JP2018161832A - Laminate film and antireflection film for molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate film and an antireflection film for molding, having good antireflection property and suitable for high magnification molding.SOLUTION: There is provided a laminate film having a cured resin layer consisting of a single layer with thickness of 170 nm or more on a substrate film directly or via an undercoat layer, in which absolute value of difference between a haze value with extension by area ratio of 130% (Hz1) and a haze value before extension (Hz0) is 0.30% or less, the cured resin layer contains a silica particle, and silica particle number contained in a zone A by 100 nm from a surface in an opposite side of the substrate film of the cured resin layer in a thickness direction is 70% or more.SELECTED DRAWING: Figure 3

Description

  The present invention relates to a laminated film and an antireflection film for molding, and in particular, relates to a laminated film and an antireflection film for molding which have good antireflection properties and are suitable for high magnification molding applications.

  Proposal of anti-reflective film used for in-mold molding and insert molding to protect and decorate casings for electronic devices such as portable personal computers, mobile devices, mobile phones, electronic notebooks, and in-vehicle display panels (For example, Patent Documents 1 and 2).

JP 2014-166750 A Japanese Unexamined Patent Publication No. 2016-20049

  The antireflection layer disclosed in the above patent document is a layer in which a high refractive index layer and a low refractive index layer are sequentially laminated. Such a sequentially laminated antireflection layer tends to generate cracks more strongly when the molding ratio (stretching ratio) is larger than that of a single-layer antireflection layer.

  In addition, the above-mentioned patent document specifically discloses an antireflection film that is free from cracks and cloudiness even when molded at a high magnification, for example, stretched to an area ratio of 130% or more, and in which an increase in haze value is suppressed. Not.

  Therefore, an object of the present invention is to provide a laminated film and an antireflection film for molding which have good antireflection properties and are suitable for high magnification molding.

The above object of the present invention is achieved by the following invention.
[1] A laminated film having a cured resin layer composed of a single layer having a thickness of 170 nm or more on a base film directly or through an undercoat layer, and having a haze value (Hz1) when stretched to an area ratio of 130% ) And the haze value (Hz0) before stretching is 0.30% or less, the cured resin layer contains silica particles, and the surface of the cured resin layer opposite to the base film is from A laminated film, wherein the number of silica particles contained in the region A up to 100 nm in the thickness direction is 70% or more of the total number of silica particles contained in the cured resin layer.
[2] The laminated film according to [1], wherein the silica particle number density in the region A is 2.0 times or more of the silica particle number density in the entire region B except the region A.
[3] The laminated film according to [1] or [2], wherein the luminous reflectance before stretching is less than 1.70%.
[4] The laminated film according to any one of [1] to [3], wherein the silica particles are surface-treated with a fluorine compound.
[5] The laminated film according to any one of [1] to [4], wherein the cured resin layer further contains metal oxide particles.
[6] The laminated film according to [5], wherein the metal oxide particle number density in all regions B excluding the region A is 2.0 times or more the metal oxide particle number density in the region A.
[7] An antireflection film for molding comprising the laminated film according to any one of [1] to [5].

  According to the present invention, it is possible to provide a laminated film having good antireflection properties and suitable for high-magnification molding.

FIG. 1 is a schematic cross-sectional view of an example of the laminated film of the present invention. FIG. 2 is a schematic cross-sectional view of an example of the laminated film of the present invention. FIG. 3 is a schematic cross-sectional view of a preferred embodiment of the laminated film of the present invention.

  The laminated film has a cured resin layer composed of a single layer having a thickness of 170 nm or more on the base film directly or via an undercoat layer. When the cured resin layer contains silica particles, the region from the surface opposite to the base film of the cured resin layer to 100 nm in the thickness direction is defined as region A, and the entire region excluding the region A is defined as region B. The number of silica particles contained in A is 70% or more of the total number of silica particles contained in the cured resin layer. Here, the total number of silica particles contained in the cured resin layer is the sum of the number of silica particles contained in region A and the number of silica particles contained in region B.

  In the present specification, a cured resin layer composed of a single layer means a layer formed by applying one coating composition (coating liquid) only once. That is, although the cured resin layer is a single layer, it has a region A in which silica particles are localized at a relatively high density on the surface opposite to the base film. Thereby, the reflectance of the cured resin layer surface is lowered, and good antireflection properties can be imparted to the laminated film.

  1 and 2 are schematic cross-sectional views of an example of the laminated film of the present invention. FIG. 1 shows an embodiment in which the cured resin layer 1 is directly laminated on the base film 2, and FIG. 2 shows an embodiment in which the cured resin layer 1 is laminated on the base film 2 via the undercoat layer 3. Indicates.

  The cured resin layer 1 contains silica particles 11, and the silica particles 11 are localized at high density near the surface on the opposite side of the base film 2. That is, the cured resin layer 1 has a region A in which the silica particles 11 are localized at a relatively high density.

  The cured resin layer 1 includes a region A (region indicated by reference symbol A) from the surface 1c on the side opposite to the base film 2 to a thickness direction of 100 nm and a region B (reference symbol B) excluding the region A. Area). Region A is a region from the surface 1c to a boundary line 1d (shown by a dotted line) drawn substantially parallel to the surface 1c at a position of 100 nm in the thickness direction, and region B is a boundary line on the base film side from the boundary line 1d. It is an area up to 1e. Here, it is defined that the silica particles 11a existing on the boundary line 1d are contained in the region A.

  The number of silica particles contained in the region A and the region B of the cured resin layer can be obtained from a photographed image (cross-sectional photograph) of the cross section of the cured resin layer, for example, a cross-sectional photographed image using a transmission electron microscope (TEM). The specification of the boundary line 1d between the region A and the region B and the specification of the region A and the region B in the cross-sectional image (cross-sectional photograph) of the cured resin layer will be described in detail in the section of the example.

  In order to impart good antireflection properties to the laminated film, it is preferable that the region A functions sufficiently as a low refractive index layer, and it is preferable that the region A localizes silica particles at a relatively high density. . From this viewpoint, the number of silica particles contained in the region A is preferably 80% or more of the total number of silica particles contained in the cured resin layer, and more preferably 90% by mass or more. The upper limit is 100%.

  Moreover, it is preferable that the silica particle number density (Asi) in the region A is sufficiently higher than the silica particle number density (Bsi) in the region B from the viewpoint of imparting good antireflection properties to the laminated film. Specifically, (Asi) is preferably 2.0 times or more of (Bsi), more preferably 5.0 times or more, and particularly preferably 8.0 times or more. The higher the magnification, the better. The upper limit is not particularly limited. That is, (Bsi) includes 0.

  The number density of the silica particles in the region A and the region B can be obtained from a photographed image (cross-sectional photograph) of a cross section of the cured resin layer, for example, a sectional photographed image by a transmission electron microscope (TEM). Details will be described in the section of the embodiment.

  As described above, since the cured resin layer has the region A in which the silica particles are localized at a relatively high density, the luminous reflectance on the surface of the cured resin layer is less than 1.70%, and further 1.50. % Can be realized. The luminous reflectance is that before stretching of the laminated film.

  The cured resin layer preferably further contains metal oxide particles. When the cured resin layer contains the metal oxide particles, the silica particles are easily localized in the region A. When the silica particles are localized in the region A, the metal oxide particles are easily localized in the region B.

  The cured resin layer preferably has a metal oxide particle number density in the region B higher than the metal oxide particle number density in the region A.

  That is, the cured resin layer contains at least silica particles and metal oxide particles, and has a region A where the silica particles are localized at a relatively high density on the surface opposite to the base film of the cured resin layer, It is preferable to have the region B where the metal oxide particles are localized at a relatively high density on the base film side.

  FIG. 3 is a schematic cross-sectional view of an example of a preferred embodiment of the laminated film of the present invention, and illustrates an embodiment in which the cured resin layer further contains metal oxide particles. Region B (region represented by symbol B) is a region in which the metal oxide particles 12 are localized at a relatively high density.

  FIG. 3 shows a preferred embodiment of FIG. 1, but the cured resin layer of FIG. 2 also has a relatively high density of metal oxide particles in the region B as in the cured resin layer of FIG. A localized region is preferred.

  The metal oxide particle number density in the region A and the region B can be obtained from a cross-sectional image taken by a transmission electron microscope (TEM) in the same manner as the measurement of the silica particle number density. Details will be described in the section of the embodiment.

  In order to obtain good antireflection properties, the region B preferably functions sufficiently as a high refractive index layer. From this viewpoint, the metal oxide particle number density (Bm) in the region B is determined by the metal oxide in the region A. It is preferable that it is sufficiently higher than the particle number density (Am). Specifically, (Bm) is preferably 2.0 times or more of (Am), more preferably 5.0 times or more, and particularly preferably 8.0 times or more. The higher the magnification, the better. The upper limit is not particularly limited. That is, (Am) includes 0.

  As described above, it is preferable that the silica particles are localized at high density in the region A and the metal oxide particles are localized at high density in the region B. That is, the cured resin layer preferably has a structure in which silica particles and metal oxide particles are phase-separated. Thereby, the antireflection property of the laminated film is further improved. Specifically, it is possible to realize a luminous reflectance of less than 0.70%, and further less than 0.50%. The luminous reflectance is that before stretching of the laminated film.

