JP6103306B2 - Laminated film and transparent conductive film - Google Patents

Description

  The present invention relates to a laminated film having high transparency and good blocking resistance, and more particularly to a laminated film suitable for a transparent conductive film.

  A laminated film in which an active energy ray-curable resin layer is laminated on a base film is used as a surface protective film (hard coat film) or optical film (antireflection film) for displays and touch panels, or as a base for transparent conductive films for touch panels. It is used as a film.

  The laminated film used for these applications is required to have high transparency and good blocking resistance.

  In order to improve the blocking resistance of the hard coat film, it has been proposed to provide protrusions with particles on the surface (Patent Documents 1 to 4).

JP 2010-122323 A JP 2010-241937 A JP 2011-68087 A JP 2011-136490 A

  Regarding the thickness of the hard coat layer in the hard coat film, it is preferable that the thickness of the hard coat layer is relatively small from the viewpoints of curling suppression, productivity, raw material costs, transparency, and the like. For example, the thickness of the hard coat layer is preferably less than 2 μm. However, when the thickness of the hard coat layer is reduced, the blocking resistance tends to decrease.

  The above patent document does not disclose a technique for simultaneously satisfying transparency and blocking resistance in a hard coat layer having a relatively small thickness (for example, a hard coat layer having a thickness of less than 2 μm).

  Therefore, in view of the above-mentioned problems of the prior art, the object of the present invention is high transparency and blocking resistance even when the thickness of the active energy ray-curable resin layer is relatively small (less than 2 μm). It is in providing a favorable laminated film. Another object of the present invention is to provide a laminated film suitable for a transparent conductive film.

The above object of the present invention has been achieved by the following invention.
[1] A resin layer is laminated on at least one surface of a base film, and a first active energy ray-curable resin layer is laminated directly on the resin layer, and the first active energy ray-curable resin layer Is a laminated film containing particles and having protrusions formed by the particles on the surface of the first active energy ray-curable resin layer, wherein the thickness (d) of the first active energy ray-curable resin layer is less than 2 μm, 1 The ratio (r / d) of the average particle diameter (r: μm) of the particles to the thickness (d: μm) of the active energy ray-curable resin layer is 0.5 or less, and the wetting tension of the resin layer surface Is 52 mN / m or less, The laminated film characterized by the above-mentioned.
[2] The laminated film according to [1], wherein the laminated film has a haze value of 0.5% or less.
[3] The laminated film according to [1] or [2], wherein the base film is a polyethylene terephthalate film.
[4] The laminated film according to any one of [1] to [3], wherein the centerline average roughness (Ra1) of the surface of the first active energy ray-curable resin layer is less than 30 nm.
[5] The laminated film according to any one of [1] to [4], wherein the average particle diameter (r) of the particles is in the range of 0.03 to 0.5 μm.
[6] The content of particles in the first active energy ray-curable resin layer is 3 to 17% by mass with respect to 100% by mass of the total solid content of the first active energy ray-curable resin layer. ] The laminated film according to any one of [5] to [5].
[7] The substrate film has a second active energy ray-curable resin layer on the opposite side of the surface on which the first active energy ray-curable resin layer is provided, with an easy-adhesion layer interposed therebetween. Any of [1] to [6] above, wherein the energy ray curable resin layer has a thickness of less than 2.5 μm and a center line average roughness (Ra2) of the second active energy ray curable resin layer surface of 25 nm or less. The laminated film of crab.
[8] The base film is a polyethylene terephthalate film having a refractive index of 1.61-1.70, the refractive index of the easy-adhesion layer is 1.55-1.60, and the second active energy ray curing is performed. The laminated film according to [7], wherein the refractive index of the conductive resin layer is 1.48 to 1.54.
[9] A transparent conductive film having a transparent conductive film on at least one surface of the laminated film according to any one of [1] to [8].

  According to the present invention, a laminated film having high transparency and good blocking resistance can be provided. The laminated film of the present invention is suitable for a base film of a transparent conductive film.

FIG. 1 is an example of a surface photograph taken by a scanning electron microscope on the surface of the first active energy ray-curable resin layer of the present invention. FIG. 2 is an example of a surface photograph taken by a scanning electron microscope on the surface of the first active energy ray-curable resin layer of the present invention. FIG. 3 is an example of a surface photograph taken by a scanning electron microscope on the surface of the first active energy ray-curable resin layer of the present invention.

  In the laminated film of the present invention, a resin layer is laminated on at least one surface of a base film, and a first active energy ray-curable resin layer is laminated directly on the resin layer.

  The thickness (d) of the first active energy ray-curable resin layer is less than 2 μm, and the ratio of the average particle diameter (r: μm) of the particles to the thickness (d: μm) of the first active energy ray-curable resin layer It contains particles having (r / d) of 0.5 or less, and has projections formed by these particles on the surface of the active energy ray-curable resin layer. The resin layer has a surface wetting tension of 52 mN / m or less.

In the present invention, having the protrusions due to particles on the surface of the first active energy ray-curable resin layer was measured in detail by the method described later, and the average height and number of protrusions on the surface of the first active energy ray-curable resin layer were measured. Sometimes, it means that the average height of the protrusions is 0.02 μm or more, and there are two or more protrusions on an average of 2 μm square (area 4 μm ² ). Details of the measurement method and determination method are shown in the examples.

  It is important that the thickness (d) of the first active energy ray-curable resin layer is less than 2 μm. By setting the thickness of the first active energy ray-curable resin layer to less than 2 μm, the transparency of the first active energy ray-curable resin layer is increased (the haze value is reduced) and curling of the laminated film is suppressed. There are advantages such as improved productivity, reduced raw material costs, and the like.

  The first active energy ray-curable resin layer contains particles having an average particle diameter (r: μm) of 0.5 times or less of the thickness (d: μm), and has protrusions formed by the particles. That is, in the present invention, the ratio (r / d) of the average particle diameter (r: μm) of the particles to the thickness (d: μm) of the first active energy ray-curable resin layer is 0.5 or less. is important. When the first active energy ray-curable resin layer contains particles satisfying such a relationship, the transparency is improved, and the protrusions formed by the particles are formed on the surface of the first active energy ray-curable resin layer. Good blocking resistance.

  However, when protrusions are formed on the first active energy ray-curable surface by such particles (particles having an average particle diameter (r: μm) of 0.5 times or less of the thickness (d: μm)), the first activity If the thickness (d) of the energy ray curable resin layer is less than 2 μm, sufficient protrusions that can provide good blocking resistance may not be stably formed.

  Therefore, by directly laminating the first active energy ray-curable resin layer having the above-described configuration on the resin layer having a wetting tension of 52 mN / m or less, particles are formed on the surface of the first active energy ray-curable resin layer. Protrusions are easily formed, and as a result, it has been found that a laminated film having good blocking resistance can be obtained, and the present invention has been achieved.

  Hereinafter, each component which comprises the laminated | multilayer film of this invention is demonstrated in detail.

[Base film]
The base film of the present invention is preferably a plastic film. Examples of 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. 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, uniaxially stretching, or biaxially stretching these resins can be used as a base film.

  Among the above-mentioned substrate films, polyester films are preferred because of their excellent transparency, dimensional stability, mechanical properties, heat resistance, electrical properties, chemical resistance, etc., and particularly polyethylene terephthalate films (PET films). Among these, a biaxially stretched PET film is preferably used.

  The range of 20-300 micrometers is suitable for the thickness of a base film, the range of 30-200 micrometers is preferable, and the range of 50-150 micrometers is more preferable.

[Resin layer]
The resin layer is provided between the base film and the first active energy ray-curable resin layer. The resin layer is preferably laminated directly on the base film. The resin layer preferably has a function of improving the adhesion between the base film and the first active energy ray-curable resin layer.

  The resin layer has a surface wetting tension of 52 mN / m or less. When the wetting tension on the surface of the resin layer exceeds 52 mN / m, sufficient protrusions due to particles are not formed on the surface of the first active energy ray-curable resin layer, and good blocking resistance cannot be obtained.

  The wetting tension on the surface of the resin layer is further 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 particularly preferably 40 mN / m or more. When the wetting tension on the surface of the resin layer is less than 35 mN / m, the adhesion of the first active energy ray-curable resin layer may be lowered.

  From the above viewpoint, that is, from the viewpoint of sufficiently forming projections by particles on the surface of the first active energy ray-curable resin layer, and the adhesion between the base film and the first active energy ray-curable resin layer From the viewpoint of improving the thickness, the thickness of the resin layer is preferably 0.005 μm or more, more preferably 0.01 μm or more, and particularly preferably 0.015 μm or more. The upper limit is preferably 0.3 μm or less, preferably 0.2 μm or less, particularly preferably 0.15 μm or less. When the thickness of the resin layer exceeds 0.3 μm, the hardness and blocking resistance after the first active energy ray-curable resin layer is laminated may be lowered.

  The resin layer is a layer containing a resin as a main component. That is, 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. Further, 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. The upper limit is preferably 98% by mass or less, more preferably 95% by mass or less, and particularly preferably 90% by mass or less.

  Examples of the resin constituting 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.

  From the viewpoint of controlling the wetting tension on the surface of the resin layer to 52 mN / m or less, and from the viewpoint of improving the adhesion between the base film and the first active energy ray-curable resin layer, Is preferably at least one selected from the group consisting of a polyester resin, an acrylic resin and a polyurethane resin, more preferably a polyester resin and / or an acrylic resin, and particularly at least a polyester resin as the resin. Is preferred.

  The polyester resin has an ester bond in the main chain or side chain. For example, a polyester resin obtained by polycondensation from a polyvalent carboxylic acid component and a diol component can be used.

  Examples of the polyvalent carboxylic acid component include terephthalic acid, isophthalic acid, orthophthalic acid, phthalic acid, 2,5-dimethylterephthalic acid, 5-sodium sulfoisophthalic acid, 1,4-naphthalenedicarboxylic acid, and 2,6-naphthalene. Dicarboxylic acid, biphenyldicarboxylic acid, 1,2-bisphenoxyethane-p, p'-dicarboxylic acid, phenylindanedicarboxylic acid, succinic acid, adipic acid, sebacic acid, dodecanedioic acid, dimer acid, 1,3-cyclopentane Dicarboxylic acids such as dicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, 4-methylcyclohexene-1,2, 3-tricarboxylic acid, trimesic acid, 1,2,3 4-butanetetracarboxylic acid, 1,2,3,4-pentanetetracarboxylic acid, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, 5- (2,5-dioxotetrahydrofurfuryl) -3 -Methyl-3-cyclohexene-1,2-dicarboxylic acid, 5- (2,5-dioxotetrahydrofurfuryl-3-cyclohexene-1,2-dicarboxylic acid, cyclopentanetetracarboxylic acid, 2,3,6, 7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, ethylene glycol bistrimellitate, 2,2 ′, 3,3′-diphenyltetracarboxylic acid, thiophene-2,3,4,5 -Trivalent or higher polyvalent carboxylic acids such as tetracarboxylic acid and ethylenetetracarboxylic acid.

