JP2019168633A - Resin composition for fingerprint fitting low refractive index layer and anti-reflection film - Google Patents

Abstract

An antireflection film having an excellent appearance on a painted surface, invisible fingerprints, and excellent fingerprint wiping properties is provided. In order to solve the above-mentioned problem, an antireflection film comprising a hard coat layer and a fingerprint-compatible low-refractive index layer in this order on one surface of a thermoplastic transparent base film, comprising: The refractive index layer comprises the following components (a) to (e): (a) a fluorine-containing ultraviolet-curable adamantane derivative, (b) an ultraviolet-curable resin copolymerizable with (a), and (c) hollow silica. It contains fine particles, (d) metal oxide fine particles, and (e) a photopolymerization initiator, the content of the component (a) is 10.0 to 20.0% by mass, and the content of the component (b) is 19.0. 61.9 mass%, the content of the component (c) is 27.0 to 69.9 mass%, the content of the component (d) is 0.1 to 3.0 mass%, and the content of the component (e). Is a cured product of a resin composition having a content of 1.0 to 10.0% by mass. [Selection diagram] Fig. 1

Description

  The present invention relates to an antireflection film that is applied to the surface of a touch panel and has excellent antifouling properties.

  Currently, touch panels are widely used as devices capable of inputting information by directly touching an image display unit. An antireflection film is generally attached to the surface of the touch panel in order to reduce the deterioration of visibility due to reflected light from outside light. However, since the touch panel comes into contact with the outside air or is touched by human hands almost daily, dirt, fingerprints and the like adhere to the surface, resulting in problems such as deterioration of visibility and loss of aesthetics.

  In order to solve this problem, an antireflection film that has been subjected to an antifouling treatment in which a silicone or fluorine antifouling agent is applied to the film surface has been proposed (Patent Documents 1 and 2). In Patent Document 1, the addition of a silicone material having a polydimethylsiloxane structure to the low refractive index layer imparts antifouling properties by water and oil repellency. Further, in Patent Document 2, antifouling property is imparted by water and oil repellency by adding a fluorosurfactant to the low refractive index layer. Due to the antifouling property due to these water and oil repellency, the attached fingerprint is suppressed and the wiping property is improved.

  Further, a hard coat film subjected to an antifouling treatment in which a water repellent and lipophilic antifouling agent is applied to the film surface has been proposed (Patent Document 3). In Patent Document 3, the addition of a polymerizable group-containing fluorinated adamantane derivative to the hard coat layer imparts antifouling properties due to water repellency and lipophilicity. This reduces the poor visibility due to scattering because the oil content of the attached fingerprint is adapted by the antifouling property due to the water repellency and lipophilicity.

However, the antireflective films described in Patent Document 1 and Patent Document 2 have excellent fingerprint adhesion and wiping properties, but have a problem that the adhered fingerprint is repelled and the stains are conspicuous. If a silicone or fluorine antifouling agent is not applied to prevent the attached fingerprint from repelling oil, the coating surface uniformity during film formation will be impaired and the coating surface will be uneven and the fingerprint will be difficult to wipe off. . Therefore, an antireflection film with a water-repellent / lipophilic antifouling agent is assumed, but not only the appearance of the coated surface is excellent, but also the surface has high strength, excellent wear resistance, and scratch resistance. Also, it is easy to wipe off dirt, it is difficult to satisfy all, and there is no proposal.
Further, in the hard coat layer of Patent Document 3, dirt is inconspicuous because the oil content of the attached fingerprint is familiar, but there is a problem that reflection is strong because there is no antireflection function. Therefore, an antireflection film having a water repellent and lipophilic antifouling agent on the film surface is assumed. However, if a necessary amount of a water-repellent / lipophilic antifouling agent is applied to satisfy the appearance of the coated surface, the fingerprint adhesion and wiping properties are excellent, but the surface strength and wear resistance are poor, and scratches are easily formed. If the water-repellent / lipophilic antifouling agent is insufficient, the coating uniformity during film formation is impaired, and unevenness of the coating surface occurs, and fingerprints are difficult to wipe off. In addition to the excellent appearance of the coated surface, the surface has high strength and excellent wear resistance, is not easily scratched, and is easy to wipe off dirt.

  Thus, there is a demand for an antireflection film that has not only excellent appearance on the coated surface, but also excellent fingerprint compatibility and fingerprint wiping, high surface strength, excellent wear resistance, and scratch resistance. It is.

JP 2011-154177 A JP 2008-122603 A JP 2012-022173 A

  An object of the present invention is to provide an antireflection film having excellent coating surface appearance, fingerprint invisibility, excellent fingerprint wiping property, and excellent wear resistance and scratch resistance.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have determined that a resin composition using a specific amount of a specific fluorine-containing UV-curable adamantane derivative and metal oxide fine particles in the structure of the low refractive index layer The present inventors have found the knowledge of solving the above problems by curing and applying an object, and have completed the present invention.
That is, the present invention includes the following [1] and [2].
[1] An antireflection film comprising a hard coat layer and a fingerprint-familiar low refractive index layer in this order on one surface of a thermoplastic transparent substrate film,
The fingerprint-familiar low refractive index layer comprises the following components (a) to (e):
(A) a fluorine-containing UV-curable adamantane derivative,
(B) an ultraviolet curable resin copolymerizable with (a),
(C) hollow silica fine particles,
It contains (d) metal oxide fine particles and (e) a photopolymerization initiator, the content of (a) component is 10.0 to 20.0% by mass, and the content of (b) component is 19.0. 61.9 mass%, the content of component (c) is 27.0-69.9 mass%, the content of component (d) is 0.1-3.0 mass%, and the content of component (e) Is an antireflection film, which is a cured product of a resin composition having 1.0 to 10.0% by mass.
[2] The contact angle with respect to oleic acid is 30 ° or less, and the arithmetic average roughness (Ra) defined in JIS B0601-1994 is 0.001 to 0.020 μm. [1] The antireflection film according to [1].

  According to the present invention, by appropriately setting the resin composition of the fingerprint conforming low refractive index layer, the coating film smoothness, fingerprint conformability, fingerprint wiping properties are excellent, and the surface has high strength and excellent wear resistance. An antireflection film that is difficult to scratch can be provided.

It is a schematic longitudinal cross-sectional view which shows an example of the antireflection film of one embodiment of this invention.

