.
  • the first hard coat layer is formed by applying the active energy ray-curable composition containing the polymerizable compound by a wet coating method, drying it as necessary, and then irradiating the active energy ray to cure. It is preferable that
  • ... (Meth) acrylate includes two compounds “... acrylate” and “... methacrylate”.
  • Examples of the monomer include methyl (meth) acrylate, lauryl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl ( Monofunctional acrylates such as (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxy (meth) acrylate, neopentyl glycol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythrito Rutetra (meth) acrylate, dipentaerythritol tri
  • polyfunctional monomers having 3 or more polymerizable functional groups in one molecule are preferably used.
  • oligomer examples include polyester (meth) acrylate, polyurethane (meth) acrylate, epoxy (meth) acrylate, polyether (meth) acrylate, alkit (meth) acrylate, melamine (meth) acrylate, and silicone (meth) acrylate. be able to.
  • polyfunctional urethane (meth) acrylate oligomers having 3 or more polymerizable functional groups in one molecule are preferably used.
  • a polyfunctional urethane (meth) acrylate oligomer a commercially available product can be used.
  • the content of the polymerizable compound in the active energy ray-curable composition is preferably 50% by mass or more and 55% by mass or more with respect to 100% by mass of the total solid content of the active energy ray-curable composition. More preferably, it is more preferably 60% by mass or more, and particularly preferably 70% by mass or more.
  • the upper limit is preferably 97% by mass or less, and more preferably 95% by mass or less.
  • the active energy ray curable composition preferably contains a photopolymerization initiator.
  • the photopolymerization initiator include acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, benzophenone, 2-chlorobenzophenone, 4,4′-dichlorobenzophenone, 4,4′-bisdiethylaminobenzophenone, Michler's ketone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, methyl benzoylformate, p-isopropyl- ⁇ -hydroxyisobutylphenone, ⁇ -hydroxyisobutylphenone, 2, Carbonyl compounds such as 2-dimethoxy-2-phenylacetophenone and 1-hydroxycyclohexyl phenyl ket
  • photopolymerization initiators are generally commercially available and can be used.
  • Irgacure registered trademark
  • Irgacure 907 Irgacure 379
  • Irgacure 819 Irgacure 127
  • Irgacure 500 Irgacure 754
  • Irgacure 250 Irgacure 1800
  • Irgacure 1870 Irgacure OXEDA
  • ROCIA OXEDA manufactured by Ciba Specialty Chemicals Co., Ltd.
  • the range of the content of the photopolymerization initiator is suitably in the range of 0.1 to 10% by mass with respect to 100% by mass of the total solid content of the active energy ray-curable composition, and 0.5 to 8% by mass.
  • the range of is preferable.
  • the active energy ray-curable composition can further contain various additives such as an antioxidant, an ultraviolet absorber, a leveling agent, a particle dispersant, an organic antistatic agent, a lubricant, a colorant, and a pigment. .
  • the active energy ray-curable composition contains particles for forming protrusions on the surface of the first hard coat layer.
  • particles that have been subjected to the above-described surface treatment or hydrophobic treatment are preferably used.
  • the range of the content of particles in the active energy ray-curable composition is preferably 2.5 to 17% by mass with respect to 100% by mass of the total solid content of the active energy ray-curable composition, and preferably 3 to 15% by mass. Is more preferable, and a range of 4 to 12% by mass is particularly preferable.
  • the refractive index range of the first hard coat layer is preferably from 1.48 to 1.54, more preferably from 1.50 to 1.54.
  • the active energy ray-curable composition described above is applied by a wet coating method, dried as necessary, and then irradiated with active energy rays to form a first hard coat layer, whereby the refractive index is reduced.
  • a first hard coat layer in the range of 1.48 to 1.54 can be obtained.
  • the range of the thickness of the first hard coat layer is suitably from 0.5 ⁇ m to less than 10 ⁇ m, preferably from 0.8 ⁇ m to 7 ⁇ m, more preferably from 1 ⁇ m to 5 ⁇ m, particularly from 1 ⁇ m to 3 ⁇ m. The following is preferred.
  • the thickness of the first hard coat layer is less than 0.5 ⁇ m, the hardness of the first hard coat layer is lowered and scratches are easily formed.
  • the thickness of the first hard coat layer is 10 ⁇ m or more, inconveniences such as slipperiness and blocking resistance may decrease, curl may increase, and transmittance may decrease.
  • the hard coat film has a first hard coat layer on at least one surface of the base film.
  • the hard coat film may have a first hard coat layer only on one side of the base film, or may have a first hard coat layer on both sides of the base film.
  • the first hard coat layer is provided on one side of the base film, and the first hard coat layer of the base film is provided on the other side of the base film (that is, Examples thereof include a hard coat film having a second hard coat layer (on the side opposite to the provided surface).
  • stacked on the other surface of a base film takes the completely same structure as the 1st hard coat layer laminated
  • the first hard coat layer is laminated on both sides of the first hard coat layer, it may be referred to as a second hard coat layer in order to distinguish it from the first hard coat layer on one side.