  Examples of the diol component include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1, 6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 2,4-dimethyl-2-ethylhexane-1,3-diol, Neopentyl glycol, 2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-2-isobutyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,2,4 -Trimethyl-1,6-hexanediol, 1,2-cyclohexanedi Tanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 4,4′-thiodiphenol, bisphenol A, 4, 4'-methylenediphenol, 4,4 '-(2-norbornylidene) diphenol, 4,4'-dihydroxybiphenol, o-, m-, and p-dihydroxybenzene, 4,4'-isopropylidenephenol, 4 , 4′-isopropylidenevindiol, cyclopentane-1,2-diol, cyclohexane-1,2-diol, cyclohexane-1,4-diol, and the like.

  Further, in order to facilitate the water-solubilization or water-dispersion of the polyester resin, a trivalent or higher polyvalent carboxylic acid or a dicarboxylic acid having a sulfo group is copolymerized to form a hydrophilic group (carboxyl group or sulfo group) on the side chain. It is preferable to use a polyester resin having a group.

  Examples of the acrylic resin include a copolymer selected from methyl methacrylate, ethyl acrylate, n-butyl acrylate, 2-hydroxyethyl acrylate, acrylamide, N-methylol acrylamide, N, N-dimethyl acrylamide, and glycidyl methacrylate. Furthermore, it is preferable to copolymerize a compound having a sulfo group or a compound having a carboxyl group (such as acrylic acid or methacrylic acid) in order to facilitate the water-solubilization or water-dispersion of the acrylic resin.

  The resin layer preferably further contains a crosslinking agent. The resin layer is a layer formed using the above-described resin and a crosslinking agent, and is preferably a layer cured by heat (thermosetting layer). By making the resin layer such a thermosetting layer, the adhesion between the base film and the first active energy ray-curable resin layer can be further improved. 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 upper limit is preferably 300 ° C. or lower. The heating time is preferably in the range of 5 to 300 seconds, and more preferably in the range of 10 to 200 seconds.

  Examples of the crosslinking agent 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. Among these, melamine crosslinking agents, oxazoline crosslinking agents, carbodiimide crosslinking agents, isocyanate crosslinking agents, aziridine crosslinking agents, and epoxy 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 content of the crosslinking agent in the resin layer is preferably in the range of 0.5 to 30% by mass, more preferably in the range of 1 to 25% by mass, particularly 2 to 20% by mass with respect to 100% by mass of the total solid content of the resin layer. % Range is preferred.

  The wetting tension on the surface of the resin layer can also 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 resin layer can further contain a surfactant. Examples of such surfactants include polyoxyethylene alkylphenyl ether, polyoxyethylene-fatty acid ester, sorbitan fatty acid ester, glycerin fatty acid ester, fatty acid metal soap, alkyl sulfate, alkyl sulfonate, alkyl sulfosuccinate, Examples thereof include quaternary ammonium tallow salt, alkylamine hydrochloride, betaine type surfactant and the like.

  The content of the surfactant in the resin layer is preferably in the range of 0.1 to 20% by mass and more preferably in the range of 0.5 to 15% by mass with respect to 100% by mass of the total solid content of the resin layer.

  It is preferable that a resin layer contains particle | grains from a viewpoint of ensuring appropriate slipperiness and winding-up property in the manufacturing process of a laminated film.

  The particles to be contained in the resin layer are not particularly limited, but inorganic particles such as silica, titanium oxide, aluminum oxide, zirconium oxide, calcium carbonate, zeolite, acrylic particles, silicone particles, polyimide particles, Teflon (registered trademark) particles, etc. Organic particles. The organic particles may be crosslinked polymer particles such as crosslinked polyester particles and crosslinked polystyrene particles, or may be core-shell particles. Among these, silica particles are preferable, and colloidal silica is particularly preferable.

  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 0.5% relative to 100% by mass of the total solid content of the resin layer. A range of ˜5 mass% is preferred. When 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. When the content of the particles exceeds 10% by mass, the transparency is lowered. Or the applicability of the first active energy ray-curable resin layer may deteriorate, or the adhesion between the base film and the first active energy ray-curable resin layer may be reduced.

  The particles contained in the resin layer preferably have an average particle size larger than the thickness of the resin layer. Specifically, the average particle diameter of the particles 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.

  By directly laminating the first active energy ray-curable resin layer of the present invention on a resin layer containing particles having an average particle size larger than the thickness of the resin layer, blocking resistance is further improved.

  The average particle size of the particles to be contained in the resin layer is appropriately selected according to the thickness design of the resin layer. Specifically, the average particle size of the particles is preferably in the range of 0.02 to 1 μm. A range of 05 to 0.7 μm is more preferable, and a range of 0.1 to 0.5 μm is particularly preferable. If the average particle size of the particles is less than 0.02 μm, the blocking resistance may be lowered. If the average particle diameter of the particles exceeds 1 μm, the particles may fall off, the transparency may be lowered, or the appearance may be deteriorated.

  It is preferable that the resin layer is applied on the base film by a wet coating method, heated and cured to be laminated. Further, 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 heated and cured to be 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.

[First active energy ray-curable resin layer]
The first active energy ray-curable resin layer has a thickness of less than 2 μm. By setting the thickness of the first active energy ray-curable resin layer to less than 2 μm, the transparency of the first active energy ray-curable resin layer is increased (the haze value is reduced) and curling of the laminated film is suppressed. There are advantages such as improved productivity, reduced raw material costs, and the like.

  From the above viewpoint, the thickness of the first active energy ray-curable resin layer is preferably 1.7 μm or less, more preferably 1.5 μm or less, and particularly preferably 1.3 μm or less. The lower limit thickness is preferably 0.5 μm or more, and more preferably 0.7 μm or more from the viewpoint of imparting hard coat properties and suppressing oligomer precipitation from the base film.

  The first active energy ray-curable resin layer contains particles, and protrusions due to the particles are formed on the surface of the first active energy ray-curable resin layer.

  The ratio (r / d) of the average particle diameter (r: μm) of the particles contained in the first active energy ray-curable resin layer to the thickness (d: μm) of the first active energy ray-curable resin layer is 0. It is important that it is 5 or less. When the ratio (r / d) exceeds 0.5, the haze value of the first active energy ray-curable resin layer increases, and the transparency decreases.

  The ratio (r / d) is further preferably 0.4 or less, more preferably 0.3 or less, and particularly preferably 0.2 or less. The lower limit is preferably 0.01 or more, more preferably 0.02 or more, and particularly preferably 0.03 or more. When the ratio (r / d) is less than 0.01, protrusions due to particles are not sufficiently formed on the surface of the first active energy ray-curable resin layer, and good blocking resistance may not be obtained.

  Specifically, the average particle diameter (r) of the particles contained in the first active energy ray-curable resin layer is preferably in the range of 0.03 to 0.5 μm, more preferably in the range of 0.04 to 0.4 μm. A range of 0.05 to 0.3 μm is particularly preferable.

  When the average particle diameter (r) of the particles contained in the first active energy ray-curable resin layer is less than 0.03 μm, good blocking resistance may not be obtained, while the average particle diameter (r) is If it exceeds 0.5 μm, the haze value may increase and transparency may be lowered.

  The protrusions formed by the particles on the surface of the first active energy ray-curable resin layer may form protrusions individually or in a state where a plurality of particles are aggregated. May be.

  FIG. 1 is an example of a surface photograph when individual particles independently form individual protrusions. FIG. 2 is an example of a surface photograph when a plurality of particles are randomly aggregated to form protrusions. FIG. 3 is an example of a surface photograph when a plurality of particles aggregate in a bead shape to form protrusions. 1 to 3 are surface photographs when the surface of the first active energy ray-curable resin layer is observed with a scanning electron microscope (SEM).

The number of protrusions on the surface of the first active energy ray-curable resin layer is preferably 200 or more per unit area (100 μm ² ) on the surface of the first active energy ray-curable resin layer, and is preferably 300 or more. More preferably, it is particularly preferably 400 or more. The upper limit is preferably 10,000 or less, more preferably 7000 or less, and particularly preferably 4000 or less. Here, the number of protrusions means a protrusion formed by one particle.

  In FIG. 1, since one projection is formed by one particle, the numerical value obtained by measuring the projection per unit area in the surface photograph is the number of projections per unit area.

  In FIG. 2 and FIG. 3, a plurality of particles form protrusions in an aggregated state, but individual particles forming protrusions are adjusted by adjusting the magnification of surface observation with a scanning electron microscope (SEM). The number of particles forming protrusions can be measured.

When the number of protrusions on the surface of the first active energy ray-curable resin layer is less than 200/100 μm ² , good blocking resistance may not be obtained. On the other hand, if the number of protrusions exceeds 10,000 / 100 μm ² , the haze value may increase and transparency may decrease.

  The average height of the protrusions is preferably in the range of 0.02 to 0.3 μm, more preferably in the range of 0.03 to 0.25 μm, and particularly preferably in the range of 0.04 to 0.2 μm. If the average height of the protrusions is less than 0.02 μm, good blocking resistance may not be obtained. On the other hand, when the average height of the protrusions exceeds 0.3 μm, the haze value increases and transparency may be lowered.

  The height of the protrusions can be measured from a cross-sectional photograph taken with a transmission electron microscope (TEM) of the first active energy ray-curable resin layer.

  In order to form protrusions as described above, the content of the particles contained in the first active energy ray-curable resin layer is 3 with respect to 100% by mass of the total solid content of the first active energy ray-curable resin layer. The range of -17 mass% is preferable, the range of 4-15 mass% is more preferable, The range of 5-12 mass% is especially preferable. When the content of the particles is less than 3% by mass, the blocking resistance may be lowered, and when the content of the particles exceeds 17% by mass, the haze value may be increased and the transparency may be lowered.

  Examples of the particles to be contained in the first active energy ray curable resin layer include organic particles and inorganic particles.

As the resin constituting the organic particles, an acrylic resin, a styrene resin, a polyester resin, a polyurethane resin, a polycarbonate resin, a polyamide resin, a silicone resin, a fluorine resin, or 2 used for the synthesis of the above resin. Examples thereof include copolymer resins of more than one type of monomer. Among these, acrylic resin particles are preferably used. As acrylic resin particles, acrylic resin particles, methacrylic resin particles, acrylic monomers or methacrylic monomers and other monomers (for example, styrene, urethane acrylate, urethane methacrylate, polyester acrylate, polyester) And copolymer resin particles such as methacrylate, silicone acrylate, and silicone methacrylate).

  These organic particles are preferably synthesized by an emulsion polymerization method, and organic particles having an average particle size of 0.5 μm or less can be obtained by synthesis by an emulsion polymerization method.

  Examples of the inorganic particles include inorganic particles such as silica, titanium oxide, aluminum oxide, zirconium oxide, calcium carbonate, and zeolite. Among these, silica particles are preferable, and colloidal silica is particularly preferable.

  The first active energy ray curable resin is composed of particles having a ratio (r / d) of the average particle diameter (r: μm) to the thickness (d: μm) of the first active energy ray curable resin layer of 0.5 or less. In order to form sufficient protrusions (protrusions sufficient to obtain good blocking resistance) on the surface of the layer, it is preferable that a relatively large amount of particles be present near the surface of the first active energy ray-curable resin layer. That is, it is preferable that a part of the particles contained in the first active energy ray-curable resin layer move (float) near the surface of the layer to increase the particle density near the surface.