  Here, adopting the phase separation structure means that the interface between the region A where the silica particles are localized at a high density and the region B where the metal oxide particles are localized at a high density can be clearly confirmed. The interface can be confirmed by a cross-sectional image taken with a transmission electron microscope (TEM). Details will be described in the section of the embodiment.

  In the laminated film, the absolute value of the difference between the haze value (Hz1) when stretched to an area ratio of 130% and the haze value (Hz0) before stretching is 0.30% or less. That is, the laminated film does not generate cracks even when stretched to an area ratio of 130%, or it is very slight even if cracks occur, and it means that changes in appearance cannot be confirmed. Here, stretching to an area ratio of 130% means that a laminated film cut into a square is biaxially stretched at the same aspect ratio (1.14 times).

  The laminated film having the above-described characteristics can be applied to a high-magnification molding application, and is particularly suitable as an antireflection film for molding.

  As described above, the cured resin layer composed of a single layer is clearly distinguished from a general laminated structure of a conventional antireflection film, that is, a laminated structure in which a high refractive index layer and a low refractive index layer are sequentially laminated. . And the cured resin layer which consists of a single layer has the feature that the crack generation tendency at the time of extending | stretching becomes small compared with the conventional laminated structure. This is because cracks are likely to occur at the interface between the high refractive index layer and the low refractive index layer during stretching in the conventional laminated structure, but cracks occur because the single cured resin layer is a continuous film in the thickness direction. Presumably difficult to do.

  Moreover, the cured resin layer which consists of a single layer has the feature that the raise of the luminous reflectance after extending | stretching is suppressed compared with the antireflection layer of the conventional sequential laminated structure.

Hereinafter, each element which comprises the laminated | multilayer film of this invention is demonstrated in detail.
[Hardened resin layer]
The cured resin layer is laminated on the base film directly or via an undercoat layer.

  The cured resin layer is a layer obtained by curing a coating composition containing at least silica particles and a resin component. In order to form the region A in which silica particles are localized at a relatively high density on the opposite surface of the base film of the cured resin layer, for example, silica particles surface-treated with a fluorine compound are used as the silica particles. Is preferred. Silica particles surface-treated with a fluorine compound have a relatively small surface free energy and move to the air side interface (the side opposite to the base film) during the drying or curing process of the applied coating composition. It is assumed that the region A is easily formed.

  Examples of the method for surface-treating silica particles with a fluorine compound include the following methods (i) and (ii). In view of efficient surface treatment, the method (ii) is preferable.

  (I) at least selected from the group consisting of an organosilane compound having a fluorine atom represented by the following general formula (1), a hydrolyzate of the organosilane, and a partial condensate of the hydrolyzate of the organosilane Surface treatment with one compound.

Rf ¹ -R ¹ -Si (Q ¹ ) ₃ ... General formula (1)

In general formula (1), Rf ¹ represents a fluoroalkyl group, R ¹ represents an alkylene group or alkyleneoxy group having 1 to 6 carbon atoms, and Q ¹ represents an alkoxy group having 1 to 5 carbon atoms, a halogen atom, or a hydroxyl group.

Here, the fluoroalkyl group of Rf ¹ is a substituent in which part or all of the hydrogen of the alkyl group is substituted with a fluorine atom. The number of carbon atoms in the fluoroalkyl group is preferably in the range of 2-20, more preferably in the range of 3-15, and particularly preferably in the range of 4-12.

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) C l2
_{C 6 F 13 CH 2 CH 2} CH 2 CH 2 Si (OH) (OC 2 H 5) 2

(Ii) at least one compound selected from the group consisting of an organosilane compound represented by the following general formula (2), a hydrolyzate of the organosilane, and a partial condensate of the hydrolyzate of the organosilane A method of treating and then surface-treating with a fluorine compound represented by the following general formula (3).

B—R ² —Si (Q ² ) ₃ ... General formula (2)
DR ³ -Rf ² ... General formula (3)

In the general formulas (2) and (3), B and D each independently represent a reactive site, R ² and R ³ each independently represent an alkylene group or alkyleneoxy group having 1 to 6 carbon atoms, and Q ² Represents an alkoxy group having 1 to 5 carbon atoms, a halogen atom or a hydroxyl group, and Rf ² represents a fluoroalkyl group.

  Examples of the reactive site represented by B and D include a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, an acryloyloxy group, a methacryloyloxy group, an epoxy group, a carboxyl group, and a hydroxyl group.

Rf ² is a fluoroalkyl group, which is a substituent in which part or all of the hydrogen of the alkyl group is substituted with a fluorine atom. The number of carbon atoms in the fluoroalkyl group is preferably in the range of 2-20, more preferably in the range of 3-15, and particularly preferably in the range of 4-12.

  Specific examples of the general formula (2) include acryloxyethyltrimethoxysilane, acryloxypropyltrimethoxysilane, acryloxybutyltrimethoxysilane, acryloxypentyltrimethoxysilane, acryloxyhexyltrimethoxysilane, acryloxyheptyltri Methoxysilane, methacryloxyethyltrimethoxysilane, methacryloxypropyltrimethoxysilane, methacryloxybutyltrimethoxysilane, methacryloxyhexyltrimethoxysilane, methacryloxyheptyltrimethoxysilane, methacryloxypropylmethyldimethoxysilane, methacryloxypropylmethyldimethoxy Silane and compounds in which the methoxy group in these compounds is substituted with another alkoxyl group, halogen atom or hydroxyl group Things and the like.

  Specific examples of the general formula (3) include 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (meth) acrylate, and 2-perfluorobutylethyl. (Meth) acrylate, 3-perfluorobutyl-2-hydroxypropyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, 3-perfluorohexyl-2-hydroxypropyl (meth) acrylate, perfluorooctylmethyl (Meth) acrylate, 2-perfluorooctylethyl (meth) acrylate, 3-perfluorooctyl-2-hydroxypropyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, 2-perfluoro-3-methyl Butylethyl (meth) acrylate 3-perfluoro-3-methoxybutyl-2-hydroxypropyl (meth) acrylate, 2-perfluoro-5-methylhexylethyl (meth) acrylate, 3-perfluoro-5-methylhexyl-2-hydroxypropyl (meth) ) Acrylate, 2-perfluoro-7-methyloctyl-2-hydroxypropyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, octafluoropentyl (meth) acrylate, dodecafluoroheptyl (meth) acrylate, hexadecafluorononyl (Meth) acrylate, hexafluorobutyl (meth) acrylate, 2,2,2-trifluoroethyl methacrylate and the like can be mentioned.

  Here, “... (Meth) acrylate” is a generic name including “... Acrylate” and “methacrylate”. The same applies to the following description.

  As the silica particles, hollow silica particles and porous silica particles are preferably used. In particular, hollow silica particles are preferred. The refractive index of the hollow silica particles is 1.20 to 1.40, which is smaller than the refractive index of 1.45 to 1.47 of ordinary silica particles, so that the cured resin layer contains hollow silica particles, and the hollow silica particles By having the region A localized at a relatively high density, the antireflection property is further improved.

  The hollow silica particles are silica particles having cavities inside the particles, and the porous silica particles are silica particles having pores on the surface and inside of the particles.

  Since the hollow silica has a relatively small specific gravity, it is easy to form a region A in which silica particles are localized at a relatively high density on the surface opposite to the base film of the cured resin layer, and the refractive index of the region A Can be made relatively small, so that the antireflection property of the laminated film can be enhanced.

  The number average particle diameter of the silica particles is preferably 100 nm or less from the viewpoint of stably forming the region A where the silica particles are localized at a relatively high density on the surface of the cured resin layer and from the viewpoint of transparency. Is more preferable, and 70 nm or less is particularly preferable. The lower limit of the number average particle diameter of the silica particles is not particularly limited, but the number average particle diameter of the silica particles obtained in a practically stable manner is about 5 nm.

  In addition, the number average particle diameter of a silica particle says the particle diameter calculated | required with the transmission electron microscope (TEM). For example, a sample in a state where the silica particle dispersion is evaporated and dried is observed with a transmission electron microscope, the measurement magnification at that time is 100,000, and the maximum diameter of 100 particles existing on the photographing screen is set. The average value was measured.

  The resin component contained in the coating composition will be described. The resin component is preferably a compound (monomer or oligomer) that is polymerized by active energy rays. Such compounds include compounds having at least one ethylenically unsaturated group in the molecule. Here, examples of the ethylenically unsaturated group include a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, an acryloyloxy group, a methacryloyloxy group, an allyl group, and a vinyl group.

  The laminated film is required to have no crack in the cured resin layer even when stretched to an area ratio of 130%, or to be extremely slight even if a crack occurs. That is, if the polymerization density of the resin component is increased, cracks are likely to occur in the cured resin layer during stretching, so it is preferable to balance the molecular weight of the resin component with the number of functional groups (the number of ethylenically unsaturated groups).

  On the other hand, if the molecular weight of the resin component becomes too large, the localized region (region A) of silica particles may not be formed in the cured resin layer. For example, when the molecular weight (weight average molecular weight in the case of an oligomer) exceeds 25,000, the region A may not be formed.

  From the above viewpoint, it is preferable that the resin component contains at least one compound selected from the group consisting of the following (i) to (iv).