<Antireflection film>
The antireflection film of the present invention comprises a hard coat layer and a fingerprint familiar low refractive index layer in this order on one surface of a thermoplastic transparent substrate film (hereinafter referred to as a substrate film). Below, the component of this antireflection film is demonstrated in order.

<Transparent substrate film>
As the transparent substrate film, a film made of polyester resin, polycarbonate resin, triacetyl cellulose resin, norbornene resin, or cycloolefin resin can be used. As a film made of polyester resin, a PET film (Lumirror U-403) made by Toray Industries, Inc. As a film made of polycarbonate resin, a polycarbonate film (PC-2151) made by Teijin Chemicals Ltd., a film made of triacetyl cellulose resin Is a triacetyl cellulose film (Fujitac) manufactured by Fuji Film Co., Ltd., an arton film manufactured by JSR Co. as a film made of norbornene resin, and a ZEONOR film (ZF14, manufactured by Nippon Zeon Co., Ltd.). ZF16) and the like.

The film thickness of the transparent substrate film is usually about 25 to 500 μm, and the lower limit is preferably 50 μm or more, and more preferably 75 μm or more. The upper limit is preferably 250 μm or less, more preferably 150 μm or less, and particularly preferably 120 μm or less.
The refractive index of the transparent substrate film is usually from 1.49 to 1.67, and the lower limit is preferably 1.52 or more, more preferably 1.56 or more. As an upper limit, Preferably it is 1.63 or less, More preferably, it is 1.59 or less.

<Hard coat layer>
The hard coat layer is a layer provided on the transparent substrate film for improving the surface hardness.
The refractive index of the hard coat layer is 1.49 to 1.59, and the lower limit is preferably 1.49 or more, and more preferably 1.50 or more. As an upper limit, Preferably it is 1.56 or less, More preferably, it is 1.54 or less. If the refractive index is within this range, interference fringes will not occur due to the difference in refractive index between the transparent substrate film and the hard coat layer, and light caused by a high refractive index material from an excessive amount of use will not be generated. The hard coat layer is not colored due to absorption and light scattering, and the total light transmittance does not decrease. Moreover, the film thickness after dry-hardening of a hard-coat layer is 1-20 micrometers, As a lower limit, Preferably it is 2 micrometers or more, More preferably, it is 4 micrometers or more. As an upper limit, Preferably it is 15 micrometers or less, More preferably, it is 10 micrometers or less. If the film thickness is within this range, sufficient surface hardness can be obtained, and problems such as lowering of flexibility do not occur.

<Resin composition for hard coat layer>
The material used for the resin composition for the hard coat layer is not particularly limited as long as it is a known material conventionally used for antireflection films and the like. For example, a reactive silicon compound such as tetraethoxysilane or an active energy ray curable resin can be used, and these may be mixed. Then, a hard coating layer coating solution prepared by adding a photopolymerization initiator to these is irradiated with an active energy ray such as ultraviolet light or electron beam and cured to form a first hard coating layer and a second hard coating layer. be able to. Examples of the active energy ray-curable resin include monofunctional (meth) acrylate and polyfunctional (meth) acrylate. Specifically as monofunctional (meth) acrylate, (meth) acrylic acid alkyl ester, (meth) acrylic acid (poly) ethylene glycol group-containing (meth) acrylic acid ester and the like are preferable. Examples of the polyfunctional (meth) acrylate include ester compounds of polyhydric alcohol and (meth) acrylic acid, polyfunctional polymerizable compounds containing two or more (meth) acryloyl groups such as urethane-modified acrylate, and the like. In the present specification, “(meth) acrylate” refers to acrylate and methacrylate. Similarly, “(meth) acrylic monomer” described later refers to an acrylic monomer and a methacrylic monomer, and “(meth) acryloyl group” refers to an acryloyl group and a methacryloyl group.

  Examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t- Butyl (meth) acrylate, pentyl (meth) acrylate, t-amyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) Acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate , Tetradecyl (meth) acrylate, hexamethyl (meth) acrylate, octadecyl (meth) acrylate and other alkyl (meth) acrylates having 1 to 20 carbon atoms; 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) Alkoxyalkyl (meth) acrylates such as acrylate, 3-methoxypropyl (meth) acrylate, 3-methoxybutyl (meth) acrylate; cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, adamantyl (meth) acrylate, isobornyl (meth) (Meth) acrylate having an alicyclic hydrocarbon group such as acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate Hydroxyl group-containing such as relations (meth) acrylate; (meth) and the like carboxyl group-containing monomers such as acrylic acid.

Polyfunctional polymerizable compounds include ethylene glycol di (meth) acrylate, propylene glycol (meth) acrylate, butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hexanediol di (meth) acrylate, and nonanediol. Bifunctional (meth) acrylates such as di (meth) acrylate and tricyclo [5.2.1.0 ^2,6 ] decandimethanol di (meth) acrylate; trimethylolethane tri (meth) acrylate, trimethylolpropane tri Trifunctional (meth) acrylates such as (meth) acrylate, glycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate ) Acrylate; pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ditrimethylolpropane penta (meth) acrylate, dipenta Examples include tetrafunctional or higher functional (meth) acrylates such as erythritol hexa (meth) acrylate and ditrimethylolpropane hexa (meth) acrylate.

  Among these, from the viewpoint of achieving both productivity and hardness, a cured product of a composition containing an active energy ray-curable resin having a pencil hardness (evaluation method: JIS K5600-5-4) of H or higher is preferable. Although it does not specifically limit as a composition containing such an active energy ray curable resin, For example, 2 or more types of well-known active energy ray curable resins or well-known active energy ray curable resins were mixed. And those commercially available as ultraviolet curable hard coat materials can be used.

The photopolymerization initiator is used as a polymerization initiator when a coating film is formed by curing the coating liquid for the first hard coat layer or the coating liquid for the second hard coat layer with active energy rays such as ultraviolet rays (UV). . The photopolymerization initiator is not particularly limited as long as it initiates polymerization upon irradiation with active energy rays, and known compounds can be used. For example, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1 -One, acetophenone polymerization initiators such as 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, benzoin, 2,2-dimethoxy 1,2 -Benzoin polymerization initiators such as diphenylethane-1-one, benzophenone, [4- (methylphenylthio) phenyl] phenylmethanone, 4-hydroxybenzophenone, 4-phenylbenzophenone, 3,3 ', 4,4' -Benzophenone polymerization initiators such as tetra (t-butylperoxycarbonyl) benzophenone, 2-chlorothio Sandton, such thioxanthone type polymerization initiators such as 2,4-diethyl thioxanthone, and the like.
The solvent of the coating solution is not particularly limited as long as it is a known one that has been conventionally used for the coating solution for forming each layer in this type of antireflection film, and examples thereof include alcohol-based, ketone-based, and ester-based solvents. Can be selected in a timely manner.