  The particles contained in the first active energy ray-curable resin layer are preferably particles in which part of the particles easily move (float) near the surface of the layer, and inorganic particles are preferably used from this viewpoint. Furthermore, from the above viewpoint, the inorganic particles that have been subjected to a surface treatment that reduces the surface free energy, the inorganic particles that have been treated with a surfactant, or a hydrophobizing treatment to make the surface of the particles hydrophobic. It is preferable to use inorganic particles. The inorganic particles that have been subjected to such treatment are likely to move (float) near the surface of the layer.

Examples of the surface treating agent for reducing the surface free energy of the inorganic particles include an organosilane compound having a fluorine atom, a hydrolyzate of the organosilane, or a partial condensate of the hydrolyzate of the organosilane. As these compounds, compounds represented by the following general formula (1) are preferable.
_{C n F 2n + 1 - (} CH 2) m -Si (Q) 3 ···· general formula (1)
(In General Formula (1), 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 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
In addition, the following fluorine-treated inorganic particles are also preferably used as the inorganic particles subjected to the treatment for reducing the surface free energy. That is, it is a particle obtained by treating inorganic particles (for example, silica particles) with a compound represented by the following general formula (2) and further surface-treating with a fluorine compound represented by the following general formula (3).
B—R ⁴ —SiR ⁵ _n (OR ⁶ ) _3-n ... General formula (2)
DR ⁷ -Rf ² ... General formula (3)
(In the general formulas (2) and (3), 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 alkyl 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, and n represents an integer of 0 to 2.)
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 and hydroxyl groups.

  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, 2-perfluorooctylethyl acrylate, 3-perfluorooctyl-2-hydroxypropyl acrylate, 2- Perfluorodecylethyl acrylate, 2-perfluoro-3-methylbutylethyl acrylate, 3-perfluoro-3-methoxybutyl-2-hydroxypropyl acrylate, 2-perfluoro-5-methylhexylethyl acrylate 3-perfluoro-5-methylhexyl-2-hydroxypropyl acrylate, 2-perfluoro-7-methyloctyl-2-hydroxypropyl acrylate, tetrafluoropropyl acrylate, octafluoropentyl acrylate, dodecafluoroheptyl acrylate, hexadeca Fluorononyl acrylate, hexafluorobutyl acrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3,3-pentafluoropropyl methacrylate, 2-perfluorobutylethyl methacrylate, 3-perfluorobutyl-2 -Hydroxypropyl methacrylate, 2-perfluorooctylethyl methacrylate, 3-perfluorooctyl-2-hydroxypropyl methacrylate, 2-perfluoro Decylethyl methacrylate, 2-perfluoro-3-methylbutylethyl methacrylate, 3-perfluoro-3-methylbutyl-2-hydroxypropyl methacrylate, 2-perfluoro-5-methylhexylethyl methacrylate, 3-perfluoro-5- Methylhexyl-2-hydroxypropyl methacrylate, 2-perfluoro-7-methyloctylethyl methacrylate, 3-perfluoro-7-methyloctylethyl methacrylate, tetrafluoropropyl methacrylate, octafluoropentyl methacrylate, octafluoropentyl methacrylate, dodecafluoro Heptyl methacrylate, hexadecafluorononyl methacrylate, 1-trifluoromethyltrifluoroethyl methacrylate, hexafur Examples include orobutyl methacrylate.

  Examples of the inorganic particles treated with the aforementioned surfactant include inorganic particles obtained by treating silica particles (preferably colloidal silica) with a surfactant having an ethyleneoxy group in the molecule.

Examples of the surfactant having an ethyleneoxy group in the molecule include cations such as octyl dimethyl ethyl ammonium ethyl sulfate, lauryl dimethyl ethyl ammonium ethyl sulfate, valmityl dimethyl ethyl ammonium ethyl sulfate, stearyl dimethyl hydroxyethyl ammonium paratoluene sulfonate, and the like. Active surfactant,
Polyoxyethylene alkyl ether phosphate, polyoxyalkylene alkyl ether phosphate, polyoxyalkylene alkyl phenyl ether phosphate, polyoxyethylene tridecyl ether phosphate, polyoxyethylene alkyl ether phosphate, polyoxyethylene Alkyl ether phosphate monoethanolamine salt, polyoxyethylene lauryl ether phosphate ester, polyoxyethylene trilauryl ether phosphate monoethanolamine salt, polyoxyethylene styrenated phenyl ether phosphate ester, polyoxyethylene lauryl ether acetic acid Sodium, polyoxyethylene sulfosuccinate lauryl disodium, polyoxyethylene alkyl sulfosuccinate ninatate , Polyoxystyrenated phenyl ether ammonium sulfate, polyoxyalkylene branched sodium decyl ether sulfate, polyoxyethylene isodecyl ether ammonium sulfate, polyoxyethylene tridecyl ether sodium sulfate, polyoxyethylene lauryl ether sodium sulfate, polyoxyethylene lauryl ether ammonium sulfate Anionic surfactants such as sodium polyoxyethylene alkyl ether sulfate, ammonium polyoxyethylene oleyl cetyl ether sulfate, sodium polyoxyethylene oleyl cetyl ether sulfate, and
Polyoxyalkylene decyl ether, polyoxyethylene tridecyl ether, polyoxyalkylene tridecyl ether, polyoxyalkylene alkyl ether, polyoxyethylene isodecyl ether, polyoxyalkylene lauryl ether, polyoxyethylene styrenated phenyl ether, polyoxyethylene Naphthyl ether, polyoxyethylene phenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyethylene lauryl ether, polyoxyethylene oleyl cetyl ether, polyoxyethylene oleate, polyoxyethylene stearate, polyoxyethylene sorbitan monococo Ate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbie Nmonooreto, isostearic acid polyoxyethylene glyceryl, nonionic surfactants such as polyoxyethylene alkyl amines,
Is mentioned.

  Examples of the hydrophobic compound for subjecting the particle surface to the hydrophobic treatment 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.

  In the following description, a compound having a fluoroalkyl group having 4 or more carbon atoms and a reactive site is referred to as a fluorine compound, and a compound having a hydrocarbon group having 8 or more carbon atoms and a reactive site is referred to as a long-chain hydrocarbon compound. A compound having a siloxane group and a reactive site is called a silicone compound.

  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.

  The long-chain hydrocarbon compound represents a compound having a hydrocarbon group having 8 or more carbon atoms that is a hydrophobic group and a reactive site in the molecule. 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.

  Specific examples of long-chain hydrocarbon compounds 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.

  Examples of the silicone compound include compounds having a siloxane group that is a hydrophobic group in the molecule and a reactive site. As the reactive site of the silicone compound, a (meth) acryloyloxy group is preferably used.

Moreover, as a siloxane group, the polysiloxane group shown by following General formula (4) is used preferably.
^{- (Si (R 8) (} R 9) -O) m - ···· formula (4)
(In the general formula (4), R ⁸ and R ⁹ are each independently an alkyl group having 1 to 6 carbon atoms, phenyl group, 3-acryloxy-2-hydroxypropyl-oxypropyl group, 2-acryloxy-3-hydroxypropyl. -An oxypropyl group, a polyethylene glycol propyl ether group having a terminal acrylate group, or a polyethylene glycol propyl ether group having a terminal hydroxy group, m represents an integer of 10 to 200.)
Specific examples of the 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.) and the like.

  General formula (5) is as follows.

  (In the formula, R represents alkyl having 1 to 7 carbon atoms, k represents an integer of 0 or 1, and m represents an integer of 10 to 200).

  Another specific example of the silicone compound having a polysiloxane group represented by the general formula (4) and a reactive site as a hydrophobic group is 3-acryloxy-2-hydroxy represented by the general formula (6). Examples thereof include a compound having a propyl-oxypropyl group and a methyl group and a compound having a 2-acryloxy-3-hydroxypropyl-oxypropyl group and a methyl group represented by the general formula (7).

  General formula (6) is as follows.

  General formula (7) is as follows.

  (In General Formulas (6) and (7), R represents alkyl having 1 to 7 carbon atoms, k represents an integer of 0 or 1, and m represents an integer of 10 to 200).

  Furthermore, another specific example of the silicone compound having a polysiloxane group represented by the general formula (4) and a reactive site as a hydrophobic group is polyethylene represented by the general formula (8) and having an acryloyloxy group at the terminal. Examples thereof include a compound having a glycol propyl ether 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).

  General formula (8) is as follows.

  General formula (9) is as follows.

  (In General Formulas (8) and (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, and m represents 10 to 200. Represents an integer).

  A fluorine compound having a fluoroalkyl group having 4 or more carbon atoms and a reactive site will be described. Here, the fluoroalkyl group may have a linear structure or a branched structure. The fluoroalkyl group preferably has 4 to 8 carbon atoms. As such a 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.

  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 active energy ray-curable resin layer preferably has a high hardness in order to suppress the occurrence of scratches on the surface of the laminated film, and the pencil hardness defined by JIS K5600-5-4 (1999) F or more is preferable, and H or more is more preferable. The upper limit is about 9H.

  The first active energy ray curable resin layer is a layer obtained by curing an active energy ray curable composition containing at least an active energy ray curable resin and particles. The first active energy ray-curable resin layer is preferably a layer obtained by applying an active energy ray-curable composition by a wet coating method and drying it, and then irradiating and curing the active energy ray.

  As the wet coating method, for example, a coating method such as a reverse coating method, a spray coating method, a bar coating method, a gravure coating method, a rod coating method, a die coating method, a spin coating method, or an extrusion coating method can be used.

  Examples of active energy rays include ultraviolet rays, visible rays, infrared rays, electron beams, rays, β rays, and γ rays. Among these active energy rays, ultraviolet rays and electron beams are preferable, and ultraviolet rays are particularly preferably used.

  Although it does not specifically limit as a light source for irradiating an ultraviolet-ray, For example, an ultraviolet fluorescent lamp, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp etc. can be used. . An ArF excimer laser, a KrF excimer laser, an excimer lamp, synchrotron radiation, or the like can also be used. Among these, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, and a metal halide lamp are preferably used. In addition, when irradiating with ultraviolet rays, it is preferable to perform irradiation in an atmosphere having a low oxygen concentration, for example, an atmosphere having an oxygen concentration of 500 ppm or less because it can be cured efficiently.

Irradiation light amount of the ultraviolet rays is preferably from 50 mJ / cm ² or more, 100 mJ / cm ² or more, and particularly 150 mJ / cm ² or more. The upper limit is preferably 2000 mJ / cm ² or less, and more preferably 1000 mJ / cm ² or less.

  The active energy ray-curable resin means a resin that is polymerized and cured by active energy rays. Examples of such active energy ray-curable resins include compounds (monomers and oligomers) having at least one ethylenically unsaturated group in the molecule. Here, examples of the ethylenically unsaturated group include acryloyl group, methacryloyl group, acryloyloxy group, methacryloyloxy group, allyl group, and vinyl group. In the present invention, a compound having two or more such ethylenically unsaturated groups in the molecule is preferred, and a compound having three or more ethylenically unsaturated groups in the molecule is particularly preferably used.