(I) A monomer or oligomer having two ethylenically unsaturated groups in the molecule and a molecular weight of 300 to 1,000 (ii) having 2 to 5 ethylenically unsaturated groups in the molecule and a molecular weight of 1 1,000 to 10,000 oligomers.
(Iii) an oligomer having 3 to 10 ethylenically unsaturated groups in the molecule and a molecular weight of 10,000 to 15,000 (iv) having 4 to 25 ethylenically unsaturated groups in the molecule, and having a molecular weight Of 15,000 to 25,000

  The molecular weight of the oligomers (i) to (iv) is a weight average molecular weight. In the following description, the number of ethylenically unsaturated groups in one molecule may be referred to as the number of functional groups. For example, the case of having two ethylenically unsaturated groups in the molecule may be bifunctional and the case of having ten ethylenically unsaturated groups may be ten functional.

  Examples of the monomer (i) include epoxy di (meth) acrylate having a bisphenol skeleton in the molecule and di (meth) acrylate having a polyalkylene glycol (ethylene glycol, polypropylene glycol, etc.) skeleton in the molecule. Among these, epoxy di (meth) acrylate having a bisphenol skeleton in the molecule is preferable.

  Examples of the epoxy di (meth) acrylate having a bisphenol skeleton in the molecule include an acrylic acid or methacrylic acid adduct of bisphenol A diglycidyl ether and an acrylic acid or methacrylic acid adduct of hydrogenated bisphenol A diglycidyl ether.

  The oligomer (i) is preferably a urethane (meth) acrylate oligomer. For example, phenyl glycidyl ether (meth) acrylate hexamethylene diisocyanate urethane oligomer, phenyl glycidyl ether (meth) acrylate isophorone diisocyanate urethane oligomer, propylene glycol diglycidyl ether (meth) acrylate hexamethylene diisocyanate urethane oligomer, propylene glycol diglycidyl ether (meth) Examples thereof include acrylate isophorone diisocyanate urethane oligomers.

  As the oligomers (ii) to (iv), urethane (meth) acrylate oligomers are preferable. For example, a urethane (meth) acrylate oligomer obtained by reacting a polyisocyanate compound (for example, hexamethylene diisocyanate, isophorone diisocyanate, phenylene diisocyanate, etc.) with a hydroxyl group of an epoxy di (meth) acrylate having a bisphenol skeleton in the molecule, In order to increase the urethane bond to the urethane (meth) acrylate oligomer, a diol compound (for example, ethylene glycol, propylene glycol, polyethylene glycol, pentanediol, neopentyl glycol, etc.) is reacted, or the ethylenically unsaturated group is increased. (Meth) acrylate compounds having a hydroxyl group (for example, 2-hydroxyethyl (meth) acrylate, trimethylolethane (meta) Acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) urethane obtained by reacting the acrylate) (meth) acrylate oligomer and the like.

  The coating composition can further contain a (meth) acrylate monomer having 3 to 8 ethylenically unsaturated groups in the molecule and a molecular weight of 1,000 or less. The content of the (meth) acrylate monomer is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, with respect to 100 parts by mass of the total amount of the compounds (i) to (iv). Is particularly preferred. The lower limit is 0 to 2 parts by mass.

  Examples of the (meth) acrylate monomer include trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, glycerin propoxytri (meth) 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 Examples include octa (meth) acrylate.

  The coating composition preferably further 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 (registered trademark) 184, Irgacure 907, Irgacure 379, Irgacure 819, Irgacure 127, Irgacure 500, Irgacure 754, Irgacure 250, Irgacure 1800, Irgacure 1870, Irgacure OXEDA, manufactured by Ciba Specialty Chemicals Co., Ltd. (Registered trademark) TPO, DAROCUR1173, etc., Speedcure (registered trademark) MBB, Speedcure PBZ, Speedcure ITX, Speedcure CTX, Speedcure EDB, Ecure (registered trademark) ONE KAYACURE (registered trademark) D TX-S, KAYACURE CTX, KAYACURE BMS, KAYACURE DMBI, and the like.

  The content of the photopolymerization initiator is preferably in the range of 0.1 to 10% by mass, more preferably in the range of 0.5 to 8% by mass with respect to 100% by mass of the total solid content of the coating composition.

The coating composition preferably further contains metal oxide particles. Such metal oxide particles preferably have a refractive index of 1.60 to 2.50. For example, zirconium oxide (ZrO ₂ ), titanium oxide (TiO ₂ ), aluminum oxide (Al ₂ O ₃ ), indium oxide (In ₂ O ₃ ), zinc oxide (ZnO), tin oxide (SnO ₂ ), antimony oxide (Sb ₂ O ₃ ), and indium tin oxide (In ₂ O ₃ ). Among these metal oxide particles, zirconium oxide (ZrO ₂ ) and titanium oxide (TiO ₂ ) are preferable, and zirconium oxide (ZrO ₂ ) is particularly preferable.

  The number average particle diameter of the metal oxide particles is preferably 70 nm or less, more preferably 50 nm or less, and particularly preferably 30 nm or less. The lower limit of the number average particle diameter that can be practically produced is about 1 nm.

  The number average particle size of the metal oxide particles refers to the particle size obtained with a transmission electron microscope (TEM). For example, a sample in a state where the metal oxide particle dispersion is evaporated and dried is observed with a transmission electron microscope, the measurement magnification at that time is 100,000, and the maximum of 100 particles existing on the photographing screen The diameter was measured and taken as the average value.

The cured resin layer having the region A in which the silica particles are localized at a relatively high density and the region B in which the metal oxide particles are localized at a relatively high density is composed of silica particles surface-treated with a fluorine compound, metal oxide It can be obtained by curing the coating composition containing the product particles and the resin component.
In order to facilitate formation of the region B where the metal oxide particles are relatively dense and localized, the metal oxide particles are selected from the group consisting of the general formula (2) and the following general formula (4). The surface treatment is preferably performed with at least one selected compound.

R ⁴ n-Si (Q ³ ) _4-n ... General formula (4)

In the general formula (4), R ⁴ represents an alkyl group, Q ³ represents an alkoxy group having 1 to 5 carbon atoms, a halogen atom or a hydroxyl group, and n represents any integer of 1 to 3.

  Specific examples of the general formula (4) include, for example, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, tetraethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltri Examples include methoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, decyltrimethoxysilane, and decyltrimethoxysilane.

  The cured resin layer has a thickness of 170 nm or more. By setting the thickness of the cured resin layer to 170 nm or more, a region A in which silica particles are localized at a relatively high density is easily formed on the surface of the cured resin layer opposite to the base film, and as a result. Good antireflection properties can be obtained. From the above viewpoint, the thickness of the cured resin layer is preferably 180 nm or more, and particularly preferably 190 nm or more. On the other hand, if the thickness of the cured resin layer becomes too large, it becomes difficult to form the region A in which the silica particles are localized at a relatively high density. Therefore, the upper limit thickness is preferably less than 1,000 nm, and more preferably 800 nm or less. Furthermore, 500 nm or less is preferable, and 250 nm or less is particularly preferable.

  The cured resin layer contains silica particles and metal oxide particles, and has a region A in which silica particles are localized at a relatively high density on the surface opposite to the substrate film of the cured resin layer. In the aspect having the region B in which the metal oxide particles are localized at a relatively high density on the film side, from the viewpoint of facilitating the formation of the phase separation structure of the region A and the region B, the thickness of the cured resin layer is: The range of 170 to 800 nm is preferable, the range of 180 to 500 nm is more preferable, and the range of 190 to 250 nm is particularly preferable.

  In the embodiment in which the cured resin layer contains silica particles and metal oxide particles, the thickness of the cured resin layer is 180 from the viewpoint that the bottom wavelength (minimum reflectance wavelength) in the reflection spectrum is positioned near 550 nm. The range of ˜250 nm is preferable, the range of 180 to 230 nm is more preferable, and the range of 190 to 220 nm is particularly preferable. It is preferable to set the bottom wavelength (minimum reflectance wavelength) in the reflection spectrum at around 550 nm, for example, 550 nm ± 20 nm, because the luminous reflectance becomes small.

[Coating composition]
As described above, the coating composition for obtaining the cured resin layer is preferably prepared by dissolving or dispersing silica particles surface-treated with a fluorine compound, a resin component, and a photopolymerization initiator in an organic solvent. The resin component preferably contains at least one compound selected from the group consisting of the aforementioned (i) to (iv).

  The organic solvent is not particularly limited, but an organic solvent having a boiling point of 200 ° C. or less at normal pressure is preferable. For example, methanol, ethanol, isopropyl alcohol, isobutanol, n-butanol, tert-butanol, ethoxyethanol, butoxyethanol, diethylene glycol monoethyl ether, benzyl alcohol, phenethyl alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethylene glycol Examples thereof include monobutyl ether and propylene glycol monomethyl ether, and these can be used singly or in combination.

  The coating composition preferably further contains the aforementioned metal oxide particles. That is, the coating composition for obtaining the cured resin layer preferably contains silica particles surface-treated with a fluorine compound, resin components, metal oxide particles, a photopolymerization initiator, and an organic solvent. Furthermore, the metal oxide particles are preferably surface-treated with at least one compound in the group consisting of the above-described general formula (2) and the following general formula (4).