  • the second hard coat layer preferably has a high hardness in order to suppress the occurrence of scratches on the hard coat film surface, and the pencil hardness defined by JIS K5600-5-4 (1999) is H or more. It is preferable and 2H or more is more preferable. The upper limit of pencil hardness is about 9H.
  • the surface of the second hard coat layer is preferably relatively smooth and clear.
  • the center line average roughness (Ra2) of the surface of the second hard coat layer is preferably 25 nm or less, more preferably 20 nm or less, and particularly preferably 15 nm or less.
  • the lower limit is not particularly limited, but is practically about 1 nm.
  • the second hard coat layer has a center line average roughness (Ra2) of the second hard coat layer surface of 25 nm or less
  • the second hard coat layer substantially contains particles having an average particle diameter of more than 0.5 ⁇ m. It is preferable not to contain.
  • the fact that the second hard coat layer does not substantially contain particles having an average particle size larger than 0.5 ⁇ m means that the coating liquid for forming the second hard coat layer (for example, active energy ray-curable composition) Means that particles having an average particle size of more than 0.5 ⁇ m are not intentionally added to the product.
  • the surface of the second hard coat layer is preferably relatively smooth and clear. Accordingly, it is preferable that substantially no protrusions due to particles exist on the surface of the second hard coat layer.
  • the fact that there are substantially no protrusions due to particles on the surface of the second hard coat layer means that the number of protrusions per unit area (100 ⁇ m 2 ) on the surface of the second hard coat layer is 100 or less. To do.
  • the number of protrusions per unit area (100 ⁇ m 2 ) on the surface of the second hard coat layer is 50 or less, more preferably 30 or less, and particularly preferably 0.
  • the second hard coat layer can contain particles having an average particle size of 0.5 ⁇ m or less, but it is preferable to adjust the average particle size of the particles contained in the second hard coat layer from the above viewpoint.
  • the average particle diameter of the particles is preferably 0.2 ⁇ m or less, and more preferably 0.1 ⁇ m or less.
  • the range of the content of such particles is suitably in the range of 0.1 to 15% by mass with respect to 100% by mass of the total solid content of the second hard coat layer, and in the range of 0.5 to 10% by mass. More preferably, the range of 1 to 8% by mass is particularly preferable.
  • the second hard coat layer preferably contains a thermosetting resin or an active energy ray curable resin as the resin, and particularly preferably contains an active energy ray curable resin.
  • the active energy ray-curable resin means a resin that is polymerized and cured by active energy rays such as ultraviolet rays and electron beams.
  • the same compounds as those described in the first hard coat layer can be used.
  • the second hard coat layer is coated with an active energy ray-curable composition containing a polymerizable compound by a wet coating method, dried as necessary, and then irradiated with active energy rays. It is preferably formed by curing.
  • the refractive index range of the second hard coat layer is preferably in the range of 1.48 to 1.54, more preferably in the range of 1.50 to 1.54.
  • the second hard coat layer is formed by applying the active energy ray-curable composition described above by a wet coating method, drying it as necessary, and then irradiating and curing with an active energy ray, whereby the refractive index. Can be obtained in the range of 1.48 to 1.54.
  • the range of the thickness of the second hard coat layer is suitably from 0.5 ⁇ m to less than 10 ⁇ m, preferably from 0.8 ⁇ m to 7 ⁇ m, more preferably from 1 ⁇ m to 5 ⁇ m, particularly from 1 ⁇ m to 3 ⁇ m. The following is preferred.
  • the thickness of the second hard coat layer is less than 0.5 ⁇ m, the hardness of the second hard coat layer is lowered and scratches are easily formed.
  • the thickness of the second hard coat layer is 10 ⁇ m or more, inconveniences such as slipperiness and blocking resistance decrease, curl increase, and transmittance may decrease.
  • the hard coat film of this embodiment is suitable as a base film of a transparent conductive film. That is, the transparent conductive film using the hard coat film of this embodiment as a base film is obtained by laminating a transparent conductive film on at least one surface of the hard coat film of this embodiment.
  • the transparent conductive film may be laminated on only one side of the hard coat film, or may be laminated on both sides.
  • i) or iii) is preferable.
  • the first hard coat layer should be exposed without being laminated. Is preferred.
  • the hard coat layer on the surface on which the transparent conductive film is laminated is relatively smooth and clear. Therefore, in the configuration example of iii), the center line average roughness (Ra2) of the surface of the second hard coat layer is preferably 25 nm or less, more preferably 20 nm or less, and particularly preferably 15 nm or less. As described above, since the surface of the hard coat layer (for example, the second hard coat layer) on which the transparent conductive film is laminated is relatively smooth and clear, the transparency of the transparent conductive film is improved, which is preferable.
  • Transparent conductive film examples of the material for forming the transparent conductive layer include tin oxide, indium oxide, antimony oxide, zinc oxide, ITO (indium tin oxide), metal oxide such as ATO (antimony tin oxide), and metal nanowires (for example, silver Nanowire) and carbon naotube.
  • ITO indium tin oxide
  • metal oxide such as ATO (antimony tin oxide)
  • metal nanowires for example, silver Nanowire
  • carbon naotube carbon naotube.
  • ITO is preferably used.