  The hard coat layer may contain translucent fine particles. The light-transmitting fine particles form surface irregularities on the hard coat layer and improve antireflection properties (antiglare properties). Arbitrary materials can be used for the translucent fine particles. Examples of such translucent fine particles include silica, a polymer obtained by polymerizing at least one monomer selected from vinyl chloride, (meth) acrylic monomer, styrene and ethylene. It is formed. Furthermore, other additives may be contained. Examples of other additives include surface conditioners and slip agents.

<Fingerprint familiar low refractive index layer>
The refractive index of the low-refractive index layer that is compatible with the fingerprint is set to be lower than the refractive index of the hard coat layer or the high-refractive index layer that is the coating target layer, and the refractive index is 1.30 to 1.46. The lower limit is preferably 1.33 or more, and more preferably 1.37 or more. As an upper limit, Preferably it is 1.43 or less, More preferably, it is 1.40 or less. If the refractive index is within this range, a sufficiently hard layer can be formed, and sufficient antireflection performance can be obtained.

<Fingerprint familiar resin composition for low refractive index layer>
The fingerprint-familiar low refractive index layer used in the present invention comprises the following components (a) to (e):
(A) a fluorine-containing UV-curable adamantane derivative,
(B) an ultraviolet curable resin copolymerizable with (a),
(C) hollow silica fine particles,
It is a cured product of a resin composition containing (d) metal oxide fine particles and (e) a photopolymerization initiator.
(However, the sum of the components (a) to (e) is 100% by mass)

[(A) Fluorine-containing UV-curable adamantane derivative]
The fluorine-containing UV-curable adamantane derivative (a) used in the present invention is for improving the smoothness of the coating film and expressing the water-repellent / lipophilic property. It is possible to improve the adhesion of the attached fingerprint.

  The fluorine-containing UV-curable adamantane derivative used in the present invention may contain fluorine in any part of its structure, but preferably has a structure in which the hydrogen atom of the adamantane ring is substituted with a fluorine atom. Moreover, as an ultraviolet curing part, polymeric substituents, such as a vinyl group, (meth) acryloyl group, an epoxy group, and an oxetane group, are preferable.

上記の一般式（Ｉ）において、Ｆは、フッ素原子を表し、Ｚ^１は、下記の一般式（ＩＩ）または（ＩＩＩ）で表される基を示す。

上記の式（ＩＩ）または（ＩＩＩ）中、Ｒ^１〜Ｒ^４は、それぞれ独立に水素原子、ハロゲン原子、またはヘテロ原子を含んでいてもよい炭素数１〜２０、好ましくは１〜１５の脂肪族炭化水素基を示す。ハロゲン原子としては、フッ素、塩素、臭素およびヨウ素が挙げられる。 The fluorine-containing ultraviolet curable adamantane derivative (a) used in the present invention is represented by the following general formula (I).

In the above general formula (I), F represents a fluorine atom, and Z ¹ represents a group represented by the following general formula (II) or (III).

In the above formula (II) or (III), R ^{1 to} R ⁴ each independently represent a hydrogen atom, a halogen atom, or a hetero atom, which has 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms. Represents a hydrocarbon group. Examples of the halogen atom include fluorine, chlorine, bromine and iodine.

  Examples of the hydrocarbon group not containing a hetero atom include a linear or branched alkyl group having 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. N-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tetradecyl group, pentadecyl group, hexadecyl group Group, octadecyl group, eicosyl group and the like. Among these, a methyl group, an ethyl group, a propyl group, and a butyl group are preferable.

As a hydrocarbon group containing a hetero atom,
-O- (C1-C20, preferably C1-C15 linear or branched alkyl group),
-S- (C1-C20, preferably C1-C15 linear or branched alkyl group),
-CO- (C1-C19, preferably C1-C14 linear or branched alkyl group),
-NH- (C1-C20, preferably C1-C15 linear or branched alkyl group),
-N (C1-C19, preferably C1-C7 linear or branched alkyl group),
Etc.
Specific examples of the hydrocarbon group containing a hetero atom include a methoxy group, an ethoxy group, a butoxy group, a hydroxymethyl group, a hydroxyethyl group, a methylthio group, an ethylthio group, a methylamino group, a dimethylamino group, and an ethylamino group. Group and diethylamino group.

n is an integer of 0 or more, for example, an integer of 0 to 20, preferably an integer of 0 to 10, more preferably 0, 1, 2, 3, 4 or 5.
m is an integer of 0 or more, for example, an integer of 0 to 20, preferably an integer of 0 to 10, more preferably 0, 1, 2, 3, 4 or 5, particularly 0 or 1.

上記の一般式（ＩＶ）において、Ｒ^５は水素原子、メチル基またはトリフルオロメチル基を示す。上記の一般式（ＶＩ）において、Ｒ^６は炭素数１〜５の炭化水素基を示す。この炭素数１〜５の炭化水素基としては、アルキル基およびアルコキシ基などが挙げられる。アルキル基は、直鎖状、分岐状、環状のいずれであってもよく、具体例としては、メチル基、エチル基、プロピル基およびブチル基などが挙げられる。アルコキシ基としては、メトキシ基およびエトキシ基などが挙げられる。 In the above general formula (I), X ¹ represents a vinyl group, a polymerizable group represented by the following general formula (IV), the following formula (V), or the following general formula (VI).

In the above general formula (IV), R ⁵ represents a hydrogen atom, a methyl group or a trifluoromethyl group. In said general formula (VI), R < ⁶ > shows a C1-C5 hydrocarbon group. Examples of the hydrocarbon group having 1 to 5 carbon atoms include an alkyl group and an alkoxy group. The alkyl group may be linear, branched or cyclic, and specific examples include a methyl group, an ethyl group, a propyl group and a butyl group. Examples of the alkoxy group include a methoxy group and an ethoxy group.

  In the above general formula (I), Y represents a hydrogen atom, a hydrocarbon group, an alkoxy group, a halogen-substituted hydrocarbon group, a cyclic hydrocarbon group, a halogen-substituted cyclic hydrocarbon group, a hydroxyl group, a carboxyl group, and the same Two Y bonded to a carbon atom represent a group selected from C═O formed together with a carbon atom.