  From the viewpoint of efficiently forming the region A and the region B, the solid content concentration of the coating composition is preferably in the range of 2 to 20% by mass, more preferably in the range of 3 to 15% by mass, and further 4 to 10% by mass. The range is preferable, and the range of 5 to 8% by mass is particularly preferable.

  The content ratio of each component in the coating composition is appropriately adjusted according to the thickness of the formed cured resin layer. For example, when the coating composition contains silica particles surface-treated with a fluorine compound, a resin component, and a photopolymerization initiator, for example, a cured resin layer having a thickness of 170 nm to 250 nm is formed using the coating composition. In order to obtain, the total solid content of the coating composition is 100% by mass, the silica particles surface-treated with a fluorine compound are 25 to 65% by mass, the resin component is 30 to 70% by mass, and the photopolymerization initiator is 0.1%. It is preferable to contain 5-7 mass%.

  Similarly, in order to obtain a cured resin layer having a thickness of more than 250 nm to 500 nm or less, 10 to 50% by mass of silica particles surface-treated with a fluorine compound with respect to 100% by mass of the total solid content of the coating composition, a resin component It is preferable to contain 40-80 mass% and 0.5-7 mass% of photoinitiators. Similarly, in order to obtain a cured resin layer having a thickness of more than 500 nm to less than 1,000 nm, 5 to 35% by mass of silica particles surface-treated with a fluorine compound with respect to 100% by mass of the total solid content of the coating composition, It is preferable to contain 50-85 mass% of resin components and 0.5-7 mass% of photopolymerization initiators.

  When the coating composition contains silica particles surface-treated with a fluorine compound, a resin component, metal oxide particles, and a photopolymerization initiator, a cured resin layer having a thickness of 170 nm to 250 nm using the coating composition To obtain 100% by mass of the total solid content of the coating composition, 15 to 55% by mass of silica particles surface-treated with a fluorine compound, 10 to 55% by mass of resin component, and 10 of metal oxide particles It is preferable to contain -55 mass% and 0.5-7 mass% of photoinitiators.

  Similarly, in order to obtain a cured resin layer having a thickness of more than 250 nm to 500 nm or less, 10 to 30% by mass of silica particles surface-treated with a fluorine compound with respect to 100% by mass of the total solid content of the coating composition, a resin component It is preferable to contain 15-55 mass% of metal oxide particles, 20-70 mass% of metal oxide particles, and 0.5-7 mass% of a photopolymerization initiator. Similarly, in order to obtain a cured resin layer having a thickness of more than 500 nm to less than 1,000 nm, 5 to 25% by mass of silica particles surface-treated with a fluorine compound with respect to 100% by mass of the total solid content of the coating composition, It is preferable to contain 20-55 mass% of resin components, 30-65 mass% of metal oxide particles, and 0.5-7 mass% of a photopolymerization initiator.

  When the coating composition contains silica particles surface-treated with a fluorine compound, a resin component, metal oxide particles, and a photopolymerization initiator, the mass ratio of the resin component to the metal oxide particles is 60:40 to 40 : 60 is preferable, and the range of 55:45 to 45 to 55 is more preferable. By setting it as the said range, it becomes easy to form the phase-separation structure of a silica particle and a metal oxide particle, and generation | occurrence | production of the crack in high magnification extending | stretching is suppressed.

  The thickness of the cured resin layer can be adjusted by adjusting the wet film thickness at the time of application according to the solid content concentration of the coating composition. For example, when a coating composition having a solid content concentration of 5 to 8% by mass is used, the dry film thickness (after curing) is 170 nm to 250 nm by adjusting the wet film thickness at the time of application in the range of 6 to 17 μm. A cured resin layer is obtained. Similarly, a cured resin layer having a dry film thickness (after curing) of more than 250 nm to 500 nm or less is obtained by adjusting the wet film thickness in the range of 10 to 35 μm. Similarly, a cured resin layer having a dry film thickness (after curing) of more than 500 nm and less than 1,000 nm is obtained by adjusting the wet film thickness in the range of 22 to 71 μm.

[Formation of cured resin layer]
The cured resin layer can be formed by applying the above-described coating composition directly on the base film or via an undercoat layer, drying, irradiating with active energy rays and curing.
As a coating method of the coating composition, a known wet coating method can be used. Examples of the coating method include 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, and an extrusion coating method.

  Examples of active energy rays include ultraviolet rays, visible rays, infrared rays, electron beams, α 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.

[Undercoat layer]
The cured resin layer is laminated on the base film directly or via an undercoat layer. The undercoat layer may be a single layer or a laminate of a plurality of layers.

  The undercoat layer has a function of improving the adhesion between the base film and the cured resin layer, a function of protecting the base film, a function of improving the applicability of the cured resin layer, and the like.

  The undercoat layer is preferably a layer containing a resin as a main component. Here, containing the resin as a main component means that the resin is contained in an amount of 50% by mass or more, preferably 60% by mass or more, based on the total solid content of the undercoat layer of 100% by mass. More preferably, the content is 70% by mass or more, and particularly preferably 80% by mass or more.

  The undercoat layer is preferably a layer obtained by curing a coating composition containing a resin component as a main component. For example, a thermosetting resin layer or an active energy ray curable resin layer is preferable, and an active energy ray curable resin layer is particularly preferable.

  The thermosetting resin layer is a layer obtained by curing a coating composition containing at least a resin component and a crosslinking agent. Here, examples of the resin component 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. 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 crosslinking. Agents, polyamide resins, amide epoxy compounds, various silane coupling agents, various titanate coupling agents, and the like.

  The undercoat layer is required to generate no cracks even when the laminated film is stretched to an area ratio of 130%, or to be extremely slight even if it occurs. From this viewpoint, the resin component is preferably a polyester resin, an acrylic resin, a urethane resin, a polycarbonate resin, or an epoxy resin, and particularly preferably an acrylic resin or a urethane resin.

  The active energy ray-curable resin layer is a layer obtained by curing a coating composition containing a compound (monomer or oligomer) that is polymerized by active energy rays as a resin component. Examples of the compound that is polymerized by active energy rays include compounds having at least one ethylenically unsaturated group in the molecule.

  As described above, the undercoat layer is required to generate no cracks even if the laminated film is stretched by 130% in area ratio, or to be extremely slight even if it occurs. From this viewpoint, it is preferable to use the same compound as the resin component contained in the coating composition for the cured resin layer as the resin component contained in the coating composition for obtaining the active energy ray-curable resin layer.

  The coating composition for obtaining the active energy ray-curable resin layer preferably further contains a photopolymerization initiator. As the photopolymerization initiator, the same compounds as those contained in the coating composition for the cured resin layer described above can be used.

  The active energy ray-curable resin layer can be formed using the same method as the above-described cured resin layer.

  The thickness of the undercoat layer is preferably 10 μm or less, more preferably 7 μm or less, and particularly preferably 5 μm or less from the viewpoint of suppressing the occurrence of cracks. On the other hand, from the viewpoint of protecting the base film and improving the adhesion between the base film and the cured resin layer, 0.1 μm or more is preferable, 0.3 μm or more is more preferable, and 0.5 μm or more is particularly preferable. preferable.

[Base film]
As the substrate film, a plastic film is preferably used. The materials constituting the base film include polyester (for example, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc.), polymethyl methacrylate, acrylic resin, polycarbonate, polystyrene, triacetyl cellulose, polyvinyl alcohol, polyvinyl chloride, poly chloride Examples include vinylidene chloride, polyethylene, ethylene-vinyl acetate copolymer, polyvinyl butyral, metal ion-crosslinked ethylene-methacrylic acid copolymer, polyurethane, cellophane, etc., as a single film or a composite film of two or more of these materials Can be used.

  Among the above base films, a single film of polyester, polycarbonate, polymethyl methacrylate, polyurethane or a composite film of two or more kinds is preferably used from the viewpoints of transparency and stretchability. As the composite film, a composite film of a polycarbonate film and a polymethyl methacrylate film is preferably used.

  The thickness of the base film is preferably in the range of 30 to 500 μm, more preferably in the range of 50 to 400 μm, and particularly preferably in the range of 75 to 350 μm.

  From the viewpoint of enhancing the transparency of the laminated film, the haze value of the base film is preferably 1.50% or less, more preferably 1.00% or less, further preferably 0.70% or less, and 0.50% or less. Is particularly preferred. The lower limit of the haze value is 0.00%.

  In order to set the haze value of the base film to 1.5% or less, the base film preferably does not contain particles.

[Laminated film]
In the laminated film, the absolute value of the difference between the haze value (Hz1) after being stretched to an area ratio of 130% and the haze value (Hz0) before being stretched is 0.30% or less. Preferably, the absolute value of the difference between Hz1 and Hz0 is 0.20% or less, more preferably 0.10% or less.

  It is preferable that the laminated film can be applied to an application having a higher stretch ratio. That is, it is preferable that the increase in haze value of the laminated film is suppressed even when the area ratio is stretched by 150%. Here, stretching to an area ratio of 150% means that a laminated film cut into a square is biaxially stretched at the same longitudinal and lateral ratio (1.23 times).