  • the thickness of the transparent conductive film is preferably 10 nm or more, more preferably 15 nm or more, and particularly preferably 20 nm or more, from the viewpoint of ensuring good conductivity with a surface resistance value of 10 3 ⁇ / ⁇ or less. Preferably there is. On the other hand, if the thickness of the transparent conductive film is too large, the color (coloring) may become inconvenient or the transparency may be lowered. Therefore, the upper limit of the thickness of the transparent conductive film is preferably 60 nm or less. 50 nm or less is more preferable, and 40 nm or less is particularly preferable.
  • the method for forming the transparent conductive film is not particularly limited, and a conventionally known method can be used. Specifically, a dry film forming method (vapor phase film forming method) such as a vacuum vapor deposition method, a sputtering method, an ion plating method, or a wet coating method can be used.
  • the transparent conductive film formed as described above may be patterned.
  • the patterning can form various patterns depending on the application to which the transparent conductive film is applied.
  • a pattern part and a non-pattern part are formed by patterning of a transparent conductive film, as a shape of a pattern part, stripe shape, a lattice shape, etc. are mentioned, for example.
  • the patterning of the transparent conductive film is generally performed by etching.
  • a transparent conductive film is patterned by forming a patterned etching resist film on the transparent conductive film by a photolithography method, a laser exposure method, or a printing method and then performing an etching process. After the transparent conductive film is patterned, the etching resist film is peeled off with an alkaline aqueous solution.
  • etching liquid A conventionally well-known thing is used as an etching liquid.
  • inorganic acids such as hydrogen chloride, hydrogen bromide, sulfuric acid, nitric acid and phosphoric acid, organic acids such as acetic acid, and mixtures thereof, and aqueous solutions thereof are used.
  • Examples of the alkaline aqueous solution used for stripping and removing the etching resist film include 1 to 5% by mass of a sodium hydroxide aqueous solution and a potassium hydroxide aqueous solution.
  • the transparent conductive film may be directly laminated on the first hard coat layer or the second hard coat layer.
  • the transparent conductive film and the first hard coat layer or the second hard coat layer may be laminated. It is preferable to interpose a refractive index adjusting layer between the coat layer.
  • the refractive index adjustment layer will be described.
  • the refractive index adjusting layer may be composed of only one layer or may be a laminated structure of two or more layers.
  • the refractive index adjustment layer has a function for adjusting the reflection color and transmission color of the transparent conductive film laminated thereon, or a so-called “bone appearance” in which the patterned portion of the patterned transparent conductive film is visually recognized. It is a layer having a function to suppress.
  • the refractive index adjustment layer for example, a single layer configuration of a high refractive index layer having a refractive index (n1) of 1.60 to 1.80, and a low refractive index having a refractive index (n2) of 1.30 to 1.53.
  • a high refractive index layer having a refractive index (n1) of 1.60 to 1.80 and a low refractive index having a refractive index (n2) of 1.30 to 1.53.
  • the range of the refractive index (n1) of the high refractive index layer is further preferably in the range of 1.63 to 1.78, and more preferably in the range of 1.65 to 1.75.
  • the refractive index (n2) of the low refractive index layer is further preferably in the range of 1.30 to 1.50, more preferably in the range of 1.30 to 1.48, and particularly preferably in the range of 1.33 to 1.46. preferable.
  • the thickness of the refractive index adjusting layer (referring to the total thickness in the case of a multilayer structure) is preferably 200 nm or less, more preferably 150 nm or less, particularly preferably 120 nm or less, and most preferably 100 nm or less.
  • the lower limit thickness is preferably 30 nm or more, more preferably 40 nm or more, particularly preferably 50 nm or more, and most preferably 60 nm or more.
  • the refractive index adjusting layer is preferably a laminated structure of a high refractive index layer and a low refractive index layer from the viewpoint of suppressing “bone appearance”.
  • the sum (nm) of the optical thickness of the high refractive index layer and the optical thickness of the low refractive index layer satisfies (1/4) ⁇ (nm).
  • the optical thickness (nm) is the product of the refractive index and the actual layer thickness (nm)
  • ⁇ is 380 to 780 (nm) which is the wavelength range of the visible light region.
  • n1 represents the refractive index of the high refractive index layer
  • d1 represents the thickness (nm) of the high refractive index layer
  • n2 represents the refractive index of the low refractive index layer
  • d2 represents the thickness (nm) of the low refractive index layer.
  • the total of the optical thickness (n1 ⁇ d1) of the high refractive index layer and the optical thickness (n2 ⁇ d2) of the low refractive index layer is preferably 95 nm or more and 195 nm or less.
  • the total range of the optical thickness of the high refractive index layer and the optical thickness of the low refractive index layer is more preferably 95 to 163 nm, particularly preferably 95 to 150 nm, and most preferably 100 to 140 nm.
  • an active energy ray-curable composition containing metal oxide fine particles having a refractive index of 1.65 or more is applied by a wet coating method, dried as necessary, and then irradiated with active energy rays. Then, it can be formed by curing.
  • the active energy ray-curable composition is a composition containing the polymerizable compound and the photopolymerization initiator described in the first hard coat layer.