  Examples of the hydrocarbon group represented by Y include a hydrocarbon group that may contain a hetero atom. As the hydrocarbon group containing no hetero atom, the same groups as those used in the above formula (II) or (III) can be used, and a straight chain having 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms, or Examples include branched alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, and heptyl. Group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tetradecyl group, pentadecyl group, hexadecyl group, octadecyl group, iconicyl group and the like.

  As the hydrocarbon group containing a hetero atom, the same groups as those used in the above formula (II) or (III) can be used. Specifically, for example, a methoxy group, an ethoxy group, a butoxy group, Examples thereof include a hydroxymethyl group, a hydroxyethyl group, a methylthio group, an ethylthio group, a methylamino group, a dimethylamino group, an ethylamino group, and a diethylamino group.

  Examples of the cyclic hydrocarbon group represented by Y include a cycloalkyl group having 5 to 10 carbon atoms, specifically a cyclopentyl group, a methylcyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, an ethylcyclohexyl group, and a cyclooctyl group. Can be mentioned. In addition, as the halogen-substituted cyclic hydrocarbon group, a group in which one or more hydrogen atoms of the above cyclic hydrocarbon group are substituted with a halogen atom, such as a fluorocyclopentyl group, a fluorocyclohexyl group, a trifluoromethylcyclopentyl group, and a trivalent group. Examples include a fluoromethylcyclohexyl group.

In said general formula (I), s is an integer of 1-15, As a lower limit, Preferably it is 5 or more, More preferably, it is 8 or more. As an upper limit, Preferably it is 14 or less, More preferably, it is 12 or less. By setting s to 1 or more, the low-refractive-index layer familiar to fingerprints can be made a hard layer.
In said general formula (I), t is an integer of 1-15, As a lower limit, Preferably it is 4 or more, More preferably, it is 8 or more. By setting t to 1 or more, it is possible to improve the fingerprint wiping property of the low-refractive-index layer familiar to fingerprints.
In said general formula (I), u is an integer of 0-14, Preferably it is an integer of 0-4.
In the above general formula (I), s + t + u = 16.

  The fluorine-containing ultraviolet curable adamantane derivative can be obtained by a method in which perfluoroadamantanols and acrylic acid and methacrylic acid are azeotropically dehydrated under reflux of a solvent. As the raw material perfluoroadamantanol used here, perfluoro-1-adamantanol, perfluoro-1,3-adamantanediol, perfluoro-1-adamantane methanol, perfluoro-1,3-adamantane dimethanol, Examples include perfluoro-1-adamantane ethanol, perfluoro-1,3-adamantanediethanol, 1- (2-hydroxyethoxy) perfluoroadamantane, and 1,3-bis (2-hydroxyethoxy) perfluoroadamantane. As these reaction solvents, toluene, xylene and the like are preferably used.

  The fluorine-containing UV-curable adamantane derivative is contained in an amount of 10.0 to 20.0% by mass in the resin composition for a low-refractive index layer familiar with fingerprints. As a lower limit, Preferably it is 12.0 mass% or more, More preferably, it is 14.0 mass% or more. As an upper limit, Preferably it is 18.0 mass% or less, More preferably, it is 16.0 mass% or less. When the content is less than 10.0% by mass, the smoothness cannot be increased during coating, and the adhesion of the fingerprint that adheres to the surface of the low refractive index layer familiar to the fingerprint cannot be weakened. On the other hand, if it exceeds 20.0% by mass, the wear resistance and scratch resistance of the surface strength deteriorate.

[(B) UV curable resin copolymerizable with (a)]
The ultraviolet curable resin (b) copolymerizable with (a) used in the present invention can impart hardness to the low refractive index layer familiar with fingerprints.
Examples of the ultraviolet curable resin (b) copolymerizable with (a) used in the present invention include monofunctional (meth) acrylate and polyfunctional (meth) acrylate. Specifically as monofunctional (meth) acrylate, (meth) acrylic acid alkyl ester, (meth) acrylic acid (poly) ethylene glycol group-containing (meth) acrylic acid ester and the like are preferable. Examples of the polyfunctional (meth) acrylate include ester compounds of polyhydric alcohol and (meth) acrylic acid, polyfunctional polymerizable compounds containing two or more (meth) acryloyl groups such as urethane-modified acrylate, and the like.
As the ultraviolet curable resin (b) copolymerizable with (a), monofunctional (meth) acrylates, polyfunctional polymerizable compounds, and the like used in the hard coat layer resin composition can be similarly used.

  The ultraviolet curable resin (b) copolymerizable with (a) used in the present invention is contained in 19.0 to 61.9% by mass in the resin composition for a low refractive index layer familiar with fingerprints. As a lower limit, Preferably it is 25.0 mass% or more, More preferably, it is 30.0 mass% or more. As an upper limit, Preferably it is 50.0 mass% or less, More preferably, it is 40.0 mass% or less. If the content is less than 19.0% by mass, the low-refractive-index layer familiar to fingerprints is insufficient in hardness and the transmittance is lowered. On the other hand, if it exceeds 61.9% by mass, the refractive index of the coating film becomes high and the anti-reflectivity performance is lowered, which is not preferable.

[(C) Hollow silica fine particles]
The hollow silica fine particles (c) used in the present invention are blended to actively lower the refractive index. The refractive index of the hollow silica fine particles (c) varies depending on the production method, but is preferably 1.25 to 1.40. The hollow silica fine particles are not particularly limited as long as the refractive index is lowered, and known hollow silica fine particles can be used. Specific examples include acrylic modified hollow silica fine particles through rear NAU manufactured by JGC Catalysts & Chemicals.
The hollow silica fine particles (c) used in the present invention are contained in an amount of 27.0 to 69.9 mass% in the fingerprint-familiar low refractive index layer. As a lower limit, Preferably it is 25.0 mass% or more, More preferably, it is 35.0 mass% or more. As an upper limit, Preferably it is 60.0 mass% or less, More preferably, it is 45.0 mass% or less. When the content of the hollow silica fine particles (c) is less than 27.0% by mass, the refractive index of the low-refractive-index layer familiar to fingerprints cannot be in the range described later. On the other hand, when the content of silica fine particles is more than 69.9% by mass, the coating film strength becomes weak.