  Specifically, the absolute value of the difference between the haze value (Hz2) after stretching to an area ratio of 150% and the haze value (Hz0) before stretching is preferably 0.30% or less, and 0.20 % Or less is more preferable, and 0.10% or less is particularly preferable.

  The haze value before stretching of the laminated film is preferably 1.50% or less, more preferably 1.00% or less, and particularly preferably 0.50% or less from the viewpoint of imparting high transparency.

  The laminated film of the present invention is suitable as an antireflection film for molding. From this viewpoint, the laminated film preferably has a luminous reflectance (R0) before stretching of less than 1.70%, more preferably less than 1.00%, and further less than 0.70%. It is preferable that it is especially less than 0.50%. The lower limit is not particularly limited, but is practically about 0.10%.

  In the laminated film, the absolute value of the difference between the luminous reflectance (R1) when stretched to an area ratio of 130% and the luminous reflectance (R0) before stretching is preferably 0.60% or less, 0.50 % Or less is more preferable, and 0.40% or less is particularly preferable. Furthermore, the absolute value of the difference between the luminous reflectance (R2) when stretched to an area ratio of 150% and the luminous reflectance (R0) before stretching is preferably 0.80% or less, and 0.70% or less. Is more preferable, and 0.60% or less is particularly preferable.

  From the viewpoint of obtaining good antireflection properties, the laminated film preferably has no other layer laminated on the surface of the cured resin layer. When other layers are provided, the thickness of the other layers is preferably 20 nm or less from the above viewpoint. Examples of the other layer include an antifouling layer (a functional layer to which contamination such as fingerprint adhesion is suppressed and easy to wipe) and an antistatic layer.

  In addition, the laminated film has an antistatic layer, an abrasion-resistant layer, a color correction layer, a printed layer, a transparent conductive layer, a gas barrier layer, a hologram layer, on the surface opposite to the surface on which the cured resin layer of the base film is laminated. Functional layers such as a release layer, an adhesive layer, and an adhesive layer may be laminated.

  In addition, the laminated film is suitable for decorative molding, in-mold molding, or insert molding, and as an exterior film for an electric equipment housing such as a mobile phone or a notebook computer, as an icon sheet for a mobile phone, or for in-vehicle use. It is suitable as a decorative film for display panels.

  In the above molding process, the laminated film may be preformed (heated and stretched) in advance so as to fit the molding die. The heating temperature of the preform is generally in the range of 100 to 170 ° C.

  Hereinafter, the present invention will be specifically described based on examples. However, the present invention is not limited to the following examples. In addition, the evaluation method of each physical-property value used in the Example is described below.

[Evaluation method]
First, an evaluation method in each example and comparative example will be described. The number of evaluation n was n = 5 unless otherwise specified, and the arithmetic average value was obtained.

(1) Stretching test of laminated film A 66 mm square sample was cut out from the laminated film. Using an automatic biaxial stretching apparatus (IMC-167D manufactured by Imoto Seisakusho Co., Ltd.), the sample was stretched at a temperature of 150 ° C. and a stretching speed of 200 mm / min. Stretched. The haze value after stretching (Hz1) and the haze value before stretching (Hz0) were measured, and the absolute value (| Hz1-Hz0 |) of the haze value difference before and after stretching was determined.

  In the same manner as described above, the film was stretched at the same vertical and horizontal magnification (each 1.23 times) to an area ratio of 150%. The haze value after stretching (Hz2) and the haze value before stretching (Hz0) were measured, and the absolute value (| Hz2-Hz0 |) of the haze value difference before and after stretching was determined.

<Measurement of haze value>
Based on JIS K7136 (2000), it measured using the turbidimeter "NDH-4000" by Nippon Denshoku Industries Co., Ltd. In the measurement, it arrange | positions so that light may inject into the surface of the cured resin layer of a laminated | multilayer film.

(2) Measurement of luminous reflectance With respect to the sample stretched to an area ratio of 130%, the sample stretched to an area ratio of 150%, and the sample before stretching obtained in the stretching test of (1) above, the luminous reflectance was respectively obtained. Was measured. For the measurement of luminous reflectance, a measurement sample prepared by attaching a black adhesive tape to the surface of the sample (laminated film) opposite to the cured resin layer was used.

<Measurement>
Using a spectrophotometer (manufactured by Shimadzu Corporation, UV3150PC), the reflectance (single-sided reflection) is calculated in the wavelength range of 380 to 780 nm at an incident angle of 5 degrees from the measurement surface (cured resin layer surface), and the luminous reflectance ( The reflection stimulation value Y) defined in JIS Z8701-1999 was determined. The spectral solid angle is measured with a spectrophotometer, and the reflectance (single-sided light reflection) is calculated according to JIS Z8701-1999. The calculation formula is as follows.

  T = K · ∫S (λ) · y (λ) · R (λ) · dλ (however, the integration interval is 380 to 780 nm)

T: single-sided light reflectance S (λ): standard light distribution used for color display y (λ): color matching function R (λ) in XYZ display system: spectral solid angle reflectance.
T: single-sided light reflectance

(3) Measurement of thickness of cured resin layer and undercoat layer With respect to the cross section of the laminated film, an ultrathin section for transmission electron microscope (TEM) imaging was prepared using a microtome, and a transmission electron microscope (Hitachi, Ltd.) ) “H-7100FA”)) and a magnification of 10,000 to 100,000 times. The thickness of the cured resin layer and the undercoat layer was measured from this photographed image. Measurement was carried out at 30 points at equal intervals and averaged.

(4) Identification of boundary line 1d between region A and region B, and region A and region B Regarding the cross-sectional photographed image of the cured resin layer photographed in (3) above, the opposite surface of the base film of the cured resin layer 30 points are positioned at equal intervals on the line (reference numeral 1c in the drawing), and a position of 100 nm is specified from each point in the thickness direction of the cured resin layer, and a line obtained by connecting these 30 specific points with a straight line A boundary line between the region A and the region B (reference numeral 1d in the drawing) is used. The region from the opposite surface of the base film of the cured resin layer to the boundary line formed above is region A, and the entire region excluding region A is region B.

(5) Content ratio of silica particles contained in region A The number of silica particles present in region A and region B specified in (4) above is measured. Here, the silica particles existing on the boundary line between the region A and the region B are counted as being included in the region A. The total number of silica particles contained in region A and region B was taken as the total number of silica particles contained in the cured resin layer, and the ratio of the number of silica particles contained in region A to the total number of silica particles was evaluated according to the following criteria.

S; the number of silica particles contained in region A is 90% or more of the total number of silica particles A; the number of silica particles contained in region A is 80% or more and less than 90% of the total number of silica particles B; the silica particles contained in region A The number is 70% or more and less than 80% of the total number of silica particles C; the number of silica particles contained in the region A is less than 70% of the total number of silica particles

(6) Evaluation of localized state of silica particles in region A of the cured resin layer The number of silica particles present in region A and region B specified in (4) above is measured. Here, the silica particles existing on the boundary line between the region A and the region B are counted as being included in the region A.

<Contrast of number density of silica particles in region A and region B>
Since the thickness of the region A is constant at 100 nm, the number of silica particles present in the region A is defined as the silica particle number density (Asi) in the region A, and the silica particle number density (Bsi) in the region B is obtained by the following formula 1.

  Bsi = bs / (bt / 100) Formula 1

  In the formula, bs represents the number of silica particles present in the region B, and bt represents the thickness (nm) of the region B. The thickness (bt) of the region B is obtained by subtracting 100 nm (the thickness of the region A) from the thickness of the cured resin layer obtained in (3) above.

  Evaluation of the localized state of the silica particles in the region A was performed according to the following criteria. “S” to “B” mean that silica particles are localized at a relatively high density in region A, and “C” means that silica particles are located at a relatively high density in region A. Means not. “S” is the best.

S; Bsi × 8.0 ≦ Asi
A; Bsi × 5.0 ≦ Asi <Bsi × 8.0
B; Bsi × 2.0 ≦ Asi <Bsi × 5.0
C; Bsi × 2.0 <Asi

(7) Evaluation of localized state of metal oxide particles in region B of cured resin layer The metal oxide particles present in region A and region B specified in (4) above are measured. Here, the metal oxide particles present on the boundary line between the region A and the region B are counted as being included in the region A.

<Contrast of number density of metal oxide particles in region A and region B>
Since the thickness of the region A is constant at 100 nm, the number of metal oxide particles present in the region A is defined as the metal oxide particle number density (Am) in the region A, and the metal oxide particle number density (Bm) in the region B is as follows: It calculates | requires by Formula 2 of.

  Bm = bm / (bt / 100) Expression 2

  In the formula, bm is the number of metal oxide particles present in the region B, and bt is synonymous with formula 1.

  The evaluation of the localized state of the metal oxide particles in the region B was performed according to the following criteria. “S” to “B” mean that the metal oxide particles are localized at a relatively high density in the region A, and “C” is a relatively high density of the metal oxide particles in the region A. Means not localized. “S” is the best.

S; Bm × 8.0 ≦ Am
A; Bm × 5.0 ≦ Am <Bm × 8.0
B; Bm × 2.0 ≦ Am <Bm × 5.0
C; Bm × 2.0 <Am

(8) Confirmation of interface between region A and region B For a cured resin layer formed using a coating composition containing at least silica particles and metal oxide particles, observe a cross section using a transmission electron microscope (TEM). Thus, it was evaluated whether or not the interface between the region A in which the silica particles were localized at a relatively high density and the region B in which the metal oxide particles were localized at a relatively high density could be clearly confirmed.