  • the metal oxide fine particles include metal oxide particles such as titanium, zirconium, zinc, tin, antimony, cerium, iron, and indium.
  • Specific examples of the metal oxide fine particles include, for example, titanium oxide, zirconium oxide, zinc oxide, tin oxide, antimony oxide, cerium oxide, iron oxide, zinc antimonate, tin oxide-doped indium oxide (ITO), and antimony-doped tin oxide. (ATO), phosphorus-doped tin oxide, aluminum-doped zinc oxide, gallium-doped zinc oxide, fluorine-doped tin oxide, and the like. These metal oxide fine particles may be used alone or in combination.
  • titanium oxide and zirconium oxide are particularly preferable because they can increase the refractive index without reducing transparency.
  • the content of the metal oxide fine particles in the active energy ray-curable composition is preferably 30% by mass or more, more preferably 40% by mass or more, with respect to 100% by mass of the total solid content of the active energy ray-curable composition.
  • a mass% or more is particularly preferred.
  • the upper limit is preferably 70% by mass or less, and preferably 60% by mass or less.
  • the low refractive index layer is, for example, coated with an active energy ray-curable composition containing low refractive index inorganic particles and / or a fluorine-containing compound as a low refractive index material by a wet coating method and, if necessary, dried. It can be formed by irradiating with active energy rays and curing.
  • the active energy ray-curable composition is a composition containing the polymerizable compound and the photopolymerization initiator described in the first hard coat layer.
  • inorganic particles such as silica and magnesium fluoride are preferable. Further, these inorganic particles are preferably hollow or porous.
  • the content of such low refractive index inorganic particles is preferably 10% by mass or more, more preferably 20% by mass or more, and particularly preferably 30% by mass or more with respect to 100% by mass of the total solid content of the active energy ray-curable composition. Is preferred.
  • the upper limit is preferably 70% by mass or less, preferably 60% by mass or less, and particularly preferably 50% by mass or less.
  • the fluorine-containing compound examples include fluorine-containing monomers, fluorine-containing oligomers, and fluorine-containing polymer compounds.
  • the fluorine-containing monomer or fluorine-containing oligomer is a monomer or oligomer having in the molecule thereof the aforementioned polymerizable functional group (functional group containing a carbon-carbon double bond group) and a fluorine atom.
  • fluorine-containing monomers and fluorine-containing oligomers examples include 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (meth) acrylate, and 2- (perfluorobutyl).
  • fluorine-containing polymer compound examples include a fluorine-containing copolymer having a fluorine-containing monomer and a monomer for imparting a crosslinkable group as structural units.
  • fluorine-containing monomer unit examples include, for example, fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3-dioxole, etc.
  • (Meth) acrylic acid partial or fully fluorinated alkyl ester derivatives for example, Biscoat 6FM (manufactured by Osaka Organic Chemical), M-2020 (manufactured by Daikin), etc.), fully or partially fluorinated vinyl ethers, and the like.
  • a monomer for imparting a crosslinkable group in addition to a (meth) acrylate monomer having a crosslinkable functional group in the molecule in advance such as glycidyl methacrylate, it has a carboxyl group, a hydroxyl group, an amino group, a sulfonic acid group, etc. ) Acrylate monomers (for example, (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, etc.).
  • the content of the fluorine-containing compound is preferably 30% by mass or more, more preferably 40% by mass or more, and particularly preferably 50% by mass or more with respect to 100% by mass of the total solid content of the active energy ray-curable composition.
  • the upper limit is preferably 95% by mass or less, more preferably 90% by mass or less, and particularly preferably 80% by mass or less.
  • fluorine-containing monomers and fluorine-containing oligomers are preferably used. Since the fluorine-containing monomer and the fluorine-containing oligomer have a polymerizable functional group in the molecule, they contribute to the formation of a dense cross-linked structure of the low refractive index layer and can have a low refractive index.
  • the transparent conductive film which uses the hard coat film of this embodiment as a base film is preferably used as one of the constituent members of the touch panel.
  • the resistive touch panel usually has a configuration in which an upper electrode and a lower electrode are arranged via a spacer.
  • the transparent conductive film using the hard coat film of this embodiment as a base film has an upper electrode and a lower electrode. It can be used for either one or both of the electrodes.
  • the capacitive touch panel is usually composed of patterned X electrodes and Y electrodes, but the transparent conductive film using the hard coat film of this embodiment as a base film is composed of X electrodes and Y electrodes. It can be used for either one or both.
  • the transparent conductive film used for the touch panel is required to have good transparency and workability (sliding property and blocking resistance), but the transparent conductive film using the hard coat film of this embodiment as a base film. Can sufficiently satisfy the above characteristics.
  • the refractive index of the substrate film was measured at 589 nm using an Abbe refractometer according to JIS K7105 (1981).
  • Measurement device Transmission electron microscope (H-7100FA type, manufactured by Hitachi, Ltd.) ⁇ Measurement conditions: Acceleration voltage 100kV ⁇ Sample preparation: Freezing ultrathin section method ⁇ Magnification: 300,000 times
  • di is the equivalent circular diameter of the particle (the diameter of a circle having the same area as the cross-sectional area of the particle), and N is the number.