[(D) Metal oxide fine particles]
Examples of the metal oxide fine particles (d) used in the present invention include fine particles of aluminum oxide (alumina), zinc oxide, titanium oxide, zirconium oxide, cerium oxide, tin oxide, antimony oxide, tungsten oxide, beryllium oxide, and the like. Of these metal oxide fine particles, aluminum oxide fine particles are particularly preferred from the viewpoints of wear resistance and scratch resistance.

  The average particle diameter of the metal oxide fine particles (d) used in the present invention preferably does not greatly exceed the thickness of the low-refractive-index layer familiar to fingerprints, usually 0.1 μm or less, particularly preferably 10 to 100 nm. If the average particle diameter is within this range, the optical performance of the low-refractive-index layer familiar to fingerprints does not change unintentionally, such as light scattering. In addition, the influence on the transparency due to the refractive index of the metal oxide fine particles (d), the content in the layer, and the like is also important, and the metal oxide fine particles (d) so as not to reduce the transparency of the optical article. The refractive index and the content rate are adjusted. Furthermore, the metal oxide fine particles (d) can be modified on the surface of the fine particles with various coupling agents as required. As such a coupling agent, for example, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyltrimethoxy Examples include organically substituted silicon compounds such as silane. In addition, organic acid salts containing metal alkoxides such as aluminum, titanium, zirconium, and antimony can be used. In particular, by modifying the surface with a reactive group such as a (meth) acryloyl group, it is possible to form a highly reflective anti-reflection layer.

In the present invention, the metal oxide fine particles (d) are used in combination with the fluorine-containing ultraviolet curable adamantane derivative (a), so that they do not add an excessive amount by strengthening each other and wear resistance. In addition, it is possible to develop performance with respect to surface strength of scratch resistance.
Content of metal oxide microparticles | fine-particles (d) is 0.1-3.0 mass% in the resin composition for low refractive index layers. As a lower limit, Preferably it is 0.2 mass% or more, More preferably, it is 0.5 mass% or more. As an upper limit, Preferably it is 2.5 mass% or less, More preferably, it is 2.0 mass% or less. However, in the above-described aluminum oxide, since the influence on transparency is large, and a sufficient effect can be obtained with a small amount of addition, the lower limit is preferably 0.1% by mass or more, more preferably It is 0.2% by mass or more. As an upper limit, Preferably it is 1.0 mass% or less, More preferably, it is 0.5 mass% or less.

[(E) Photopolymerization initiator]
The photopolymerization initiator (e) used in the present invention is used as a polymerization initiator for forming a coating film by curing a coating solution for a low refractive index layer that is compatible with fingerprints using active energy rays such as ultraviolet rays (UV). The photopolymerization initiator (e) is not particularly limited as long as polymerization is initiated by irradiation with active energy rays, and known compounds can be used. For example, acetophenone-based polymerization initiators such as 1-hydroxycyclohexyl phenyl ketone and 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzoin, 2,2-dimethoxy 1,2-diphenylethane-1 Benzoin-based polymerization initiators such as -one, benzophenone, [4- (methylphenylthio) phenyl] phenylmethanone, 4-hydroxybenzophenone, 4-phenylbenzophenone, 3,3 ', 4,4'-tetra (t- Examples thereof include benzophenone polymerization initiators such as (butylperoxycarbonyl) benzophenone, and thioxanthone polymerization initiators such as 2-chlorothioxanthone and 2,4-diethylthioxanthone.
The content of the photopolymerization initiator (e) used in the present invention is 1.0 to 10.0% by mass in the resin composition for a low refractive index layer familiar to fingerprints, and the lower limit is preferably 2.0. It is at least mass%, more preferably at least 4.0 mass%. As an upper limit, Preferably it is 8.0 mass% or less, More preferably, it is 6.0 mass% or less. If content of a photoinitiator (e) is less than 1.0 mass%, hardening of a hard-coat layer will become inadequate. On the other hand, when the content of the photopolymerization initiator (e) exceeds 10.0% by mass, the photoinitiator is unnecessarily increased, which is not preferable.

[Other ingredients]
Further, the resin composition for a fingerprint-familiar low refractive index layer used in the present invention may contain other components in addition to the above-mentioned compounds within a range not impairing the effects of the present invention. Other components are not particularly limited, for example, inorganic or organic pigments, other polymers, thermal decomposition polymerization initiators, photopolymerization initiators, polymerization inhibitors, antioxidants, dispersants, surfactants, A light stabilizer, a leveling agent, etc. are mentioned.

The antireflective film of the present invention can contain other layers other than the hard coat layer and the fingerprint familiarity low-refractive index layer.
As the other layer, for example, a layer such as a high refractive index layer that can more effectively exhibit an antireflection effect or an easy-adhesion layer that improves the adhesion between the hard coat and the base film is preferable.

<High refractive index layer>
The high refractive index layer is a layer for exhibiting an antireflection effect due to a significant refractive index difference from the above-mentioned fingerprint familiar low refractive index layer. The refractive index of the high refractive index layer is set higher than that of the hard coat layer and the low refractive index layer familiar to fingerprints. The refractive index of the high refractive index layer is set to 1.5 to 2.4. When this refractive index is smaller than 1.5, the antireflection performance is impaired. On the other hand, it is difficult to form a high refractive index layer having a refractive index exceeding 2.4.

<Resin composition for high refractive index layer>
The material constituting the high refractive index layer is not particularly limited as long as it is a known material conventionally used for an antireflection film or the like in the range of the refractive index of the high refractive index layer. Any material can be used. Examples of the inorganic material include fine particles such as zinc oxide, titanium oxide, cerium oxide, aluminum oxide, silane oxide, antimony oxide, zirconium oxide, tin oxide, and ITO. In particular, tin oxide, antimony oxide and ITO are preferable from the viewpoint of conductivity and antistatic ability, and titanium oxide, cerium oxide, zinc oxide and zirconium oxide are preferable from the viewpoint of high refractive index.