  The interface was confirmed according to the following method. The image (50,000 to 200,000 times) which image | photographed the cross section of the cured resin layer similarly to above-mentioned (3) was affixed on presentation software (Microsoft Power Point2003) using the scanner. Next, image control processing (contrast was set to 90%) of the attached photograph was performed to enhance the contrast. In this case, a case where a clear boundary can be drawn at the interface between the region A where the silica particles are localized at a relatively high density and the region B where the metal oxide particles are located at a relatively high density. , It was considered that there is a clear interface ("○" indicates that a clear boundary can be drawn, and "x" indicates that a clear boundary cannot be drawn). .

(9) Measurement of haze value of substrate film Based on JIS K7136 (2000), it was measured using a turbidimeter “NDH-4000” manufactured by Nippon Denshoku Industries Co., Ltd.

[Dispersions and coating compositions used in Examples and Comparative Examples]
<Preparation of silica particle dispersion b1>
As silica particles, isopropyl alcohol dispersion of hollow silica particles (hollow silica manufactured by JGC Catalysts & Chemicals Co., Ltd .: solid content concentration 20 mass%, number average particle diameter 60 nm) is added to 1.37 methacryloxypropyltrimethoxysilane. A mass part, 0.17 mass part of 10 mass% formic acid aqueous solution, and 0.306 mass part of water were mixed, and it stirred at 70 degreeC for 1 hour. Next, after adding 1.38 parts by mass of perfluorooctylmethyl acrylate and 0.057 parts by mass of 2,2-azobisisobutyronitrile as a fluorine compound, the mixture was heated and stirred at 90 ° C. for 60 minutes. Subsequently, isopropyl alcohol was added for dilution to prepare a dispersion (solid dispersion of silica particles surface-treated with a fluorine compound) having a solid content of 3.5% by mass.

<Silica particle dispersion b2>
As the silica particles, an isopropyl alcohol dispersion of hollow silica particles (JGC Catalysts & Chemicals, Inc. hollow silica: solid content concentration 20 mass%, number average particle diameter 60 nm) was used as it was. The silica particles are not surface-treated with a fluorine compound.

<Zirconium oxide dispersion c1>
Using 167 parts by mass of zirconium oxide methanol dispersion (manufactured by Nissan Chemical Co., Ltd .: solid content concentration 31% by mass, number average particle size 15 nm), 15 parts by mass of methacryloxypropyltrimethoxysilane was added dropwise and stirred uniformly. Next, 2.0 parts by mass of a 20% aqueous acetic acid solution and 5.4 parts by mass of ion-exchanged water were added dropwise thereto, and reacted at 35 ° C. for 30 minutes and at 60 ° C. for 3 hours. Furthermore, 200 parts by mass of methyl isobutyl ketone was added as a substitution solvent, and methanol removal treatment was performed at 50 ° C. and 680 mmHg with a rotary evaporator. Finally, the solid content concentration was adjusted to 30% by mass with methyl isobutyl ketone, and microfiltration was performed. Thus, a dispersion (zirconium oxide particle dispersion surface-treated with the compound of the general formula (2)) was obtained.

[Coating composition for cured resin layer]
<Coating composition a1>
As a resin component, 21.0 parts by mass of a bifunctional epoxy acrylate having a bisphenol skeleton (epoxy ester 3000A of Kyoeisha Chemical Co., Ltd .; molecular weight 484), tridecafluorooctyl acrylate (“Biscoat” manufactured by Osaka Organic Chemical Industry Co., Ltd.) (Registered Trademark) Model No. 13F) is 5.0 parts by mass, the silica particle dispersion b1 is 27.8 parts by mass in terms of solid content, and a photopolymerization initiator (Irgacure 907 manufactured by Ciba Specialty Chemicals Co., Ltd.). 1.4 parts by mass is dissolved, dispersed and diluted with an organic solvent (13: 1 (mass ratio) mixed solvent of methyl isobutyl ketone and ethylene glycol monobutyl ether), and a solid content concentration is 6.4% by mass A composition was prepared.

<Coating composition a2>
As a resin component, 21.0 parts by mass of a bifunctional urethane acrylate oligomer ("Art Resin" (registered trademark) UN-353 (weight average molecular weight 5,000) manufactured by Negami Kogyo Co., Ltd.), tridecafluorooctyl acrylate (Osaka) 5.0 parts by mass of “Biscoat” (registered trademark) Model No. 13F) manufactured by Organic Chemical Industry Co., Ltd., 27.8 parts by mass of the silica particle dispersion b1 in terms of solid content, a photopolymerization initiator ((Ciba 1.4 parts by mass of Irgacure 907 manufactured by Specialty Chemicals Co., Ltd. is dissolved, dispersed and diluted with an organic solvent (13: 1 (mass ratio) mixed solvent of methyl isobutyl ketone and ethylene glycol monobutyl ether) to obtain a solid. A coating composition having a partial concentration of 6.4% by mass was prepared.

<Coating composition a3>
As a resin component, 21.0 parts by mass of a 20-functional urethane acrylate oligomer (trade name “Acryt 8BR-930MB” of Taisei Fine Chemical Co., Ltd., weight average molecular weight 16,000), tridecafluorooctyl acrylate (Osaka Organic Chemical Industry) "Biscoat" (Registered Trademark) Model No. 13F) manufactured by Co., Ltd., 5.0 parts by mass, 27.8 parts by mass of the silica particle dispersion b1 in terms of solid content, a photopolymerization initiator ((Ciba Specialty Chemicals) (Irgacure 907) 1.4 parts by mass was dissolved, dispersed and diluted with an organic solvent (13: 1 (mass ratio) mixed solvent of methyl isobutyl ketone and ethylene glycol monobutyl ether), and the solid content concentration was A coating composition of 6.4% by mass was prepared.

<Coating composition a4>
As a resin component, 21.0 parts by mass of 3-4 functional pentaerythritol (tri / tetra) acrylate (trade name “NK Ester A-TMM-3L”, molecular weight 298-382) manufactured by Shin-Nakamura Chemical Co., Ltd., 5.0 parts by mass of decafluorooctyl acrylate (Osaka Organic Chemical Co., Ltd. “Biscoat” (registered trademark) model number 13F), 27.8 parts by mass of the above silica particle dispersion b1 in terms of solid content, photopolymerization 1. Initiator (Ciba Specialty Chemicals Co., Ltd. Irgacure 907) 1. Part by mass is dissolved and dispersed in an organic solvent (13: 1 (mass ratio) mixed solvent of methyl isobutyl ketone and ethylene glycol monobutyl ether). By diluting, a coating composition having a solid content concentration of 6.4% by mass was prepared.

<Coating composition a5>
As a resin component, 21.0 parts by mass of hexafunctional dipentaerythritol hexaacrylate ("DPHA" trade name, molecular weight 524, manufactured by Daicel Cytec Co., Ltd.), tridecafluorooctyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.) "Biscoat" (registered trademark) model number 13F) is 5.0 parts by mass, the silica particle dispersion b1 is 27.8 parts by mass in terms of solid content, a photopolymerization initiator (Irgacure manufactured by Ciba Specialty Chemicals Co., Ltd.) 907) 1.4 parts by mass is dissolved, dispersed, and diluted with an organic solvent (13: 1 (mass ratio) mixed solvent of methyl isobutyl ketone and ethylene glycol monobutyl ether) to obtain a solid content concentration of 6.4% by mass. A coating composition was prepared.

<Coating composition a6>
As a resin component, 21.0 parts by mass of a 10-functional urethane acrylate oligomer (trade name “KRM8452” manufactured by Daicel Ornex Co., Ltd., weight average molecular weight 1,200), tridecafluorooctyl acrylate (Osaka Organic Chemical Industry ( "Biscoat" (Registered Trademark) Model No. 13F), 5.0 parts by mass, 27.8 parts by mass of the silica particle dispersion b1 in terms of solid content, a photopolymerization initiator ((Ciba Specialty Chemicals ( Irgacure 907) 1.4 parts by mass is dissolved, dispersed, and diluted with an organic solvent (13: 1 (mass ratio) mixed solvent of methyl isobutyl ketone and ethylene glycol monobutyl ether) to obtain a solid content concentration of 6 A 4% by weight coating composition was prepared.

<Coating composition a7>
As a resin component, 17.3 parts by mass of a bifunctional epoxy acrylate having a bisphenol skeleton (epoxy ester 3000A of Kyoeisha Chemical Co., Ltd .; molecular weight 484) and 27.8 parts by mass of the above silica particle dispersion b1 in terms of solid content , 18.1 parts by mass of the above-mentioned metal oxide particle (zirconium oxide particle) dispersion c1 in terms of solid content and 1.4 parts by mass of a photopolymerization initiator (Irgacure 907 manufactured by Ciba Specialty Chemicals Co., Ltd.) Then, it was dissolved, dispersed and diluted in an organic solvent (13: 1 (mass ratio) mixed solvent of methyl isobutyl ketone and ethylene glycol monobutyl ether) to prepare a coating composition having a solid content concentration of 6.4% by mass.