  • a black adhesive tape (Nitto Denko “Vinyl Tape No. 21 Tokuhaba Black”) is applied to the surface of the first hard coat layer of the hard coat film, and the reflection color of the second hard coat layer surface is set to three wavelengths in the dark room. It observed visually under the fluorescent lamp and performed on the following references
  • the hard coat film is cut to produce two sheet pieces (20 cm ⁇ 15 cm). The two sheets are superposed such that the first hard coat layer surface and the second hard coat layer surface face each other. Next, a sample in which two sheet pieces are overlapped is sandwiched between glass plates, and a weight of about 3 kg is placed thereon and left in an atmosphere of 50 ° C. and 90% (RH) for 48 hours. Next, the overlapping surface was visually observed to confirm the occurrence of Newton rings, and then both were peeled off and evaluated according to the following criteria.
  • A Newton rings are not generated before peeling, and light peeling is performed without making a peeling sound at the time of peeling.
  • B Some Newton rings are generated before peeling, and peeling is performed while making a small peeling sound during peeling.
  • C Newton rings are generated on the entire surface before peeling, and are peeled off with a loud peeling sound during peeling.
  • Pencil hardness of the first and second hard coat layers The surface of the first hard coat layer and the surface of the first hard coat layer of the hard coat film are based on JIS K5600-5-4 (1999), respectively. It was measured. The load is 750 g, and the speed is 30 mm / min. As the measuring device, a surface hardness tester (HEIDON; type 14DR) manufactured by Shinto Kagaku Co., Ltd. was used. The environment at the time of measurement is 23 ° C. ⁇ 2 ° C. and relative humidity 55% ⁇ 5%.
  • C A pattern part can be visually recognized.
  • Resin layer forming coating solution a In terms of solid content, Tg (glass transition temperature) of 120 ° C. is 26% by mass of polyester resin a, Tg is 80 ° C. of polyester resin b is 54% by mass, melamine-based crosslinking agent is 18% by mass, and particles are 2% by mass. % Was mixed to prepare an aqueous dispersion coating solution.
  • Polyester resin a polyester resin obtained by copolymerizing 43 mol% of 2,6-naphthalenedicarboxylic acid, 7 mol% of 5-sodium sulfoisophthalic acid, and 50 mol% of a diol component containing ethylene glycol; polyester resin b; Polyester resin and melamine-based crosslinking agent obtained by copolymerization of 38 mol% terephthalic acid, 12 mol% trimellitic acid, and 50 mol% diol component containing ethylene glycol; "Nikarac MW12LF” manufactured by Sanwa Chemical Co., Ltd. ⁇ Particles: colloidal silica with an average particle size of 0.19 ⁇ m
  • aqueous dispersion coating solution was prepared by mixing 80% by mass of the following acrylic resin, 18% by mass of the melamine-based crosslinking agent, and 2% by mass of the particles in a solid content mass ratio.
  • Acrylic resin (acrylic resin consisting of the following copolymer composition) Methyl methacrylate 63% by weight Ethyl acrylate 35% by weight Acrylic acid 1% by weight N-methylolacrylamide 1% by weight ⁇ Melamine-based cross-linking agent; “Nicarac MW12LF” manufactured by Sanwa Chemical Co., Ltd. ⁇ Particles: colloidal silica with an average particle size of 0.19 ⁇ m
  • ⁇ Surface treatment silica particle dispersion> 150 parts by mass of colloidal silica (“organosilica sol IPA-ST-ZL” manufactured by Nissan Chemical Industries, Ltd.) is mixed with 13.7 parts by mass of methacryloxypropyltrimethoxysilane and 1.7 parts by mass of a 10% by mass formic acid aqueous solution. , And stirred at 70 ° C. for 1 hour.
  • colloidal silica (“organosilica sol IPA-ST-ZL” manufactured by Nissan Chemical Industries, Ltd.)
  • Example 1 A hard coat film was prepared in the following manner.
  • a resin layer was in-line coated on both sides of a polyethylene terephthalate film (PET film) having a refractive index of 1.65 and a thickness of 100 ⁇ m within the PET film manufacturing process. That is, the coating liquid a for forming a resin layer is applied to both surfaces of a PET film uniaxially stretched in the longitudinal direction by a bar coating method, dried at 100 ° C., then biaxially stretched in the width direction, and heated at 230 ° C. for 20 seconds. The PET film in which the resin layer was laminated
  • the following active energy ray-curable composition a is applied by a gravure coating method on a resin layer on one side of a PET film having a resin layer laminated on both sides, dried at 90 ° C., and then irradiated with ultraviolet rays 400 mJ / cm 2 . And cured to form a first hard coat layer.
  • the first hard coat layer had a thickness of 2.6 ⁇ m and a refractive index of 1.51.
  • the second hard coat is applied to the resin layer on the other side of the PET film (the side opposite to the side on which the first hard coat layer is laminated) using the active energy ray-curable composition a in the same manner as described above.
  • a layer was formed to prepare a hard coat film.
  • the second hard coat layer had a thickness of 2.6 ⁇ m and a refractive index of 1.51.