  Although the compound which has an ethylenically unsaturated group in a molecule | numerator is illustrated below, this invention is not limited to these compounds. In the following description, the expression “... (Meth) acrylate” includes two compounds “... acrylate” and “... methacrylate”.

  Compounds having two ethylenically unsaturated groups in the molecule include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) ) Acrylate, 1,6-hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polyethylene Examples include glycol di (meth) acrylate and polypropylene glycol di (meth) acrylate.

  Examples of the compound having 3 or more ethylenically unsaturated groups in the molecule include trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, glycerin propoxytri (meta ) Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (Meth) acrylate, tripentaerythritol tri (meth) acrylate, tripentaerythritol hexa (meth) acrylate, pentaeryth Torutori (meth) acrylate hexamethylene diisocyanate urethane oligomer, pentaerythritol tri (meth) acrylate toluene diisocyanate urethane oligomer, pentaerythritol tri (meth) acrylate isophorone diisocyanate urethane oligomer and the like.

  Moreover, what is marketed can be used as a polyfunctional urethane (meth) acrylate oligomer. For example, urethane acrylate AH series, urethane acrylate AT series, urethane acrylate AT series, urethane acrylate UA series manufactured by Kyoeisha Chemical Co., Ltd., UN-3320 series, UN-900 series manufactured by Negami Kogyo Co., Ltd., Shin-Nakamura Chemical Co., Ltd. NK Oligo U series, Ebecryl 1290 series manufactured by Daicel UCB, and the like.

  As the active energy ray-curable resin, a compound having two or more ethylenically unsaturated groups in the molecule as described above is preferable, and a compound having three or more ethylenically unsaturated groups in the molecule is preferably used. These compounds can be used in combination with a compound having one ethylenically unsaturated group in the molecule.

  Examples of the compound having one ethylenically unsaturated group in the molecule include methyl (meth) acrylate, lauryl (meth) acrylate, ethyl diethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, and methoxytriethylene glycol (meth). Acrylate, phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, isobornyloxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate 2-hydroxy-3-phenoxy (meth) acrylate, 2-ethylhexyl (meth) acrylate, acrylamide, (meth) acryloylmorpholine, 7-amino 3,7-dimethyloctyl (meth) acrylate, isobutoxymethyl (meth) acrylamide, t-octyl (meth) acrylamide, diacetone (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, etc. It is done.

  The content of the active energy ray-curable resin in the active energy ray-curable composition is preferably 50% by mass or more, more preferably 60% by mass or more, based on 100% by mass of the total solid content of the active energy ray-curable composition. 70 mass% or more is particularly preferable. The upper limit is preferably 97% by mass or less, more preferably 95% by mass or less.

  When ultraviolet rays are used as the active energy ray, the active energy ray curable composition preferably contains a photopolymerization initiator. Specific examples of such photopolymerization initiators include, for example, 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-α-hydroxyisobutylphenone, α-hydroxyisobutylphenone, 2, Carbonyl compounds such as 2-dimethoxy-2-phenylacetophenone and 1-hydroxycyclohexyl phenyl ketone, tetramethylthiuram monosulfide, teto Sulfur compounds such as lamethylthiuram disulfide, thioxanthone, 2-chlorothioxanthone, and 2-methylthioxanthone can be used. These photopolymerization initiators may be used alone or in combination of two or more.

Moreover, generally the photoinitiator is marketed and they can be used. For example,
Irgacure 184, Irgacure 907, Irgacure 379, Irgacure 127, Irgacure 127, Irgacure 500, Irgacure 250, Irgacure 1800, Irgacure 1870, Irgacure OXE01, DAROCURO Sipecure MBB, Speedcure PBZ, Speedcure ITX, Speedcure CTX, Speedcure EDB, Escure ONE, Esacure KIP150, Esacure KTO46, etc. CURE DMBI etc. are mentioned.

  The content of the photopolymerization initiator is suitably in the range of 0.1 to 10% by mass and in the range of 0.5 to 8% by mass with respect to 100% by mass of the total solid content of the active energy ray-curable composition. Is preferred.

  As described above, the first active energy ray-curable resin layer contains particles. Therefore, the active energy ray-curable composition for forming the first active energy ray-curable resin layer also contains particles. These particles are the same as those described above, and a description thereof is omitted here.

  The active energy ray-curable composition can further contain various additives such as an antioxidant, an ultraviolet absorber, a leveling agent, an organic antistatic agent, a lubricant, a colorant, and a pigment.

  The first active energy ray-curable resin layer preferably has a relatively large number of protrusions on the surface. On the other hand, from the viewpoint of reducing the haze value of the laminated film, the first active energy ray-curable resin layer is used. The surface is preferably relatively smooth. That is, the center line average roughness (Ra1) on the surface of the first active energy ray-curable resin layer is preferably less than 30 nm. By adjusting the number and height of the protrusions on the surface of the first active energy ray-curable resin layer described above, the center line average roughness (Ra1) of the surface of the first active energy ray-curable resin layer is controlled to be less than 30 nm. be able to.

  The center line average roughness (Ra1) on the surface of the first active energy ray-curable resin layer is preferably 25 nm or less, more preferably 20 nm or less, and particularly preferably 18 nm or less. On the other hand, if the centerline average roughness (Ra1) on the surface of the first active energy ray-curable resin layer is too small, the anti-blocking property may decrease, so the lower limit centerline average roughness (Ra1) is 3 nm or more. Is preferable, and 5 nm or more is more preferable.

[Laminated film]
The laminated film of the present invention has a resin layer and a first active energy ray-curable resin layer in this order on at least one surface of the base film. The laminated film of the present invention may have a resin layer and a first active energy ray-curable resin layer only on one side of the base film, or a resin layer and a first active energy ray cure on both sides of the base film. May have a functional resin layer.

  Further, as another preferred embodiment of the laminated film of the present invention, the base film has a resin layer and a first active energy ray-curable resin layer on one surface, and the other surface of the base film (that is, a base film). The laminated film which has a 2nd active energy ray curable resin layer on the surface opposite to the surface in which the 1st active energy ray curable resin layer of the material film was provided is mentioned.

  The laminated film of the present invention is suitable as a base film of a transparent conductive film as will be described later. Since the transparent conductive film is required to have high transparency, the base film (laminated film) preferably has a small haze value.

  From the above viewpoint, the laminated film of the present invention preferably has a haze value of 0.5% or less, more preferably 0.4% or less, and particularly preferably 0.3% or less. The lower haze value is preferably as small as possible, and is not particularly limited.

  By employing the configuration of the laminated film of the present invention (the configuration having the resin layer and the first active energy ray-curable resin layer in this order on at least one surface of the base film), the haze value is 0.5% or less. A certain laminated film can be obtained, but in order to obtain a laminated film having a smaller haze value, the resin film and the first active energy ray-curable resin layer are provided on one surface of the substrate film, It is preferable to use a laminated film having the following second active energy ray-curable resin layer on the other surface.

[Second active energy ray-curable resin layer]
Hereinafter, the 2nd active energy ray curable resin layer provided in the other surface of a base film is demonstrated.

  The thickness of the second active energy ray-curable resin layer is preferably less than 2.5 μm, and more preferably 2.0 μm or less. The lower limit thickness is preferably 0.5 μm or more, and more preferably 1.0 μm or more.

  When the thickness of the second active energy ray-curable resin layer is 2.5 μm or more, there are cases where inconveniences such as an increase in curling of the laminated film and a decrease in transmittance may occur. On the other hand, when the thickness of the second active energy ray-curable resin layer is less than 0.5 μm, the hardness of the second active energy ray-curable resin layer is lowered, and scratches are easily formed.

  The second active energy ray-curable resin layer preferably has a high hardness from the viewpoint of suppressing the occurrence of scratches on the surface of the laminated film, and has a pencil hardness defined by JIS K5600-5-4 (1999). , H or more is preferable, and 2H or more is more preferable. The upper limit is about 9H.

  As described above, from the viewpoint of reducing the haze value of the laminated film, the surface of the second active energy ray-curable resin layer is preferably smooth. That is, the center line average roughness (Ra2) of the surface of the second active energy ray-curable resin 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 0.1 nm.

  The second active energy ray-curable resin layer has an average particle size of the second active energy ray-curable resin layer so that the centerline average roughness (Ra2) of the surface of the second active energy ray-curable resin layer is 25 nm or less. It is preferable that particles having a diameter larger than 0.5 μm are not substantially contained. Here, the fact that the second active energy ray-curable resin layer does not substantially contain particles having an average particle size larger than 0.5 μm means that the coating liquid for forming the second active energy ray-curable resin layer ( For example, it means that particles having an average particle size larger than 0.5 μm are not intentionally added to the active energy ray-curable composition). In addition, the average diameter of the particle | grains contained in a 2nd active energy ray curable resin layer is calculated | required by the method similar to the measuring method of the average diameter of the particle | grains contained in a 1st active energy ray curable resin layer.

  The second active energy ray-curable resin layer preferably has no protrusions due to particles on the surface thereof. The second active energy ray-curable resin layer can contain particles having an average particle size of 0.5 μm or less. From the above viewpoint, the average particle size of particles to be contained in the second active energy ray-curable resin layer Is preferably adjusted.

  When the particles are contained in the second active energy ray-curable resin layer, the average particle diameter of the particles is preferably 0.2 μm or less, and more preferably 0.1 μm or less. 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 active energy ray-curable resin layer, and is 0.5 to 10% by mass. A range is more preferable, and a range of 1 to 8% by mass is particularly preferable.

  Most preferably, the second active energy ray-curable resin layer contains no particles.

  The second active energy ray curable resin layer is a layer obtained by curing an active energy ray curable composition containing at least an active energy ray curable resin. The second active energy ray-curable resin layer is preferably a layer obtained by applying an active energy ray-curable composition by a wet coating method and drying it, and then irradiating and curing the active energy ray.

  The wet coating method and the active energy ray are the same as those used for forming the first active energy ray-curable resin layer.

Irradiation dose in the case of using ultraviolet rays as the active energy ray is preferably 50 mJ / cm ² or more, 100 mJ / cm ² or more, and particularly 150 mJ / cm ² or more. The upper limit is preferably 2000 mJ / cm ² or less, and more preferably 1000 mJ / cm ² or less.

  As the active energy ray curable resin, the same active energy ray curable resin as that contained in the active energy ray curable composition for forming the first active energy ray curable resin layer described above may be used. it can. Further, the content of the active energy ray-curable resin is the same as the content in the active energy ray-curable composition for forming the first active energy ray-curable resin layer.

  The active energy ray-curable composition for forming the second active energy ray-curable resin layer preferably contains a photopolymerization initiator. As the photopolymerization initiator, the same photopolymerization initiator as that contained in the active energy ray-curable composition for forming the first active energy ray-curable resin layer described above can be used. Further, the content of the photopolymerization initiator is the same as the content in the active energy ray-curable composition for forming the first active energy ray-curable resin layer described above.

  The refractive index of the second active energy ray-curable resin layer is preferably in the range of 1.48 to 1.54, and more preferably in the range of 1.50 to 1.53. The second active energy ray-curable resin layer is formed by applying the above-described active energy ray-curable composition by a wet coating method, drying as necessary, and then irradiating and curing the active energy ray. Thus, a second active energy ray-curable resin layer having a refractive index in the range of 1.48 to 1.54 can be obtained.