<Coating composition a8>
As a resin component, 17.3 parts by mass of a bifunctional urethane acrylate oligomer (“Art Resin” (registered trademark) UN-353, weight average molecular weight 5,000, manufactured by Negami Kogyo Co., Ltd.), the above silica particle dispersion b1 27.8 parts by mass in terms of solid content, 18.1 parts by mass of the above metal oxide particle (zirconium oxide particle) dispersion c1 in terms of solid content, photopolymerization initiator ((Ciba Specialty Chemicals Co., Ltd.) Irgacure 907) 1.4 parts by mass was dissolved, dispersed, and diluted with an organic solvent (13: 1 (mass ratio) mixed solvent of methyl isobutyl ketone and ethylene glycol monobutyl ether) to obtain a solid content concentration of 6.4. A mass% coating composition was prepared.

<Coating composition a9>
As a resin component, 17.3 parts by mass of a 20-functional urethane acrylate oligomer (trade name “Acryt 8BR-930MB” of Taisei Fine Chemical Co., Ltd., weight average molecular weight 16,000), and the silica particle dispersion b1 as a solid content 27.8 parts by weight in terms of conversion, 18.1 parts by weight in terms of solid content of the above-mentioned metal oxide particle (zirconium oxide particle) dispersion c1, and a photopolymerization initiator (Irgacure 907 manufactured by Ciba Specialty Chemicals Co., Ltd.) ) 1.4 parts by mass is dissolved, dispersed and diluted with an organic solvent (13: 1 (mass ratio) mixed solvent of methyl isobutyl ketone and ethylene glycol monobutyl ether) to obtain a solid content concentration of 6.4% by mass. A coating composition was prepared.

<Coating composition a10>
As a resin component, 17.3 parts by mass of 3-4 functional pentaerythritol (tri / tetra) acrylate (Shin Nakamura Chemical Co., Ltd., trade name “NK Ester A-TMM-3L”, molecular weight 298-382), 27.8 parts by weight of the silica particle dispersion b1 in terms of solid content, 18.1 parts by weight of the metal oxide particle (zirconium oxide particle) dispersion c1 in terms of solids, and a photopolymerization initiator ((Ciba 1.4 parts by mass of Irgacure 907 manufactured by Specialty Chemicals Co., Ltd. is dissolved, dispersed and diluted with an organic solvent (13: 1 (mass ratio) mixed solvent of methyl isobutyl ketone and ethylene glycol monobutyl ether) to obtain a solid. A coating composition having a partial concentration of 6.4% by mass was prepared.

<Coating composition a11>
As the resin component, 17.3 parts by mass of hexafunctional dipentaerythritol hexaacrylate (“DPHA” trade name, molecular weight 524, manufactured by Daicel Cytec Co., Ltd.) and 27.8 of the above silica particle dispersion b1 in terms of solid content are used. Parts by weight, 18.1 parts by weight of the above-mentioned metal oxide particle (zirconium oxide particle) dispersion c1 in terms of solid content, 1.4 parts by weight of photopolymerization initiator (Irgacure 907 manufactured by Ciba Specialty Chemicals Co., Ltd.) Parts are dissolved, dispersed and diluted with an organic solvent (13: 1 (mass ratio) mixed solvent of methyl isobutyl ketone and ethylene glycol monobutyl ether) to prepare a coating composition having a solid content concentration of 6.4% by mass. did.

<Coating composition a12>
As a resin component, 10 functional urethane acrylate oligomer (trade name “KRM8452” manufactured by Daicel Ornex Co., Ltd., weight average molecular weight 1,200) is 17.3 parts by mass, and the above silica particle dispersion b1 is converted into solid content 27.8 parts by mass, 18.1 parts by mass of the above metal oxide particle (zirconium oxide particle) dispersion c1 in terms of solid content, a photopolymerization initiator (Irgacure 907 manufactured by Ciba Specialty Chemicals Co., Ltd.) 1.4 parts by mass is dissolved, dispersed and diluted with an organic solvent (13: 1 (mass ratio) mixed solvent of methyl isobutyl ketone and ethylene glycol monobutyl ether), and a solid content concentration is 6.4% by mass A composition was prepared.

<Paint composition a13>
As a resin component, 21.6 parts by mass of a bifunctional urethane acrylate oligomer ("Art Resin" (registered trademark) UN-353; weight average molecular weight 5,000, manufactured by Negami Kogyo Co., Ltd.), the above silica particle dispersion b1 18.3 parts by mass in terms of solid content, 22.5 parts by mass of the above-mentioned metal oxide particle (zirconium oxide particle) dispersion c1 in terms of solid content, photopolymerization initiator ((Ciba Specialty Chemicals Co., Ltd.) 1.7 parts by mass of Irgacure 907) are dissolved, dispersed, and diluted with an organic solvent (13: 1 (mass ratio) mixed solvent of methyl isobutyl ketone and ethylene glycol monobutyl ether) to obtain a solid content concentration of 6.4. A mass% coating composition was prepared.

<Paint composition a14>
As a resin component, 25.1 parts by mass of a bifunctional urethane acrylate oligomer ("Art Resin" (registered trademark) UN-353 (weight average molecular weight 5,000) manufactured by Negami Kogyo Co., Ltd.), the above silica particle dispersion b1 Is 10.6 parts by mass in terms of solid content, 26.2 parts by mass of the above metal oxide particle (zirconium oxide particle) dispersion c1 in terms of solid content, and a photopolymerization initiator ((Ciba Specialty Chemicals Co., Ltd.). Irgacure 907) 2.0 parts by mass is dissolved, dispersed, and diluted with an organic solvent (13: 1 (mass ratio) mixed solvent of methyl isobutyl ketone and ethylene glycol monobutyl ether) to obtain a solid content concentration of 6.4. A mass% coating composition was prepared.

<Coating composition a15>
As a resin component, 27.2 parts by weight of a bifunctional urethane acrylate oligomer ("Art Resin" (registered trademark) UN-353 (weight average molecular weight 5,000) manufactured by Negami Kogyo Co., Ltd.), the above silica particle dispersion b1 6.6 parts by mass in terms of solid content, 28.3 parts by mass of the above metal oxide particle (zirconium oxide particle) dispersion c1 in terms of solid content, photopolymerization initiator ((Ciba Specialty Chemicals Co., Ltd.) Irgacure 907) 2.1 parts by mass was dissolved, dispersed, and diluted with an organic solvent (13: 1 (mass ratio) mixed solvent of methyl isobutyl ketone and ethylene glycol monobutyl ether) to obtain a solid content concentration of 6.4. A mass% coating composition was prepared.

<Coating composition a16>
As the resin component, 21.0 parts by mass of hexafunctional dipentaerythritol hexaacrylate (“DPHA” trade name, molecular weight 524, manufactured by Daicel Cytec Co., Ltd.) and 27.8 of the above silica particle dispersion b2 in terms of solid content are used. Parts by weight, 1.4 parts by weight of a photopolymerization initiator (Irgacure 907 manufactured by Ciba Specialty Chemicals Co., Ltd.), 13: 1 (mass ratio) mixed solvent of an organic solvent (methyl isobutyl ketone and ethylene glycol monobutyl ether) ) Was dissolved, dispersed, and diluted to prepare a coating composition having a solid content concentration of 6.4% by mass.

<Coating composition a17>
As the resin component, 17.3 parts by mass of hexafunctional dipentaerythritol hexaacrylate (“DPHA” trade name, molecular weight 524, manufactured by Daicel Cytec Co., Ltd.) and 27.8 of the above silica particle dispersion b2 in terms of solid content are used. Parts by weight, 18.1 parts by weight of the above-mentioned metal oxide particle (zirconium oxide particle) dispersion c1 in terms of solid content, 1.4 parts by weight of photopolymerization initiator (Irgacure 907 manufactured by Ciba Specialty Chemicals Co., Ltd.) Parts are dissolved, dispersed and diluted with an organic solvent (13: 1 (mass ratio) mixed solvent of methyl isobutyl ketone and ethylene glycol monobutyl ether) to prepare a coating composition having a solid content concentration of 6.4% by mass. did.

[Coating composition for undercoat layer (UC layer)]
<Coating composition d1>
100 parts by mass of difunctional urethane acrylate oligomer (Negami Kogyo Co., Ltd. “Art Resin” (registered trademark) UN-6200; weight average molecular weight 6,500), dipentaerythritol hexaacrylate (manufactured by Daicel Cytec Co., Ltd., “DPHA”) "Product name, molecular weight 524) 20 parts by weight, photopolymerization initiator (Ciba Specialty Chemicals" Irgacure "(registered trademark) 184) 5 parts by weight diluted with an organic solvent (methyl ethyl ketone), The solid concentration was adjusted to 20% by mass.

[Coating composition of high refractive index layer and low refractive index layer for sequential lamination]
<Coating composition e1 for high refractive index layer>
As a resin component, 17.5 parts by mass of a bifunctional epoxy acrylate having a bisphenol skeleton (epoxy ester 3000A of Kyoeisha Chemical Co., Ltd .; molecular weight 484) and the above-mentioned metal oxide particle (zirconium oxide particle) dispersion c1 as a solid content 18.1 parts by mass in terms of conversion, 1.4 parts by mass of a photopolymerization initiator (Irgacure 907 manufactured by Ciba Specialty Chemicals Co., Ltd.), 13: 1 of an organic solvent (methyl isobutyl ketone and ethylene glycol monobutyl ether) A coating composition having a solid content concentration of 3.7% by mass was prepared by dissolving, dispersing, and diluting with (mass ratio) mixed solvent).