  • Example 2 A hard coat film was produced in the same manner as in Example 1 except that the second hard coat layer was changed to the following active energy ray-curable composition b.
  • the second hard coat layer had a thickness of 2.6 ⁇ m and a refractive index of 1.52.
  • Example 3 A hard coat film was produced in the same manner as in Example 1 except that the active energy ray-curable composition for forming the first and second hard coat layers was changed to the following active energy ray-curable composition c. .
  • the first and second hard coat layers each had a thickness of 2.6 ⁇ m and a refractive index of 1.51.
  • Example 4 A hard coat film was produced in the same manner as in Example 3 except that the second hard coat layer was changed to the active energy ray-curable composition b.
  • the second hard coat layer had a thickness of 2.6 ⁇ m and a refractive index of 1.52.
  • Example 5 A hard coat film was produced in the same manner as in Example 1 except that the active energy ray-curable composition for forming the first and second hard coat layers was changed to the following active energy ray-curable composition d. .
  • the first and second hard coat layers each had a thickness of 2.6 ⁇ m and a refractive index of 1.51.
  • Example 6 A hard coat film was produced in the same manner as in Example 5 except that the second hard coat layer was changed to the active energy ray-curable composition b.
  • the second hard coat layer had a thickness of 2.6 ⁇ m and a refractive index of 1.52.
  • Example 7 A hard coat film was produced in the same manner as in Example 1 except that the active energy ray-curable composition for forming the first and second hard coat layers was changed to the following active energy ray-curable composition e. .
  • the first and second hard coat layers each had a thickness of 2.6 ⁇ m and a refractive index of 1.51.
  • ⁇ Active energy ray-curable composition e 50 parts by mass of dipentaerythritol hexaacrylate, 37 parts by mass of an acrylate compound (“Aronix M111” manufactured by Toa Gosei Co., Ltd.), 8 parts by mass of the surface-treated silica particle dispersion D in terms of solid content, a photopolymerization initiator (Ciba 5 parts by mass of “Irgacure 184” manufactured by Specialty Chemicals Co., Ltd. was mixed with an organic solvent (methyl ethyl ketone).
  • Example 8 A hard coat film was produced in the same manner as in Example 7 except that the second hard coat layer was changed to the active energy ray-curable composition b.
  • the second hard coat layer had a thickness of 2.6 ⁇ m and a refractive index of 1.52.
  • Example 9 A hard coat film was produced in the same manner as in Example 1 except that the active energy ray-curable composition for forming the first and second hard coat layers was changed to the following active energy ray-curable composition f. .
  • the first and second hard coat layers each had a thickness of 2.6 ⁇ m and a refractive index of 1.51.
  • Example 10 A hard coat film was produced in the same manner as in Example 9 except that the second hard coat layer was changed to the active energy ray-curable composition b.
  • the second hard coat layer had a thickness of 2.6 ⁇ m and a refractive index of 1.52.
  • Example 1 A hard coat film was produced in the same manner as in Example 1 except that the active energy ray-curable composition for forming the first and second hard coat layers was changed to the following active energy ray-curable composition g. .
  • the first and second hard coat layers each had a thickness of 2.6 ⁇ m and a refractive index of 1.51.
  • organic solvent a mixed solvent of methyl ethyl ketone and cyclohexanone having a mass ratio of 8: 2.
  • Comparative Example 2 A hard coat film was produced in the same manner as in Comparative Example 1 except that the second hard coat layer was changed to the active energy ray-curable composition b.
  • the second hard coat layer had a thickness of 2.6 ⁇ m and a refractive index of 1.52.
  • Example 3 A hard coat film was produced in the same manner as in Example 1 except that the active energy ray-curable composition for forming the first and second hard coat layers was changed to the following active energy ray-curable composition h. .
  • the first and second hard coat layers each had a thickness of 2.6 ⁇ m and a refractive index of 1.52.
  • Comparative Example 4 A hard coat film was produced in the same manner as in Comparative Example 3 except that the second hard coat layer was changed to the active energy ray-curable composition b.
  • the second hard coat layer had a thickness of 2.6 ⁇ m and a refractive index of 1.52.
  • Example 11 A hard coat film was produced in the same manner as in Example 1 except that the active energy ray-curable composition for forming the first and second hard coat layers was changed to the following active energy ray-curable composition i. .
  • the first and second hard coat layers each had a thickness of 2.6 ⁇ m and a refractive index of 1.51.
  • Example 12 A hard coat film was produced in the same manner as in Example 1 except that the active energy ray-curable composition for forming the first and second hard coat layers was changed to the following active energy ray-curable composition j. .
  • the first and second hard coat layers each had a thickness of 2.6 ⁇ m and a refractive index of 1.51.
  • Example 13 A hard coat film was produced in the same manner as in Example 1 except that the active energy ray-curable composition for forming the first and second hard coat layers was changed to the following active energy ray-curable composition k. .
  • the first and second hard coat layers each had a thickness of 2.6 ⁇ m and a refractive index of 1.51.