As the organic material, for example, a composition containing a polymerizable monomer having a refractive index of 1.5 to 1.8 that has been polymerized and cured can be used. Examples of such a polymerizable monomer include 2-vinylnaphthalene, 4-bromostyrene, 9-vinylanthracene and the like.
Further, as the material constituting the high refractive index layer, fine particles of inorganic material and organic material can be used in combination. In this case, the refractive index of the polymerized cured product described above is 1.6 to 1.8. In addition to such polymerizable monomers, other polymerizable monomers and compositions containing these polymers can be used as the active energy ray-curable resin during wet coating. The average particle size of the fine particles of the inorganic material preferably does not greatly exceed the thickness of the high refractive index layer, and is particularly preferably 0.15 μm or less. If the average particle size of the fine particles of the inorganic material is larger than the thickness of the high refractive index layer, the optical performance of the high refractive index layer tends to deteriorate, such as light scattering.

<Easily adhesive layer>
The easy-adhesion layer has a function of enhancing the adhesion between the base film and the hard coat layer without adversely affecting the optical properties. The film thickness of this easy adhesion layer is 5 to 30 nm. As a minimum, Preferably it is 10 nm or more, More preferably, it is 15 nm or more. As an upper limit, Preferably it is 25 nm or less, More preferably, it is 20 nm or less.
The material for forming the easy adhesion layer is not particularly limited, but a material having a refractive index that does not cause interference fringes or the like is preferable.

The antireflection film of the present invention will be described with reference to FIG.
The antireflection films 10 and 10A shown in FIGS. 1A and 1B are a hard coat layer 2 on a transparent base film 1, a high refractive index layer 3 formed as necessary, and a fingerprint as an outermost layer. The familiar low refractive index layer 4 is laminated.

<Formation of hard coat layer, high refractive index layer and fingerprint-familiar low refractive index layer>
The hard coat layer, the high refractive index layer and the fingerprint familiar low refractive index layer are formed by sequentially applying each resin composition onto the transparent substrate film and then curing it by irradiation with active energy rays.
The coating method of the hard coat layer, high refractive index layer and fingerprint familiar low refractive index layer is not particularly limited. For example, roll coating method, spin coating method, dip coating method, spray coating method, bar coating method, knife coating method, die coating method. Any known method such as a method, an ink jet method, or a gravure coating method can be adopted. The type of active energy ray is not particularly limited, but it is preferable to use ultraviolet rays from the viewpoint of convenience and the like. In addition, in order to improve the adhesiveness of the hard coat layer to the transparent substrate film, it is possible to pre-treat the surface of the transparent substrate film such as a corona discharge treatment in advance.

Further, from the viewpoint of coatability, each resin composition is preferably diluted with a solvent for coating. The solvent is not particularly limited as long as it is a known one that has been conventionally used for coating liquids for forming each layer. For example, alcohol-based, ketone-based, and ester-based solvents can be selected as appropriate, such as uneven drying on the film surface, etc. Therefore, it is preferable to use a plurality of solvents having different vapor pressures.
What is necessary is just to perform drying after apply | coating by said coating method etc. suitably using a dryer etc. The drying temperature can be appropriately set depending on the vapor pressure and solid content concentration of the solvent, but it is preferable to increase the temperature stepwise in order to prevent drying unevenness on the film surface, distorted skin, and the like. What is necessary is just to set drying time suitably with the vapor pressure and solid content concentration of a solvent.

  Since the resin composition used in the present invention contains the components (a) to (d) in the specified amount range of the present invention, the antireflection film of the present invention preferably has a contact angle with respect to oleic acid due to the action of the cured product. It is 30 ° or less, more preferably 20 ° or less. Since the smaller the contact angle, the better. The lower limit is not particularly defined, but it is preferably 5 ° or more. The antireflection film of the present invention preferably has an arithmetic average roughness (Ra) defined in JIS B0601-1994 of 0.001 to 0.020 μm. From the values of contact angle and arithmetic mean roughness (Ra), in the antireflection film of the present invention, the resin constituting the low refractive index layer that is compatible with fingerprints is easily compatible with lipid components derived from living organisms, and the attached fingerprint is visible. It is presumed that a function that is difficult to be performed can be expressed. At the same time, in the antireflection film of the present invention, the visibility of a display image or the like is not deteriorated due to irregular reflection of light from the formation of microdroplets of a lipid component derived from a living body.

Hereinafter, the embodiment will be described more specifically with reference to examples and comparative examples.
(L1-1 to L1-11 (Preparation of composition for low refractive index layer familiar with fingerprint for Examples))
The following raw materials are used as a resin composition for a fingerprint-familiar low refractive index layer, and each raw material has the composition described in Table 1 below: (a) a fluorine-containing ultraviolet curable adamantane derivative, (b) (a) and Ultraviolet curable resin that can be copolymerized, (c) hollow silica fine particles, (d) metal oxide fine particles, and (e) a photopolymerization initiator are mixed, and the resin composition L1-1 for a low refractive index layer familiar with fingerprints. L1-11 was prepared. In addition, the compounding quantity of each material has described the mass% of solid content. The results are shown in Table 1.

The refractive index was measured using the following method.
(1) Each coating solution is dried on an acrylic resin plate ("Delagrass A", manufactured by Asahi Kasei Chemicals Corporation) with a refractive index of 1.49 by means of a dip coater (manufactured by Sugiyama Genki Riki Co., Ltd.). The layer thickness was adjusted so that the optical film thickness was about 550 nm.
(2) After drying the solvent, each coating solution was cured by irradiating 400 mJ of ultraviolet rays using a 120 W high-pressure mercury lamp in a nitrogen atmosphere by an ultraviolet irradiation device (manufactured by Iwasaki Electric Co., Ltd.) as necessary.
(3) The back surface of the acrylic resin plate is roughened with sandpaper, and the one painted with black paint is measured with a spectrophotometer ("U-Best V560", manufactured by JASCO Corporation) at 5 ° at a light wavelength of 400 to 650 nm. The −5 ° regular reflectance was measured, and the minimum or maximum value of the reflectance was read.
(4) The refractive index was calculated from the extreme value of the reflectance using the following formula.

  The raw materials for the resin composition for a fingerprint-familiar low refractive index layer are as follows. (A) As fluorine-containing UV-curable adamantane derivatives, 1-perfluoroadamantyl methacrylate (manufactured by Idemitsu Kosan Co., Ltd., trade name: adamantate X-F-101), perfluoro-1,3-bis (acryloxy) Ethoxy) adamantane (made by Idemitsu Kosan Co., Ltd., trade name: adamantate X-F-201), 2-perfluoro-1,3-adamantanediol dimethacrylate (made by Idemitsu Kosan Co., Ltd., trade name: adamantate) X-F-203) was used. (B) As an ultraviolet curable resin copolymerizable with (a), KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd., and Murasakiko UV-7600B manufactured by Nippon Synthetic Chemical Industry Co., Ltd. were used. (C) As hollow silica fine particles, acrylic modified hollow silica fine particles through rear NAU (refractive index of 1.25, average particle diameter of 60 nm) manufactured by JGC Catalysts & Chemicals Co., Ltd. were used. (D) As metal oxide fine particles, alumina fine particles (refractive index: 1.76, average particle size: 40 nm) manufactured by Big Chemie Japan Co., Ltd. were used. (E) IRGACURE907 (I-907) and IRGACURE184 (I-184) manufactured by Ciba Specialty Chemicals Co., Ltd. were used as photoinitiators.