  In the present invention, the refractive index of the second active energy ray-curable resin layer and the refractive indexes of the biaxially stretched PET film, the easy-adhesion layer, and the refractive index adjustment layer described below are wavelengths 589 nm unless otherwise specified. The refractive index at.

  In order to reinforce the adhesion between the base film and the second active energy ray-curable resin layer, it is preferable to interpose an easy-adhesion layer between the base film and the second active energy ray-curable resin layer. As an easily bonding layer, the same thing as the resin layer provided between the above-mentioned base film and the 1st active energy ray hardening resin layer can be used.

  As described above, a polyethylene terephthalate film (PET film) is preferable as the base film of the laminated film, and a biaxially stretched PET film is particularly preferably used. The biaxially stretched PET film usually has a refractive index of 1.61 to 1.70, and a second active energy ray-curable resin layer having a refractive index of 1.48 to 1.54 is formed on the biaxially stretched PET film. When laminated, uneven reflection colors may occur. In order to suppress this uneven reflection color, the refractive index of the easy adhesion layer is preferably 1.55 to 1.60, more preferably 1.56 to 1.59.

  Therefore, in the laminated film of the present invention, the base film is a polyethylene terephthalate film having a refractive index of 1.61 to 1.70, the refractive index of the easy adhesion layer is 1.55 to 1.60, The refractive index of the two active energy ray-curable resin layer is particularly preferably 1.48 to 1.54.

  In order to set the refractive index of the easy-adhesion layer in the range of 1.55 to 1.60, it is preferable to use a polyester resin containing a naphthalene ring in the molecule 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 content of the polyester resin containing a naphthalene ring in the molecule in the easy adhesion 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 easy adhesion layer preferably contains a cross-linking agent. As the crosslinking agent, the same crosslinking agent as that contained in the resin layer can be used, and the content is also the same.

  The easy adhesion layer preferably contains particles. As such particles, the same particles as those contained in the resin layer described above can be used, and the content is also the same.

  The easy-adhesion layer is preferably applied on a base film by a wet coating method, and is cured by heating and laminated. Furthermore, it is preferable that the easy-adhesion 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 heated and cured to be laminated.

  The thickness of the easy adhesion layer is preferably in the range of 0.005 to 0.3 μm, more preferably in the range of 0.01 to 0.2 μm, and particularly preferably in the range of 0.015 to 0.15 μm.

[Transparent conductive film]
The laminated film of the present invention is suitable as a base film for a transparent conductive film. That is, the transparent conductive film using the laminated film of the present invention as a base film is obtained by laminating a transparent conductive film on at least one surface of the laminated film of the present invention.

  The transparent conductive film may be laminated | stacked only on either one surface of the laminated | multilayer film of this invention, and may be laminated | stacked on both surfaces.

  Some examples of the configuration of the transparent conductive film using the laminated film of the present invention as a base film are exemplified below, but the present invention is not limited thereto.

i) First active energy ray-curable resin layer / resin layer / base film / adhesive layer / first active energy ray-curable resin layer / transparent conductive film
ii) Transparent conductive film / first active energy ray-curable resin layer / resin layer / base film / resin layer / first active energy ray-curable resin layer / transparent conductive film
iii) First active energy ray-curable resin layer / resin layer / base film / adhesive layer / second active energy ray-curable resin layer / transparent conductive film
iv) / transparent conductive film / first active energy ray-curable resin layer / resin layer / base film / adhesive layer / second active energy ray-curable resin layer
v) Transparent conductive film / first active energy ray-curable resin layer / resin layer / base film / adhesive layer / second active energy ray-curable resin layer / transparent conductive film.

  Among the above configuration examples, i) or iii) is preferable, and iii) is particularly preferable. In other words, from the viewpoint of ensuring the blocking resistance of the laminated film in the lamination step and processing step of the transparent conductive film, the first active energy ray-curable resin layer should be exposed without being laminated. Is preferred.

  Furthermore, the active energy ray-curable resin layer on the surface on which the transparent conductive film is laminated is preferably relatively smooth and clear. Therefore, in the configuration example of iii), the center line average roughness Ra of the surface of the second active energy ray-curable resin layer is preferably 25 nm or less, more preferably 20 nm or less, and particularly preferably 15 nm or less.

[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. Among these, ITO is preferably used.

The thickness of the transparent conductive film is preferably 8 nm or more, and more preferably 10 nm or more, from the viewpoint of ensuring good conductivity with a surface resistance value of 10 ³ Ω / □ or less. 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.

  It does not specifically limit as a formation method of a transparent conductive film, A conventionally well-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. In addition, by patterning the transparent conductive film, a pattern portion (a portion where the transparent conductive film is laminated on the surface of the laminated film) and a non-pattern portion (a portion where the transparent conductive film is not laminated on the surface of the laminated film) are formed. However, examples of the shape of the pattern portion include a stripe shape and a lattice shape.

  The patterning of the transparent conductive film is generally performed by etching. For example, 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.

  A conventionally well-known thing is used as etching liquid. For example, 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.

[Refractive index adjusting layer]
In the configuration example of the transparent conductive film, the transparent conductive film may be directly laminated on the first active energy ray curable resin layer or the second active energy ray curable resin layer. It is preferable to interpose a refractive index adjusting layer between the 1 active energy ray curable resin layer or the second active energy ray curable resin layer. Hereinafter, 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.

  As the configuration of the refractive index adjustment layer, for example, a single layer configuration of a high refractive index layer having a refractive index of 1.60 to 1.80, and a single layer configuration of a low refractive index layer having a refractive index of 1.30 to 1.50. Or the laminated structure of the said high refractive index layer and a low refractive index layer (low refractive index layer arrange | positions at the transparent conductive film side) etc. are mentioned.

  The refractive index 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 of the low refractive index layer is further preferably in the range of 1.30 to 1.48, more preferably in the range of 1.33 to 1.46.

  The thickness of the refractive index adjusting layer (referring to the total thickness in the case of a multilayer structure) is preferably 0.2 μm or less, more preferably 0.15 μm or less, particularly preferably 0.12 μm or less, and 0.1 μm or less. Most preferred. The lower limit thickness is preferably 0.03 μm or more, more preferably 0.04 μm or more, particularly preferably 0.05 μm or more, and most preferably 0.06 μm or more.

  For the high refractive index layer, for example, 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. Here, the active energy ray-curable composition is a composition containing at least the active energy ray-curable resin and the photopolymerization initiator described in the first active energy ray-curable resin layer.

  Examples of 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. Among the metal oxide fine particles, 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. Here, the active energy ray-curable composition is a composition containing the active energy ray-curable resin and the photopolymerization initiator described in the first active energy ray-curable resin layer.

  As the low refractive index inorganic particles, 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 in the range of 1 to 50% by mass, more preferably in the range of 3 to 40% by mass with respect to 100% by mass of the total solid content of the active energy ray-curable composition. In particular, the range of 5 to 35% by mass is preferable.

  Examples of the fluorine-containing compound include fluorine-containing monomers, fluorine-containing oligomers, and fluorine-containing polymer compounds. Here, the fluorine-containing monomer or fluorine-containing oligomer is a monomer or oligomer having the above-mentioned ethylenically unsaturated group and fluorine atom in the molecule.

  Examples of the fluorine-containing monomer and fluorine-containing oligomer include 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (meth) acrylate, and 2- (perfluorobutyl). ) Ethyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 2- (perfluorooctyl) ethyl (meth) acrylate, 2- (perfluorodecyl) ethyl (meth) acrylate, β- (per Fluoro-containing (meth) acrylic esters such as fluorooctyl) ethyl (meth) acrylate, di- (α-fluoroacrylic acid) -2,2,2-trifluoroethylethylene glycol, di- (α-fluoroacrylic acid) ) -2,2,3,3,3-pentafluoropropylethylene glycol, di (Α-fluoroacrylic acid) -2,2,3,3,4,4,4-heptafluorobutylethylene glycol, di- (α-fluoroacrylic acid) -2,2,3,3,4,4,4 5,5,5-nonafluoropentylethylene glycol, di- (α-fluoroacrylic acid) -2,2,3,3,4,4,5,5,6,6,6-undecafluorohexylethylene glycol , Di- (α-fluoroacrylic acid) -2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptylethylene glycol, di- (α-fluoro Acrylic acid) -2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctylethylene glycol, di- (α-fluoroacrylic acid) -3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 8-tridecafluorooctylethylene glycol, di- (α-fluoroacrylic acid) -2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9 , 9-heptadecafluorononylethylene glycol and the like di- (α-fluoroacrylic acid) fluoroalkyl esters.

  Examples of the fluorine-containing polymer compound include a fluorine-containing copolymer having a fluorine-containing monomer and a monomer for imparting a crosslinkable group as constituent units. Specific examples of the fluorine-containing monomer unit 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 Chemicals) and M-2020 (manufactured by Daikin)), fully or partially fluorinated vinyl ethers, and the like. As a monomer for imparting a crosslinkable group, in addition to a (meth) acrylate monomer having a crosslinkable functional group in the molecule like 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 in the range of 5 to 50% by mass, more preferably in the range of 10 to 45% by mass, and particularly preferably 15 to 40% with respect to 100% by mass of the total solid content of the active energy ray-curable composition. A range of mass% is preferred.

[Touch panel]
The transparent conductive film having the laminated film of the present invention as a base fill is preferably used as one of constituent members of the touch panel.

  A resistive touch panel usually has a configuration in which an upper electrode and a lower electrode are arranged via a spacer. However, a transparent conductive film using the laminated film of the present invention as a base fill is composed of an upper electrode and a lower electrode. It can be used for either one or both.

  Capacitive touch panels are usually composed of patterned X and Y electrodes, but transparent conductive films based on the laminated film of the present invention are either X or Y electrodes. It can be used for one or both.

  The transparent conductive film used for the touch panel is required to have good transparency and workability (blocking resistance), but the transparent conductive film based on the laminated film of the present invention has the above characteristics. You can be satisfied enough.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by these Examples. In addition, the measuring method and evaluation method in a present Example are shown below.

(1) Measurement of Wetting Tension of Resin Layer A base film on which a resin layer is laminated is seasoned for 6 hours in an ordinary atmosphere (23 ° C., relative humidity 50%), and JIS-K-6768 ( 1999).

(2) Measurement of Refractive Index of Each Layer For a coating film (dry thickness of about 2 μm) formed by coating each coating solution on a silicon wafer with a spin coater, a phase difference measurement device (Nikon ( The refractive index of 589 nm was measured by NPDM-1000).

  Moreover, the refractive index of the base film (PET film) measured the refractive index of 589 nm with the Abbe refractometer according to JISK7105 (1981).

(3) Measurement of thickness of resin layer and easy-adhesion layer A cross section of the base film on which the resin layer and the easy-adhesion layer are laminated is cut into ultrathin sections, and RuO ₄ staining, OsO ₄ staining, or double staining of both. By observation with a TEM (transmission electron microscope) under the following conditions where the cross-sectional structure is visible, the thickness of the resin layer and the easy-adhesion layer is measured from the cross-sectional photograph by the dyeing ultrathin section method. The measurement location is a portion where no particles exist. In addition, five places were measured and the average value was made into the thickness of a resin layer and an easily bonding layer.
Measurement device: Transmission electron microscope (H-7100FA type, manufactured by Hitachi, Ltd.)
・ Measurement conditions: acceleration voltage 100 kV
-Sample preparation: frozen ultrathin section method-Magnification: 300,000 times.