  • ⁇ Active energy ray-curable composition k 50 parts by mass of dipentaerythritol hexaacrylate, 35 parts by mass of an acrylate compound (“Aronix M111” manufactured by Toa Gosei Co., Ltd.), 10 parts by mass of the surface-treated silica particle dispersion A in terms of solid content, a photopolymerization initiator (Ciba 5 parts by mass of “Irgacure 184” manufactured by Specialty Chemicals Co., Ltd. was mixed with an organic solvent (methyl ethyl ketone).
  • Example 14 A hard coat film was produced in the same manner as in Example 1 except that the active energy ray-curable composition for forming the first and second hard coat layers was changed to the following active energy ray-curable composition l. .
  • the first and second hard coat layers each had a thickness of 2.6 ⁇ m and a refractive index of 1.51.
  • ⁇ Active energy ray-curable composition l 50 parts by mass of dipentaerythritol hexaacrylate, 33 parts by mass of an acrylate compound (“Aronix M111” manufactured by Toa Gosei Co., Ltd.), 12 parts by mass of the surface-treated silica particle dispersion A in terms of solid content, a photopolymerization initiator (Ciba 5 parts by mass of “Irgacure 184” manufactured by Specialty Chemicals Co., Ltd. was mixed with an organic solvent (methyl ethyl ketone).
  • Example 5 A hard coat film was produced in the same manner as in Example 1 except that the active energy ray-curable composition for forming the first and second hard coat layers was changed to the following active energy ray-curable composition m. .
  • the first and second hard coat layers each had a thickness of 2.6 ⁇ m and a refractive index of 1.51.
  • Example 6 A hard coat film was produced in the same manner as in Example 1 except that the active energy ray-curable composition for forming the first and second hard coat layers was changed to the following active energy ray-curable composition n. .
  • the first and second hard coat layers each had a thickness of 2.6 ⁇ m and a refractive index of 1.51.
  • first and second hard coat layers were laminated on the above resin layer-laminated PET film in the same manner as in Comparative Example 5 to produce a hard coat film.
  • the first and second hard coat layers each had a thickness of 2.6 ⁇ m and a refractive index of 1.51.
  • Example 15 to 24 An ITO film as a transparent conductive film was laminated on the surface of the second hard coat layer of each of the hard coat films of Examples 1 to 10 by a sputtering method to produce a transparent conductive film. The slipperiness and blocking resistance of these transparent conductive films were evaluated. The results are shown in Table 4.
  • the evaluation of the slipperiness and blocking resistance of the transparent conductive film was conducted in the above-mentioned "(14) Evaluation of slipperiness” and "(15) Evaluation of blocking resistance” and the surface of the first hard coat layer was transparent. Evaluation was performed in the same manner except that the layers were overlapped so that the surface of the conductive film faced.
  • the transparent conductive films of Examples 15 to 24 were all good in slipping property and blocking resistance.
  • Examples 25 to 29 The following high refractive index layer and low refractive index layer were laminated in this order on the surface of the second hard coat layer of the hard coat films of Examples 2, 4, 6, 8, and 10, and then on the low refractive index layer.
  • the following transparent conductive film was formed to produce a transparent conductive film for a capacitive touch panel.
  • ⁇ Lamination of low refractive index layer> The following active energy ray-curable composition for forming a low refractive index layer is applied by a gravure coating method, dried at 90 ° C., and then cured by irradiation with ultraviolet rays of 400 mJ / cm 2 to form a low refractive index layer having a thickness of 40 nm. Formed.
  • the refractive index of this low refractive index layer was 1.40.
  • Di- ( ⁇ -fluoroacrylic acid) -2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-heptadecafluorononylethylene glycol It was prepared by dispersing or dissolving 87 parts by mass, 10 parts by mass of dipentaerythritol hexaacrylate, and 3 parts by mass of a photopolymerization initiator (“Irgacure 184” manufactured by Ciba Specialty Chemicals Co., Ltd.) in an organic solvent (methyl ethyl ketone).
  • An ITO film was laminated by a sputtering method so as to have a thickness of 25 nm, and a transparent conductive film was formed by pattern processing (etching treatment) into a lattice pattern.
  • the evaluation of the slipperiness and blocking resistance of the transparent conductive film was conducted in the above-mentioned "(14) Evaluation of slipperiness” and "(15) Evaluation of blocking resistance” and the surface of the first hard coat layer was transparent. Evaluation was performed in the same manner except that the layers were overlapped so that the surface of the conductive film faced.
  • Examples 31 to 40 As shown below, five types of coating liquids for forming a resin layer having different wetting tensions were prepared.
  • Polyester resin c a polyester resin composed of 43 mol% of 2,6-naphthalenedicarboxylic acid / 5 mol% of 5-sodium sulfoisophthalic acid / 45 mol% of ethylene glycol / 5 mol% of diethylene glycol.
  • Polyester resin d polyester resin composed of terephthalic acid 38 mol% / trimellitic acid 12 mol% / ethylene glycol 45 mol% / diethylene glycol 5 mol%.
  • Particles colloidal silica having an average particle size of 0.19 ⁇ m.
  • Epoxy-based crosslinking agent 1,3-bis (N, N-diglycidylamine) cyclohexane surfactant, polyoxyethylene lauryl ether particle, colloidal silica having an average particle size of 0.19 ⁇ m.