(H1-1 (Preparation of resin composition for high refractive index layer))
(F) 47.5% by mass of metal oxide fine particles, (g) 47.5% by mass of an ultraviolet curable resin, and (h) 5% by mass of a photoinitiator are mixed as a resin composition for a high refractive index layer. Then, a resin composition H1-1 for a high refractive index layer was prepared. In addition, the compounding quantity of each material has described the mass% of solid content.
The raw materials for the high refractive index layer resin composition are as follows.
(F) Metal oxide fine particles: RTTMIBK15WT% -N24 (titania dispersion) manufactured by CI Kasei Co., Ltd. (g) UV curable resin: Purple light UV-7600B manufactured by Nippon Synthetic Chemical Industry Co., Ltd.
(H) Photoinitiator: IRGACURE184 (I-184) manufactured by Ciba Specialty Chemicals

(HC1-1 to HC1-2 (Preparation of resin composition for hard coat))
The following raw materials are used as the hard coat resin composition, and each raw material has the composition described in Table 2 below, (i) an ultraviolet curable resin, (j) a surface conditioner, and (k) photo initiation. An agent was mixed to prepare hard coat resin compositions HC1-1 to HC1-2. In addition, the compounding quantity of each material has described the mass% of solid content. The results are shown in Table 2 below.

  The raw materials for the resin composition for hard coat are as follows. (I) Nippon Kayaku Co., Ltd. KAYARAD DPHA and Nippon Synthetic Chemical Industry Co., Ltd. purple light UV-7600B were used as ultraviolet curable resin. (J) BYK-306 manufactured by Big Chemie Japan Co., Ltd. was used as the surface conditioner. (K) IRGACURE184 (I-184) manufactured by Ciba Specialty Chemicals Co., Ltd. was used as a photoinitiator.

(Example 1-1)
On one side of a triacetyl cellulose (TAC) film (product name: KC8UY, film thickness: 80 μm) manufactured by Konica Minolta Opto Co., Ltd. as a transparent substrate film, a hard coat resin composition (HC1-1) and a solvent (methyl isobutyl) A hard coat layer coating solution in which a ketone) is mixed at a ratio of 1: 1 is applied with a bar coater so that the film thickness after curing is 7 μm, and is cured by irradiating 400 mJ ultraviolet rays with a 120 W high-pressure mercury lamp. Thus, a hard coat layer was formed.
Next, a fingerprint-fitted low refractive index layer coating solution prepared by mixing the resin composition (L1-1) for fingerprint-fatigue low refractive index layer and the solvent (methyl isobutyl ketone) in a ratio of 1: 5 on the hard coat layer. An anti-reflective film (AR1-1) is produced by coating with a bar coater such that the film thickness after curing is 0.1 μm, and irradiating with a UV light of 400 mJ with a 120 W high-pressure mercury lamp in a nitrogen atmosphere. did.

(Example 1-2 to Example 1-11)
An antireflection film (AR1) was prepared in the same manner as in Example 1-1 except that the resin composition for hard coat and the resin composition for a low-refractive index layer familiar to fingerprint were combined with the materials and layers described in Table 3 below. -2 to AR1-11) were prepared.
(Example 1-12)
A coating solution for a high refractive index layer obtained by mixing the resin composition for high refractive index layer (H1-1) and a solvent (methyl isobutyl ketone) in a ratio of 1: 5 on the hard coat layer formed in Example 1-1. Was coated with a bar coater such that the film thickness after curing was 0.1 μm, and was cured by irradiating with 400 mJ of ultraviolet light with a 120 W high pressure mercury lamp in a nitrogen atmosphere to form a high refractive index layer. Finally, an antireflection film (AR1-12) was prepared in the same manner as in Example 1-1, except that the resin composition for a fingerprint-familiar low refractive index layer was a combination of the materials and layers described in Table 3 below. Produced.
About the obtained antireflection film, fingerprint wiping property, scratch resistance, and minimum reflectance were measured by the following methods. The results are shown in Table 3 below.

<Minimum reflectivity>
In order to prevent back reflection of the antireflection film, the back surface was roughened with sandpaper and filled with a black paint, and a spectrophotometer [trade name: U-best 560, manufactured by JASCO Corporation] was used. A 5 ° and −5 ° specular reflection spectrum at 780 nm was measured. The minimum reflectance (%) was read from the obtained reflection spectrum.

<Haze value and total light transmittance>
NDH-2000 manufactured by Nippon Denshoku Industries Co., Ltd. was used, and the haze value and total light transmittance were measured.

<Fingerprint invisibility>
Fingerprints were attached on the surface material for display, and the sensory evaluation by visual observation was performed on the visibility in the following four stages.
4: The fingerprint due to scattering is completely invisible. 3: The fingerprint due to scattering is very slightly visible. 2: The fingerprint due to scattering is slightly visible. 1: The fingerprint due to scattering is clearly visible.