(4) Measurement of the thickness of the first and second active energy ray-curable resin layers, the high refractive index layer, and the low refractive index layer The cross section of the laminated film is cut into ultrathin sections, and the acceleration voltage is measured with a TEM (transmission electron microscope). Observation is performed at 100 kV (observation at a magnification of 1 to 300,000 times), and the thickness is measured from the cross-sectional photograph. In addition, about the layer which has a processus | protrusion on the surface like a 1st active energy ray curable resin layer, it is the thickness in the part in which a processus | protrusion does not exist. The thickness was measured at five locations, and the average value was taken as the thickness.

(5) Measurement of average particle diameter of particles contained in first active energy ray curable resin layer The cross section of the first active energy ray curable resin layer is observed with a TEM (transmission electron microscope) (approximately 10,000 to 10). The maximum length of each of 30 randomly selected particles was measured from the cross-sectional photograph, and the average value of these was taken as the average particle diameter of the particles.

(6) Measurement of average particle diameter of particles contained in resin layer and easy-adhesion layer The surface of the resin layer (easy-adhesion layer) laminated on the base film was scaled 10,000 using an SEM (scanning electron microscope). The image of the particle (light density produced by the particle) is linked to an image analyzer (for example, QTM900 manufactured by Cambridge Instrument), the data is acquired by changing the observation position, and when the total number of particles reaches 5000 or more The number average diameter d obtained by the numerical processing was defined as the average particle diameter (diameter).
・ D = Σdi / N
Here, 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.

(7) Measurement of center line average roughness Ra of surfaces of first and second active energy ray-curable resin layers Based on JIS B0601 (1982), stylus type surface roughness measuring instrument SE-3400 (Kosaka Co., Ltd.) Measured using a laboratory.

<Measurement conditions>
Feeding speed: 0.5mm / s
Evaluation length: 8mm
Cut-off value λc; 0.08 mm.

(8) Determination of presence or absence of protrusions due to particles on the surface of the first active energy ray-curable resin layer The average height and number of protrusions are measured by the following method, the average height is 0.02 μm or more, and the protrusions are It is judged that it has the protrusion by particle | grains by having two or more on average per ² micrometers square (area 4 micrometers ² ).

<Measurement of average height of protrusions>
A cut sample (20 cm × 15 cm) of a laminated film is prepared, and a cross section of the first active energy ray-curable resin layer of this cut sample is photographed at five locations with a scanning electron microscope (approximately 10,000 to 100,000 times). And five cross-sectional photographs are produced. Next, the heights of all the protrusions present in the five cross-sectional photographs are measured and averaged. In addition, the size of the cross-sectional photograph is adjusted so that the measurement length in one cross-sectional photograph is 1 μm or more.

<Measurement of the number of protrusions>
A cut sample (20 cm × 15 cm) of a laminated film is prepared, and the surface of the first active energy ray-curable resin layer of this cut sample is photographed at five locations with a SEM (scanning electron microscope) (approximately 10,000 to 100,000 times). 5 images (surface photographs). Next, for each of the five images, the number of protrusions existing in the range of ² μm square (area 4 μm ² ) of the image is measured and averaged.

(9) Measurement of haze value of laminated film Based on JIS K 7136 (2000), it measured using the turbidimeter "NDH-2000" by Nippon Denshoku Industries Co., Ltd. In the measurement, it arrange | positions so that light may inject into the surface of the side in which the 1st active energy ray curable resin layer of the laminated film is provided.

(10) Evaluation of blocking resistance One surface of the laminated film is the first surface and the other surface is the second surface.
The laminated film is cut to produce two sheet pieces (20 cm × 15 cm). The two sheets are overlapped so that the first surface and the second 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.
○: Newton ring is not generated before peeling, and light peeling is performed without making a peeling sound at the time of peeling.
(Triangle | delta): Before peeling, a part of Newton ring has generate | occur | produced and it peels, making a small peeling sound at the time of peeling.
X: Newton ring is generated on the entire surface before peeling, and peels off with a loud peeling sound during peeling.

(11) Visual evaluation of reflection color of the surface of the second active energy ray-curable resin layer of the laminated film A black adhesive tape (“Vinyl tape No. 1” manufactured by Nitto Denko Corporation) is applied to the surface of the first active energy ray-curable resin layer of the laminated film. 21 Tokuhaba black ") was applied, and the reflected color of the surface of the second active energy ray-curable resin layer was visually observed under a dark room three-wavelength fluorescent lamp, and the following criteria were used.
○: Reflection color is neutral and almost colorless.
X: The reflected color is colored.

(12) Visibility of transparent conductive film pattern A transparent conductive film was placed on a black plate, and whether or not the pattern portion of the transparent conductive film could be visually confirmed was evaluated according to the following criteria.
○: The pattern portion cannot be visually recognized.
X: A pattern part can be visually recognized.

  Subsequently, raw materials used in the following examples and comparative examples will be described.

<Resin layer forming coating solution>
(Resin layer forming coating solution a)
A water-dispersed coating solution was prepared by mixing 27% by mass of polyester resin a, 54% by mass of polyester resin b, 18% by mass of melamine-based crosslinking agent, and 1% by mass of particles in terms of solid content mass ratio.
Polyester resin a: 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 b: a polyester resin composed of terephthalic acid 38 mol% / trimellitic acid 12 mol% / ethylene glycol 45 mol% / diethylene glycol 5 mol%.
・ Melamine-based cross-linking agent; “Nicarac MW12LF” manufactured by Sanwa Chemical Co., Ltd.)
Particles: colloidal silica having an average particle size of 0.19 μm.

(Resin layer forming coating solution b)
Solid resin mass ratio: 42% by mass of polyester resin c, 42% by mass of acrylic resin a, 6% by mass of epoxy-based crosslinking agent, 9% by mass of surfactant, and 1% by mass of particles and water dispersion coating A liquid was prepared.
Polyester resin c: terephthalic acid 35 mol% / isophthalic acid 11 mol% / 5-sodium sulfoisophthalic acid 4 mol% / ethylene glycol 45 mol% / diethylene glycol 4 mol% / polyethylene glycol (number of repeating units n = 23) 1 mol % Polyester resin.
-Acrylic resin a; acrylic resin composed of 75 mol% of methyl methacrylate / 18 mol% of ethyl acrylate / 4 mol% of N-methylolacrylamide / methoxypolyethylene glycol (number of repeating units n = 10) 3 mol% of methacrylate.
-Epoxy-based crosslinking agent; 1,3-bis (N, N-diglycidylamine) cyclohexane-Surfactant; Polyoxyethylene lauryl ether-Particles; Colloidal silica having an average particle size of 0.19 [mu] m.

(Resin layer forming coating solution c)
Polyester resin d, 40% by mass, acrylic resin b, 40% by mass, melamine-based crosslinking agent, 10% by mass, surfactant, 9% by mass, and 1% by mass of particles, in a solid content mass ratio. A liquid was prepared.
Polyester resin d: 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-based crosslinking agent; manufactured by Sanwa Chemical Co., Ltd. "Nikarak MW12LF")
-Surfactant; Polyoxyethylene lauryl ether-Particles; Colloidal silica having an average particle size of 0.19 μm.

(Resin layer forming coating solution d)
Polyester resin e is 45% by mass, acrylic resin c is 45% by mass, melamine-based crosslinking agent is 5% by mass, surfactant is 4% by mass, and particles are 1% by mass. A liquid was prepared.
Polyester copolymer e: 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% by mole of methyl methacrylate / 22% by mole of ethyl acrylate / 4% by mole of N-methylolacrylamide / 4% by mole of 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 μm.

(Resin layer forming coating solution e)
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 crosslinking agent; triethylene glycol diglycidyl ether; surfactant; polyoxyethylene lauryl ether; particles; colloidal silica having an average particle size of 0.19 μm.

(Resin layer forming coating solution f)
An aqueous dispersion coating solution was prepared by mixing 90% by mass of acrylic resin d, 9% by mass of surfactant, and 1% by mass of particles in a solid content mass ratio.
Acrylic resin d: an acrylic copolymer composed of 70 mol% methyl methacrylate / 22 mol% ethyl acrylate / 4 mol% N-methylolacrylamide / 4 mol% acryloylmorpholine.
-Surfactant; Polyoxyethylene lauryl ether-Particles; Colloidal silica having an average particle size of 0.19 μm.

<Surface treatment silica particle dispersion>
(Surface treatment silica particle dispersion A)
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. Next, after adding 13.8 parts by mass of fluorine compound (H ₂ C═CH—COO—CH ₂ — (CF ₂ ) ₈ F) and 0.57 parts by mass of 2,2-azobisisobutyronitrile, A dispersion was obtained by heating and stirring at 90 ° C. for minutes.

(Surface treatment silica particle dispersion B)
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. Next, 9 parts by mass of fluorine compound (H ₂ C═CH—COO—CH ₂ — (CF ₂ ) ₈ F) and 4.8 of silicone compound (“PC-4131” manufactured by Dainippon Ink & Chemicals, Inc.) After adding 0.57 mass part of mass part and 2, 2- azobisisobutyronitrile, it heated and stirred at 90 degreeC for 60 minutes, and the dispersion liquid was obtained.

(Surface treatment silica particle dispersion C)
Colloidal silica (“organosilica sol IPA-ST-ZL” manufactured by Nissan Chemical Industries, Ltd.) 330 parts by mass, acryloyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) 8 parts by mass, tridecafluorooctyltrimethoxy After adding 2 parts by mass of silane (manufactured by GE Toshiba Silicone Co., Ltd.) and 1.5 parts by mass of diisopropoxyaluminum ethyl acetate, 9 masses of ion-exchanged water was added. After making it react at 60 degreeC for 8 hours, it cooled to room temperature and added 1.8 mass parts of acetylacetone. Next, while adding cyclohexanone to this dispersion, solvent displacement was performed by distillation under reduced pressure at a pressure of 20 kPa to obtain a dispersion.

(Surface treatment silica particle dispersion D)
150 parts by mass of colloidal silica (“organosilica sol MEK-ST-2040” manufactured by Nissan Chemical Industries, Ltd.) is mixed with 13.7 parts by mass of methacryloxypropyltrimethoxysilane and 1.7 parts by mass of 10% by mass aqueous formic acid solution. , And stirred at 70 ° C. for 1 hour. Next, after adding 13.8 parts by mass of fluorine compound (H ₂ C═CH—COO—CH ₂ — (CF ₂ ) ₈ F) and 0.57 parts by mass of 2,2-azobisisobutyronitrile, A dispersion was obtained by heating and stirring at 90 ° C. for minutes.

(Surface treatment silica particle dispersion E)
150 parts by mass of colloidal silica (“organosilica sol MEK-ST-L” 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. Next, after adding 13.8 parts by mass of fluorine compound (H ₂ C═CH—COO—CH ₂ — (CF ₂ ) ₈ F) and 0.57 parts by mass of 2,2-azobisisobutyronitrile, A dispersion was obtained by heating and stirring at 90 ° C. for minutes.