  • polyester resin f a polyester resin composed of terephthalic acid 30 mol% / isophthalic acid 15 mol% / 5-sodium sulfoisophthalic acid 5 mol% / ethylene glycol 30 mol% / 1,4-butanediol 20 mol%.
  • Acrylic resin b acrylic resin composed of 75 mol% of methyl methacrylate / 22 mol% of ethyl acrylate / 1 mol% of acrylic acid / 2 mol% of N-methylolacrylamide ⁇ Melamine cross-linking agent; manufactured by Sanwa Chemical Co., Ltd. "Nikarak MW12LF" -Surfactant; Polyoxyethylene lauryl ether-Particles; Colloidal silica having an average particle size of 0.19 ⁇ m.
  • Polyester copolymer g A polyester copolymer composed of terephthalic acid 32 mol% / isophthalic acid 12 mol% / 5-sodium sulfoisophthalic acid 6 mol% / ethylene glycol 46 mol% / diethylene glycol 4 mol%.
  • Acrylic resin c an acrylic copolymer composed of 70 mol% methyl methacrylate / 22 mol% ethyl acrylate / 4 mol% N-methylolacrylamide / 4 mol% N, N-dimethylacrylamide.
  • Melamine-based cross-linking agent “Nicarac MW12LF” manufactured by Sanwa Chemical Co., Ltd. -Surfactant; Polyoxyethylene lauryl ether-Particles; Colloidal silica having an average particle size of 0.19 ⁇ m.
  • a coating liquid was prepared by mixing 85% by mass of urethane resin, 5% by mass of epoxy-based crosslinking agent, 9% by mass of surfactant, and 1% by mass of particles in a solid content mass ratio.
  • -Urethane resin "Hydran AP-20" manufactured by Dainippon Ink & Chemicals, Inc. ⁇ Epoxy-based cross-linking agent; triethylene glycol diglycidyl ether ⁇ surfactant; polyoxyethylene lauryl ether ⁇ particles;
  • a hard coat film was prepared in the following manner.
  • a resin layer was in-line coated on both sides of a polyethylene terephthalate film (PET film) having a refractive index of 1.65 and a thickness of 100 ⁇ m within the PET film manufacturing process. That is, the resin layer forming coating solution c is applied to both surfaces of a PET film uniaxially stretched in the longitudinal direction by a bar coating method, dried at 100 ° C., then biaxially stretched in the width direction and heated at 230 ° C. for 20 seconds. The PET film in which the resin layer was laminated
  • PET film polyethylene terephthalate film having a refractive index of 1.65 and a thickness of 100 ⁇ m within the PET film manufacturing process. That is, the resin layer forming coating solution c is applied to both surfaces of a PET film uniaxially stretched in the longitudinal direction by a bar coating method, dried at 100 ° C.,
  • the active energy ray-curable composition a used in Example 1 was applied by the gravure coating method on the resin layer on one side of the PET film having the resin layers laminated on both sides, dried at 90 ° C., and then irradiated with ultraviolet rays 400 mJ. / Cm 2 was irradiated and cured to form a first hard coat layer.
  • the thickness of the first hard coat layer was 1.6 ⁇ m.
  • the active energy ray-curable composition b used in Example 2 is formed in the same manner as above on the resin layer on the other side of the PET film (the side opposite to the side on which the first hard coat layer is laminated).
  • a second hard coat layer was formed to produce a hard coat film.
  • the thickness of this second hard coat layer was 1.6 ⁇ m.
  • Examples 32 to 35 A hard coat film was produced in the same manner as in Example 31 except that the resin layer forming coating solution was changed as shown in Table 6.
  • Examples 36 to 40 A hard coat film was produced in the same manner as in Examples 31 to 35 except that the thickness of the first hard coat layer was changed to 2.6 ⁇ m and the thickness of the second hard coat layer was changed to 2.6 ⁇ m. .
  • Particles are likely to be unevenly distributed in the vicinity of the surface, and as a result, protrusions made of particles are efficiently formed. Moreover, by making the thickness of the first hard coat layer less than 2 ⁇ m, the haze value becomes smaller and the transparency is improved.
  • Protrusion 11 Protrusion 20 Horizontal straight line 30 Vertical straight line

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Abstract

La présente invention se rapporte à un film de revêtement dur qui est caractérisé par les éléments suivants : une première couche de revêtement dur qui contient des particules, est agencée sur au moins une surface d'un film de base ; des saillies formées par les particules sont présentes sur la surface de la première couche de revêtement dur à une densité qui varie entre 300 et 4 000 par 100 μm2 ; la rugosité moyenne de ligne médiane (Ra1) de la surface de la première couche de revêtement dur est inférieure à 30 nm et la valeur de trouble est inférieure à 1,5 %. Le film de revêtement dur présente une transparence élevée, une bonne glissance et des propriétés d'anti-adhérence.
PCT/JP2013/079968 2012-11-27 2013-11-06 Film de revêtement dur et film conducteur transparent Ceased WO2014084008A1 (fr)

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KR1020157010588A KR101563564B1 (ko) 2012-11-27 2013-11-06 하드 코트 필름 및 투명 도전성 필름

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