<Fingerprint wiping>
One drop of artificial finger oil (1 g of urea, 4.6 g of lactic acid, 8 g of sodium pyrophosphate, 7 g of sodium chloride and 20 mL of ethanol diluted to 1 L with distilled water) is dropped on the surface of the antireflection film. Then, use Nippon Paper Crecia Co., Ltd. Kimwipe to blend in the artificial finger oil. Then, after carrying out 5 reciprocating wiping using Toray Co., Ltd. Toraysee, the surface trace was observed visually and evaluated in the following three steps.
○: When there is no trace of artificial finger oil △: When some trace of artificial finger oil remains *: When trace of artificial finger oil remains

<Abrasion resistance>
The surface of the antireflection film is placed on the tip of an eraser abrasion tester manufactured by Honko Seisakusho Co., Ltd., and a commercially available flannel cloth is installed through a cushion made of silicone rubber. A load of 500 gf is applied, a stroke width of 25 mm, and a speed of 30 mm. The surface after 500 reciprocal frictions at / sec was visually observed and evaluated by the following ○ and ×.
○: 0 to 10 scratches and no significant discoloration ×: 11 or more scratches or significant discoloration

<Abrasion resistance>
The surface of the antireflection film was subjected to a reciprocal friction of 10 mm at a stroke width of 25 mm and a speed of 30 mm / sec by applying a load of 250 gf to # 0000 steel wool, and the surface was visually evaluated and evaluated by the following ○ and ×.
* Steel wool was gathered to about 10mmφ, and was cut and rubbed so that the surface was uniform.
○: 0 to 10 scratches ×: 11 or more scratches

<Surface roughness>
Using a surface roughness measuring machine manufactured by Kosaka Laboratory Co., Ltd., Surfcorder SE4000, with a scanning range of 1.5 mm and a scanning speed of 0.1 mm / s, the arithmetic average roughness (Ra) It was measured.

<Oleic acid contact angle>
Using a DropMaster 500 manufactured by Kyowa Interface Science Co., Ltd., the contact angle was measured with a 4 μL droplet.

<Coating appearance>
The surface of the cured film after UV irradiation was visually observed and evaluated by the following ○ and ×.
○: No noticeable unevenness, streak, repelling, etc. ×: Remarkable unevenness, streak, repelling, etc. easily visible

(L2-1 to L2-14 (production of composition for low refractive index layer for comparative example))
In addition to the above raw materials as the resin composition for low refractive index, the following raw materials are used, and the respective raw materials are mixed in the composition described in Table 4, and resin compositions for low refractive index layers L2-1 to L2-14 Was prepared. In addition, the compounding quantity of each material has described the mass% of solid content. The results are shown in Table 4.
Each raw material is as follows. As a fluorine-containing ultraviolet curable resin, Daikin Industries, Ltd. OPTOOL DAC-HP, as a silicone-based ultraviolet curable resin that does not contain fluorine, Shin-Etsu Silicone TIC-2459, as a resin that contains fluorine and does not cure ultraviolet DIC Co., Ltd. MegaFuck F-558 was used. The results are shown in Table 4 below.

(Comparative Example 1-1 to Comparative Example 1-14)
Antireflection films (AR2-1 to AR2-14) were produced in the same manner as in Example 1-1 except that the resin composition for the low refractive index layer was used as the material described in Table 4. The obtained antireflection film was measured for fingerprint wiping property, scratch resistance, and minimum reflectance. The results are shown in Table 5 below.

  In Examples 1-1 to 1-12, since the resin composition for a fingerprint-familiar low refractive index layer for forming the fingerprint-fat low refractive index layer is set within the range defined by the present invention, the antireflection function is provided. Good, haze value of 1.0% or less, excellent fingerprint invisibility and fingerprint wiping property, good wear resistance and scratch resistance, surface roughness in the range of 0.001 μm to 0,020 μm, and olein An antireflection film having an acid contact angle of 30 ° or less could be produced.

On the other hand, Comparative Example 1-1 uses (a) a low refractive index layer containing 7.0% by mass of the fluorine-containing UV-curable adamantane derivative, so that fingerprint visibility and fingerprint wiping properties are poor. As a result. In Comparative Example 1-2, (a) the low refractive index layer containing 25.0% by mass of the fluorine-containing ultraviolet curable adamantane derivative was used, and thus the results were poor in wear resistance and scratch resistance. It was. In Comparative Example 1-3, (b) the ultraviolet curable resin copolymerizable with (a) is 15.0% by mass, and (c) the blending ratio of the hollow silica fine particles is 73.9% by mass. Since the refractive index layer was used, the abrasion resistance and scratch resistance were weak, or the antireflection performance was poor. Since Comparative Example 1-4 uses a low refractive index layer in which (b) is 70.9% by mass and (c) is 18.0% by mass, the wear resistance and scratch resistance are high. The result was weak or the antireflection performance was poor.
In Comparative Examples 1-5 and 1-6, (d) the metal oxide fine particles are not blended or a low refractive index layer containing 5.0% by mass is used, so that the wear resistance and scratch resistance are weak. A result or a result with a high haze value was brought. In Comparative Examples 1-7 and 1-8, the blending ratio of the photopolymerization initiator (e) is 0.5% by mass or the fingerprint-familiar low refractive index layer of 15.0% by mass is used. Abrasion and scratch resistance were poor.
Comparative Example 1-9 was not a fluorine-containing ultraviolet curable adamantane derivative, but a low refractive index layer made of a fluorine-containing ultraviolet curable resin having no adamantane structure was used. The result was that fingerprint invisibility deteriorated due to repellency and scattering. Comparative Example 1-10 uses a low refractive index layer containing a silicone-based ultraviolet curable resin instead of a fluorine-containing ultraviolet curable resin, so that the contact angle of oleic acid is high, and the fingerprint is repelled and scattered. As a result, invisibility deteriorated. Since Comparative Example 1-11 was not a fluorine-containing ultraviolet curable resin but a low refractive index layer containing a resin containing fluorine and not ultraviolet curable, the result was poor in scratch resistance.

DESCRIPTION OF SYMBOLS 1 Transparent base film 2 Hard-coat layer 3 High refractive index layer 4 Fingerprint familiar low refractive index layer 10,10A Antireflection film

Claims (2)

On one surface of the thermoplastic transparent substrate film, an antireflection film comprising a hard coat layer and a fingerprint familiar low refractive index layer in this order,
The fingerprint-familiar low refractive index layer comprises the following components (a) to (e):
(A) a fluorine-containing UV-curable adamantane derivative,
(B) an ultraviolet curable resin copolymerizable with (a),
(C) hollow silica fine particles,
It contains (d) metal oxide fine particles and (e) a photopolymerization initiator, the content of (a) component is 10.0 to 20.0% by mass, and the content of (b) component is 19.0. 61.9 mass%, the content of component (c) is 27.0-69.9 mass%, the content of component (d) is 0.1-3.0 mass%, and the content of component (e) Is an antireflection film, which is a cured product of a resin composition having 1.0 to 10.0% by mass.   The reflection angle according to claim 1, wherein the contact angle with respect to oleic acid is 30 ° or less, and the arithmetic average roughness (Ra) defined in JIS B0601-1994 is 0.001 to 0.020 µm. Prevention film.

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