(Surface treatment silica particle dispersion F)
Silica fine particle SP-03F (manufactured by Fuso Chemical Co., Ltd.) is mixed with 300 parts by mass of KBM7103 (manufactured by Shin-Etsu Chemical Co., Ltd., fluoroalkylalkoxysilane) with 15 parts by mass and MIBK (methyl isobutyl ketone) with 2585 parts by mass. Using a paint shaker, dispersion was performed for 1 hour with zirconia beads having a particle diameter of 2 mm and for 3 hours with zirconia beads having a particle diameter of 0.1 mm. Thereafter, zirconia beads were removed, and the obtained dispersion was heated and stirred at 50 ° C. for 1 hour to obtain a dispersion.

(Surface treatment silica particle dispersion G)
Silica sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: ELCOM V-8901) Anionic surfactant having an ethyleneoxy group in the molecule in 100 parts by mass of methanol dispersion (Daiichi Kogyo Seiyaku Co., Ltd .: Prisurf A212E) 2 Mass parts were mixed and stirred for 20 hours to obtain a silica particle dispersion treated with a surfactant.

[Example 1]
A laminated film was produced in the following manner.

<Preparation of resin layer (easy adhesion layer) laminated PET film>
PET pellets (intrinsic viscosity 0.63 dl / g) substantially free of externally added particles are sufficiently vacuum-dried, then supplied to an extruder, melted at 285 ° C., extruded from a T-shaped die into a sheet shape, It was wound around a mirror-casting drum having a surface temperature of 25 ° C. using an electric application casting method and cooled and solidified. This unstretched film was heated to 90 ° C. and stretched 3.4 times in the longitudinal direction to obtain a uniaxially stretched film. After performing corona discharge treatment in air on both surfaces of this uniaxially stretched film, the resin layer coating liquid a is applied to one surface (first surface) of the uniaxially stretched film, and the following easy adhesion to the other surface (second surface). Each layer coating solution was applied.

  Next, the uniaxially stretched film coated with each coating solution on both sides is held by clips and guided to a preheating zone, dried at an ambient temperature of 75 ° C., raised to 110 ° C. using a radiation heater, and dried again at 90 ° C. After that, the film was continuously stretched 3.5 times in the width direction in a heating zone at 120 ° C., and subsequently subjected to heat treatment for 20 seconds in the heating zone at 220 ° C., thereby producing a biaxially stretched PET film in which crystal orientation was completed. . This resin layer (easy adhesion layer) laminated PET film is a PET film having a resin layer on the first surface and an easy adhesion layer on the second surface. The thickness of the resin layer (easy-adhesive layer) laminated PET film was 100 μm, the thickness of the resin layer provided on the first surface was 0.08 μm, and the thickness of the easy-adhesive layer provided on the second surface was 0.08 μm. It was.

  The refractive index of the PET film was 1.65, and the refractive index of the easily adhesive layer on the second surface was 1.58.

  In addition, the refractive index of PET film measured the refractive index of the PET film manufactured on the conditions similar to the above except not laminating | stacking a resin layer (easy-adhesion layer) on both surfaces, and made the value the refractive index of PET film .

<Easily adhesive layer coating solution>
A solid dispersion mass ratio of 27% by mass of polyester resin 1, 53% by mass of polyester resin 2, 18% by mass of melamine-based crosslinking agent, and 2% by mass of particles was mixed to prepare an aqueous dispersion coating solution.
Polyester resin 1: 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 2: a polyester resin composed of 38 mol% terephthalic acid / 12 mol% trimellitic acid / 45 mol% ethylene glycol / 5 mol% diethylene glycol.
・ Melamine-based cross-linking agent; “Nicarac MW12LF” manufactured by Sanwa Chemical Co., Ltd.)
Particles: colloidal silica having an average particle size of 0.19 μm.

<Lamination of first active energy ray-curable resin layer>
Gravure an active energy ray-curable composition a for forming the following first active energy ray-curable resin layer on the resin layer on the first surface of the resin layer (easily adhesive layer) laminated PET film obtained above. It apply | coated by the coating method, and after drying at 90 degreeC, the ultraviolet-ray 400mJ / cm < ² > was irradiated and hardened, and the 1st active energy ray curable resin layer was formed. This first active energy ray-curable resin layer had a thickness of 1.0 μm. The content of the particles (surface-treated silica particles) in the first active energy ray-curable resin layer is 9% by mass with respect to 100% by mass of the total solid content of the first active energy ray-curable resin layer. .

<Active energy ray-curable composition a>
50 parts by mass of dipentaerythritol hexaacrylate, 36 parts by mass of an acrylate compound (“Aronix M111” manufactured by Toa Gosei Co., Ltd.), 9 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 (registered trademark) 184” manufactured by Specialty Chemicals Co., Ltd. was mixed with an organic solvent (methyl ethyl ketone) to prepare a composition having a solid content concentration of 30% by mass.

<Lamination of second active energy ray curable resin layer>
Subsequently, an active energy ray-curable composition Z for forming the following second active energy ray-curable resin layer is gravured on the easy-adhesion layer on the second surface of the resin layer (easy-adhesion layer) laminated PET film. It apply | coated by the coating method, and after drying at 90 degreeC, the ultraviolet-ray 400mJ / cm < ² > was irradiated and hardened, and the 2nd active energy ray-curable resin layer was formed. This second active energy ray-curable resin layer had a thickness of 1.5 μmm and a refractive index of 1.52.

<Active energy ray-curable composition Z>
48 parts by mass of dipentaerythritol hexaacrylate, urethane acrylate oligomer (“UN-901T” from Negami Kogyo Co., Ltd .; containing 9 polymerizable functional groups in the molecule), photopolymerization initiator (Ciba Specialty) 5 parts by mass of “Irgacure (registered trademark) 184” manufactured by Chemicals Co., Ltd. was mixed with an organic solvent (methyl ethyl ketone) to prepare a composition having a solid content concentration of 30% by mass.

[Examples 2-8, Comparative Examples 1-10]
In the production of the resin layer (easy-adhesive layer) laminated PET film of Example 1, a resin layer (as in Example 1) except that the resin layer coating solution applied to the first surface is changed as shown in Table 1. Easy adhesion layer) A laminated PET film was prepared. Subsequently, each laminated film was produced in the same manner as in Example 1 except that the thickness of the first active energy ray-curable resin layer was changed as shown in Table 1.

  In Examples 1-8 and Comparative Examples 1-10, the easy-adhesion layer and the second active energy ray-curable resin layer on the second surface of the PET film are the same. The centerline average roughness (Ra2) of the surface of the active energy ray-curable resin layer on the second surface was 5 nm in all cases.

[Example 11]
In the same manner as in Example 1, a resin layer (easy adhesion layer) laminated PET film was produced. Subsequently, the active energy ray-curable composition b for forming the following first active energy ray-curable resin layer is applied on the resin layer on the first surface of the resin layer (easily adhesive layer) laminated PET film. A laminated film was produced in the same manner as in Example 1. The content of the particles (surface-treated silica particles) in the first active energy ray-curable resin layer is 9% by mass with respect to 100% by mass of the total solid content of the first active energy ray-curable resin layer. .

<Active energy ray-curable composition b>
86 parts by mass of dipentaerythritol hexaacrylate, 9 parts by mass of the surface-treated silica particle dispersion B in terms of solid content, 5 parts by mass of a photopolymerization initiator (“Irgacure (registered trademark) 184” manufactured by Ciba Specialty Chemicals) Parts were mixed with an organic solvent (methyl ethyl ketone) to prepare a composition having a solid content concentration of 30% by mass.

[Examples 12 to 18, Comparative Examples 11 to 20]
In the production of the resin layer (easy-adhesion layer) laminated PET film of Example 11, the resin layer (as shown in Example 11) except that the resin layer coating solution applied to the first surface was changed as shown in Table 2. Easy adhesion layer) A laminated PET film was prepared. Subsequently, each laminated film was produced in the same manner as in Example 11 except that the thickness of the first active energy ray-curable resin layer was changed as shown in Table 2.

  In Examples 11-18 and Comparative Examples 11-20, the easy-adhesion layer on the second surface of the PET film and the second active energy ray-curable resin layer are both the same. The centerline average roughness (Ra2) of the surface of the active energy ray-curable resin layer on the second surface was 5 nm in all cases.

[Example 21]
In the same manner as in Example 1, a resin layer (easy adhesion layer) laminated PET film was produced. Next, the active energy ray-curable composition c for forming the following first active energy ray-curable resin layer is applied on the resin layer on the first surface of the resin layer (easy-adhesive layer) laminated PET film. A laminated film was produced in the same manner as in Example 1. The content of the particles (surface-treated silica particles) in the first active energy ray-curable resin layer is 9% by mass with respect to 100% by mass of the total solid content of the first active energy ray-curable resin layer. .

<Active energy ray-curable composition c>
86 parts by weight of dipentaerythritol hexaacrylate, 9 parts by weight of the surface-treated silica particle dispersion C in terms of solid content, 5 parts by weight of a photopolymerization initiator (“Irgacure (registered trademark) 184” manufactured by Ciba Specialty Chemicals) Parts were mixed with an organic solvent (methyl ethyl ketone) to prepare a composition having a solid content concentration of 30% by mass.

[Examples 22 to 28, Comparative Examples 21 to 30]
In the production of the resin layer (easy-adhesion layer) laminated PET film of Example 21, the resin layer (as shown in Example 21) except that the resin layer coating solution applied to the first surface was changed as shown in Table 3. Easy adhesion layer) A laminated PET film was prepared. Subsequently, each laminated film was produced in the same manner as in Example 21 except that the thickness of the first active energy ray-curable resin layer was changed as shown in Table 3.

  In Examples 21 to 28 and Comparative Examples 21 to 30, the easy-adhesion layer and the second active energy ray-curable resin layer on the second surface of the PET film are the same. The centerline average roughness (Ra2) of the surface of the active energy ray-curable resin layer on the second surface was 5 nm in all cases.

[Example 31]
In the same manner as in Example 1, a resin layer (easy adhesion layer) laminated PET film was produced. Subsequently, the active energy ray-curable composition d for forming the following first active energy ray-curable resin layer is applied on the resin layer on the first surface of the resin layer (easily adhesive layer) laminated PET film. A laminated film was produced in the same manner as in Example 1. The content of the particles (surface-treated silica particles) in the first active energy ray-curable resin layer is 9% by mass with respect to 100% by mass of the total solid content of the first active energy ray-curable resin layer. .

<Active energy ray-curable composition d>
86 parts by mass of dipentaerythritol hexaacrylate, 9 parts by mass of the surface-treated silica particle dispersion D in terms of solid content, 5 parts by weight of a photopolymerization initiator (“Irgacure (registered trademark) 184” manufactured by Ciba Specialty Chemicals) Parts were mixed with an organic solvent (methyl ethyl ketone) to prepare a composition having a solid content concentration of 30% by mass.