<Coating composition f1 for low refractive index layer>
As a resin component, 17.5 parts by mass of a bifunctional epoxy acrylate having a bisphenol skeleton (epoxy ester 3000A of Kyoeisha Chemical Co., Ltd .; molecular weight 484) and 30.0 parts by mass of the above silica particle dispersion b1 in terms of solid content , 1.4 parts by mass of a photopolymerization initiator (Irgacure 907 manufactured by Ciba Specialty Chemicals Co., Ltd.) with an organic solvent (13: 1 (mass ratio) mixed solvent of methyl isobutyl ketone and ethylene glycol monobutyl ether) By dissolving, dispersing and diluting, a coating composition having a solid content concentration of 3.0% by mass was prepared.

[Example 1]
On one surface of a polyethylene terephthalate (PET) film having a thickness of 125 μm (Lumirror (registered trademark) U48 manufactured by Toray Industries, Inc., haze value 0.85), the coating composition a1 is dried with a gravure coater to a thickness of 200 nm. After being coated at 80 ° C., ultraviolet rays were irradiated with an irradiation light amount of 400 mJ / cm ² and cured to form a cured resin layer to obtain a laminated film.

[Example 2]
A cured resin layer was formed in the same manner as in Example 1 except that the coating composition a2 was changed to obtain a laminated film.

[Example 3]
A laminated resin film was obtained by forming a cured resin layer in the same manner as in Example 1 except that the composition was changed to the coating composition a3.

[Comparative Example 1]
A cured resin layer was formed in the same manner as in Example 1 except that the coating composition was changed to the coating composition a4 to obtain a laminated film.

[Comparative Example 2]
A laminated resin film was obtained by forming a cured resin layer in the same manner as in Example 1 except that the composition was changed to the coating composition a5.

[Comparative Example 3]
A laminated resin film was obtained by forming a cured resin layer in the same manner as in Example 1 except that the composition was changed to the coating composition a6.

[Comparative Example 4]
A cured resin layer was formed in the same manner as in Example 1 except that the coating composition was changed to the coating composition a16 to obtain a laminated film.

[Examples 4 to 6]
In Examples 1 to 3, the base film is a two-layer laminated film of a polycarbonate layer having a thickness of 125 μm and a polymethyl methacrylate layer (PC / PMMA; “Technoloy” (registered trademark) model number “C001” manufactured by Sumitomo Chemical Co., Ltd.). The haze value was changed to 0.30%), and a laminated film was produced in the same manner as in Examples 1 to 3 except that a cured resin layer was laminated on the polymethyl methacrylate layer (PMMA) side.

[Examples 7 to 9]
In Examples 1 to 3, laminated films were produced in the same manner as in Examples 1 to 3 except that the following undercoat layer (UC layer) was disposed between the base film and the cured resin layer.

<Lamination of undercoat layer (UC layer)>
The undercoat layer coating composition d1 was applied with a gravure coater so that the dry thickness was 2 μm, dried at 80 ° C., and then irradiated with UV light at an irradiation light amount of 400 mJ / cm ² to cure the undercoat layer. Formed.

[Evaluation]
Table 1 shows the results of measurement and evaluation of the laminated films prepared in the above Examples and Comparative Examples according to the above-described evaluation items.

[Example 11]
A laminated resin film was obtained by forming a cured resin layer in the same manner as in Example 1 except that the composition was changed to the coating composition a7.

[Example 12]
A laminated resin film was obtained by forming a cured resin layer in the same manner as in Example 1 except that the composition was changed to the coating composition a8.

[Example 13]
A cured resin layer was formed in the same manner as in Example 1 except that the composition was changed to the coating composition a9 to obtain a laminated film.

[Comparative Example 11]
A laminated resin film was obtained by forming a cured resin layer in the same manner as in Example 1 except that the coating composition was changed to the coating composition a10.

[Comparative Example 12]
A laminated resin film was obtained by forming a cured resin layer in the same manner as in Example 1 except that the coating composition was changed to the coating composition a11.

[Comparative Example 13]
A laminated resin film was obtained by forming a cured resin layer in the same manner as in Example 1 except that the composition was changed to the coating composition a12.

[Comparative Example 14]
A laminated resin film was obtained by forming a cured resin layer in the same manner as in Example 1 except that the composition was changed to the coating composition a17.

[Examples 14 to 16]
In Examples 11 to 13, the base film was formed of a two-layer laminated film of a polycarbonate layer having a thickness of 125 μm and a polymethyl methacrylate layer (PC / PMMA; “Technoloy” (registered trademark) model number “C001” manufactured by Sumitomo Chemical Co., Ltd.). The haze value was changed to 0.30%), and a laminated film was produced in the same manner as in Examples 11 to 13 except that a cured resin layer was laminated on the polymethyl methacrylate layer (PMMA) side.

[Examples 17 to 19]
In Examples 11 to 13, laminated films were produced in the same manner as in Examples 11 to 13, except that an undercoat layer (UC layer) was disposed between the base film and the cured resin layer.

<Lamination of undercoat layer (UC layer)>
The undercoat layer coating composition d1 is applied with a gravure coater so that the dry thickness is 2 μm, dried at 80 ° C., and then cured by irradiating with UV light at an irradiation light amount of 400 mJ / cm ^2. A layer was formed.

[Examples 20 to 22]
In Examples 14 to 16, laminated films were produced in the same manner as in Examples 14 to 16, except that an undercoat layer (UC layer) was disposed between the base film and the cured resin layer.

<Lamination of undercoat layer (UC layer)>
The undercoat layer coating composition d1 is applied with a gravure coater so that the dry thickness is 2 μm, dried at 80 ° C., and then cured by irradiating with UV light at an irradiation light amount of 400 mJ / cm ^2. A layer was formed.

[Comparative Example 15]
In the same manner as in Example 17, an undercoat layer (UC layer) was laminated on one surface of a base film (PET film), and a high refractive index layer and a low refractive index layer were sequentially formed on the undercoat layer in this order. To obtain a laminated film.

<Lamination of high refractive index layer>
The high refractive index layer coating composition e1 was applied with a gravure coater so that the dry thickness was 100 nm, dried at 80 ° C., and then irradiated with ultraviolet light at an irradiation light amount of 400 mJ / cm ² to be cured. A refractive index layer was formed.

<Lamination of low refractive index layer>
The low refractive index coating composition f1 is applied with a gravure coater so as to have a dry thickness of 100 nm, dried at 80 ° C., and then irradiated with UV light at an irradiation light amount of 400 mJ / cm ² to be cured. A refractive index layer was formed.

[Evaluation]
Table 2 shows the results of measurement and evaluation of the laminated films prepared in the above Examples and Comparative Examples according to the above-described evaluation items.

[Example 31]
In the same manner as in Example 7, an undercoat layer (UC layer) was laminated on one surface of a base film (PET film), and the cured resin layer coating composition a13 was dried on the undercoat layer with a gravure coater. The film was applied to a thickness of 300 nm, dried at 80 ° C., and then cured by irradiating with ultraviolet light at an irradiation light amount of 400 mJ / cm ² to form a cured resin layer, thereby obtaining a laminated film.

[Example 32]
A laminated film was obtained in the same manner as in Example 31 except that the coating composition a14 was changed and the dry thickness of the cured resin layer was changed to 500 nm.

[Example 33]
A laminated film was obtained in the same manner as in Example 31 except that the coating composition was changed to the coating composition a15 and the dry thickness of the cured resin layer was changed to 800 nm.

[Evaluation]
Table 3 shows the results of measurement and evaluation of the laminated films produced in the above examples according to the evaluation items described above.

DESCRIPTION OF SYMBOLS 1 Hardened resin layer 2 Base film 3 Undercoat layer 11 Silica particle 12 Metal oxide particle A Area | region A
B area B

Claims (7)

  A laminated film having a cured resin layer composed of a single layer having a thickness of 170 nm or more on a base film directly or through an undercoat layer, and having a haze value (Hz1) and stretching when stretched to an area ratio of 130% The absolute value of the difference from the previous haze value (Hz0) is 0.30% or less, the cured resin layer contains silica particles, and the thickness of the cured resin layer from the surface opposite to the base film is in the thickness direction. A laminated film, wherein the number of silica particles contained in the region A up to 100 nm is 70% or more of the total number of silica particles contained in the cured resin layer.   The laminated film according to claim 1, wherein the number density of silica particles in the region A is 2.0 times or more of the number density of silica particles in the entire region B except the region A.   The laminated film according to claim 1 or 2, wherein the luminous reflectance before stretching is less than 1.70%.   The laminated film according to claim 1, wherein the silica particles are surface-treated with a fluorine compound.   The laminated film according to claim 1, wherein the cured resin layer further contains metal oxide particles.   The laminated film according to claim 5, wherein the number density of metal oxide particles in all areas B excluding the area A is 2.0 times or more of the number density of metal oxide particles in the area A.   An antireflection film for molding comprising the laminated film according to claim 1.

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