[Examples 32-38 and Comparative Examples 31-40]
In the production of the resin layer (easy adhesion layer) laminated PET film of Example 31, the resin layer (as in Example 31) except that the resin layer coating liquid applied to the first surface was changed as shown in Table 4. Easy adhesion layer) A laminated PET film was prepared. Subsequently, each laminated film was produced in the same manner as in Example 31 except that the thickness of the first active energy ray-curable resin layer was changed as shown in Table 4.

  In Examples 31-38 and Comparative Examples 31-40, the easy-adhesion layer on the second surface of the PET film and the second active energy ray-curable resin layer are both the same. The centerline average roughness (Ra2) of the surface of the active energy ray-curable resin layer on the second surface was 5 nm in all cases.

[Example 41]
In the same manner as in Example 1, a resin layer (easy adhesion layer) laminated PET film was produced. Subsequently, the active energy ray-curable composition e for forming the following first active energy ray-curable resin layer is applied on the resin layer on the first surface of the resin layer (easily adhesive layer) laminated PET film. A laminated film was produced in the same manner as in Example 1. The content of the particles (surface-treated silica particles) in the first active energy ray-curable resin layer is 9% by mass with respect to 100% by mass of the total solid content of the first active energy ray-curable resin layer. .

<Active energy ray-curable composition e>
86 parts by weight of dipentaerythritol hexaacrylate, 9 parts by weight of the surface-treated silica particle dispersion E in terms of solid content, 5 parts by weight of a photopolymerization initiator (“Irgacure (registered trademark) 184” manufactured by Ciba Specialty Chemicals) Parts were mixed with an organic solvent (methyl ethyl ketone) to prepare a composition having a solid content concentration of 30% by mass.

[Examples 42 to 48, Comparative Examples 41 to 50]
In the production of the resin layer (easy adhesion layer) laminated PET film of Example 41, a resin layer (as in Example 41) except that the resin layer coating solution applied to the first surface was changed as shown in Table 5. Easy adhesion layer) A laminated PET film was prepared. Subsequently, each laminated film was produced in the same manner as in Example 41 except that the thickness of the first active energy ray-curable resin layer was changed as shown in Table 5.

  In Examples 41 to 48 and Comparative Examples 41 to 50, the easy-adhesion layer and the second active energy ray-curable resin layer on the second surface of the PET film are the same. The centerline average roughness (Ra2) of the surface of the active energy ray-curable resin layer on the second surface was 5 nm in all cases.

[Example 51]
In the same manner as in Example 1, a resin layer (easy adhesion layer) laminated PET film was produced. Subsequently, the active energy ray-curable composition f for forming the following first active energy ray-curable resin layer is applied on the resin layer on the first surface of the resin layer (easily adhesive layer) laminated PET film. A laminated film was produced in the same manner as in Example 1. The content of the particles (surface-treated silica particles) in the first active energy ray-curable resin layer is 9% by mass with respect to 100% by mass of the total solid content of the first active energy ray-curable resin layer. .

<Active energy ray-curable composition f>
86 parts by weight of dipentaerythritol hexaacrylate, 9 parts by weight of the surface-treated silica particle dispersion F in terms of solid content, 5 parts by weight of a photopolymerization initiator (“Irgacure (registered trademark) 184” manufactured by Ciba Specialty Chemicals) Parts were mixed with an organic solvent (methyl ethyl ketone) to prepare a composition having a solid content concentration of 30% by mass.

[Examples 52 to 58, Comparative Examples 51 to 60]
In the production of the resin layer (easy-adhesive layer) laminated PET film of Example 51, a resin layer (as shown in Example 51) except that the resin layer coating solution applied to the first surface was changed as shown in Table 6. Easy adhesion layer) A laminated PET film was prepared. Subsequently, each laminated film was produced in the same manner as in Example 51 except that the thickness of the first active energy ray-curable resin layer was changed as shown in Table 6.

  In Examples 51-58 and Comparative Examples 51-60, the easy-adhesion layer on the second surface of the PET film and the second active energy ray-curable resin layer are both the same. The centerline average roughness (Ra2) of the surface of the active energy ray-curable resin layer on the second surface was 5 nm in all cases.

[Example 61]
In the same manner as in Example 1, a resin layer (easy adhesion layer) laminated PET film was produced. Subsequently, the active energy ray-curable composition g for forming the following first active energy ray-curable resin layer is applied on the resin layer on the first surface of the resin layer (easily adhesive layer) laminated PET film. A laminated film was produced in the same manner as in Example 1. The content of the particles (surface-treated silica particles) in the first active energy ray-curable resin layer is 9% by mass with respect to 100% by mass of the total solid content of the first active energy ray-curable resin layer. .

<Active energy ray-curable composition g>
86 parts by weight of dipentaerythritol hexaacrylate, 9 parts by weight of the surface-treated silica particle dispersion G in terms of solid content, 5 parts by weight of a photopolymerization initiator (“Irgacure (registered trademark) 184” manufactured by Ciba Specialty Chemicals) Parts were mixed with an organic solvent (methyl ethyl ketone) to prepare a composition having a solid content concentration of 30% by mass.

[Examples 62 to 68, Comparative Examples 61 to 70]
In the production of the resin layer (easy-adhesion layer) laminated PET film of Example 61, a resin layer (as in Example 61) except that the resin layer coating solution applied to the first surface was changed as shown in Table 7. Easy adhesion layer) A laminated PET film was prepared. Subsequently, each laminated film was produced in the same manner as in Example 61 except that the thickness of the first active energy ray-curable resin layer was changed as shown in Table 7.

  In Examples 61-68 and Comparative Examples 61-70, the easy-adhesion layer and the second active energy ray-curable resin layer on the second surface of the PET film are the same. The centerline average roughness (Ra2) of the surface of the active energy ray-curable resin layer on the second surface was 5 nm in all cases.

[Evaluation]
About laminated film obtained by said Example and comparative example, blocking resistance, the centerline average roughness (Ra1) of the 1st active energy ray-curable resin layer surface, the presence or absence of the protrusion by particle | grains, the haze value of laminated film The reflection color unevenness of the second active energy ray-curable resin layer surface was evaluated and measured. The results are shown in Tables 1-7.

  Each of the examples of the present invention has good blocking resistance, and the laminated film has a small haze value and excellent transparency.

  On the other hand, in the comparative example in which the first active energy ray-curable resin layer is laminated on the resin layer having a wetting tension greater than 52 mN / m, the blocking resistance is lowered.

  Moreover, the comparative example in which the thickness of the first active energy ray-curable resin layer is 2 μm or more is not significantly affected by the wetting tension of the resin layer and has good blocking resistance, but the haze value is increased.

[Examples 71 to 84]
On the surface of the second active energy ray-curable resin layer of each laminated film obtained in Examples 1, 5, 11, 15, 22, 26, 32, 36, 43, 47, 53, 57, 64 and 68 The following high refractive index layer and low refractive index layer were laminated in this order, and then the following transparent conductive film was formed on the low refractive index layer to produce a transparent conductive film for a capacitive touch panel. .

<Lamination of high refractive index layer>
The following active energy ray-curable composition for forming a high refractive index layer is applied by a gravure coating method, dried at 90 ° C., and then cured by irradiation with ultraviolet ray 400 mJ / cm ² to give a thickness of 0.04 μm. A rate layer was formed. The refractive index of this high refractive index layer was 1.65.
(Active energy ray-curable composition for forming a high refractive index layer)
As an active energy ray-curable resin, 47 parts by mass of dipentaerythritol hexaacrylate, 50 parts by mass of zirconium oxide, and 3 parts by mass of a polymerization initiator (“Irgacure (registered trademark) 184” manufactured by Ciba Specialty Chemicals Co., Ltd.) are organic. It was prepared by dispersing and dissolving in a solvent (propylene glycol monoethyl ether). The refractive index of this composition was 1.65.

<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 cured by irradiation with ultraviolet rays of 400 mJ / cm ² to have a thickness of 0.04 μm. A rate layer was formed. The refractive index of this low refractive index layer was 1.40.
(Active energy ray-curable composition for forming a low refractive index layer)
84 parts by mass of dipentaerythritol hexaacrylate, 14 parts by mass of hollow silica as an active energy ray curable resin, 2 parts by mass of a monomer polymerization initiator (“Irgacure (registered trademark) 184” manufactured by Ciba Specialty Chemicals) A part was prepared by dispersing and dissolving in an organic solvent (a mixed solvent of methyl isobutyl ketone and propylene glycol monoethyl ether having a mass ratio of 1: 1). The refractive index of this composition was 1.46.

<Lamination of transparent conductive film>
An ITO film was laminated by a sputtering method so as to have a thickness of 22 nm, and a transparent conductive film was formed by pattern processing (etching process) into a lattice pattern.

[Evaluation]
About the transparent conductive film of Examples 71-84, the visibility of blocking resistance and the transparent conductive film pattern was evaluated. The results are shown in Table 8.

  In addition, evaluation of blocking resistance of a transparent conductive film is made so that the surface of the first active energy ray-curable resin layer and the surface of the transparent conductive film face each other in the above-mentioned “(10) Evaluation of blocking resistance”. Evaluations were made in the same manner except that they were changed to overlap. The results are shown in Table 8.

  All the transparent conductive films of Examples 71 to 84 had good blocking resistance and visibility of the transparent conductive film pattern.

Claims (9)

  A resin layer is laminated on at least one surface of the base film, and a first active energy ray-curable resin layer is laminated directly on the resin layer, and the first active energy ray-curable resin layer contains particles. A laminated film having protrusions of the particles on the surface of the first active energy ray-curable resin layer, the thickness (d) of the first active energy ray-curable resin layer being less than 2 μm, The ratio (r / d) of the average particle diameter (r: μm) of the particles to the thickness (d: μm) of the linear curable resin layer is 0.5 or less, and the wetting tension of the resin layer surface is 52 mN / A laminated film characterized by being m or less.   The laminated film according to claim 1, wherein the laminated film has a haze value of 0.5% or less.   The laminated film according to claim 1 or 2, wherein the base film is a polyethylene terephthalate film.   The laminated film according to any one of claims 1 to 3, wherein a center line average roughness (Ra1) of the surface of the first active energy ray-curable resin layer is less than 30 nm.   The laminated film according to any one of claims 1 to 4, wherein an average particle diameter (r) of the particles is in a range of 0.03 to 0.5 µm.   The content of particles in the first active energy ray-curable resin layer is 3 to 17% by mass with respect to 100% by mass of the total solid content of the first active energy ray-curable resin layer. The laminated film according to any one of the above.   The substrate film has a second active energy ray-curable resin layer on the opposite side of the surface on which the first active energy ray-curable resin layer is provided, with an easy-adhesion layer interposed therebetween, and the second active energy ray-curable resin is cured. The laminated film according to any one of claims 1 to 6, wherein the thickness of the conductive resin layer is less than 2.5 µm and the center line average roughness (Ra2) of the surface of the second active energy ray-curable resin layer is 25 nm or less. .   The base film is a polyethylene terephthalate film having a refractive index of 1.61-1.70, the refractive index of the easy-adhesion layer is 1.55-1.60, and the second active energy ray-curable resin layer. The laminated film according to claim 7, having a refractive index of 1.48 to 1.54.   The transparent conductive film which has a transparent conductive film in the at least one surface of the laminated | multilayer film in any one of Claims 1-8.