JP6790827B2 - Laminated film and its manufacturing method - Google Patents

Description

The present invention relates to a laminated film having a polyester layer and a resin layer, wherein at least one surface layer is a resin layer.

Thermoplastic resin films, especially biaxially stretched polyester films, have excellent mechanical properties, electrical properties, dimensional stability, transparency, chemical resistance, etc., and therefore are used in many magnetic recording materials, packaging materials, etc. Widely used in applications. Particularly in recent years, it has been used in various optical films including display member applications such as touch panels, liquid crystal display panels (LCDs), plasma display panels (PDPs), and organic electroluminescence (organic ELs).

In these optical films, a layer having a different refractive index (hereinafter referred to as an optical adjustment layer) is laminated on a polyester film, and then a conductive layer is provided, which is often used as a conductive film. Here, generally, when laminating the optical adjustment layer, a functional coating agent is applied to a base film wound in a roll shape, cured, and then wound in a roll shape, so-called roll-to-roll. Processed in shape. Further, the conductive layer is formed by forming a metal oxide film on a roll film by sputtering in a vacuum environment.
Therefore, in such an application, a laminated film in which a scratch-resistant layer is laminated on a polyester film is used in order to prevent scratches during transportation of the film roll.

As this laminated film, a hard coat film in which a layer made of a UV curable resin is laminated as a scratch resistant layer is used. When used in optical applications, transparency is required, so the surface of the resin layer is smoothed in order to improve transparency. However, if the surface of the resin layer is smoothed, it will be formed into a film roll. Blocking (sticking) occurs. Therefore, in recent years, a laminated film having blocking resistance has been demanded.
In addition to scratch resistance, laminated films used for optical applications are also required to have adhesiveness and transparency not only at room temperature but also at high temperature and high humidity. Further, since it is often used on the surface of a display or the like, visibility and design are required for a laminated film used for optical applications.

In response to such a requirement, Patent Document 1 proposes a method of reducing the contact area of a hard coat film and exhibiting anti-blocking property by laminating a coating film containing particles larger than the coating film thickness. Further, Patent Document 2 proposes a method of obtaining a laminated film having excellent antiglare and scratch resistance by laminating a coating film containing acrylic particles smaller than the coating film thickness.

Japanese Unexamined Patent Publication No. 2014-228833 Japanese Unexamined Patent Publication No. 2011-186287

However, the method described in Patent Document 1 has a problem that light is scattered and transparency is impaired because the particle size of the particles existing in the coat layer is large. Further, also in the method described in Patent Document 2, since the particle size of the acrylic particles existing in the coat layer having a film thickness of 6 to 8 μm is as large as about 2 to 5 μm, it is a region where light scattering occurs. There is a problem with transparency in optical applications that require high transparency.

Therefore, it is an object of the present invention to eliminate the above-mentioned drawbacks and to provide a laminated film having excellent transparency, scratch resistance, and antiblocking property.

In order to solve the above problems, the laminated film of the present invention has the following constitution.
[I] A laminated film having a polyester layer and a resin layer, wherein at least one surface layer is a resin layer, and the resin layer having the surface layer is a micro surface roughness (Ra-) determined by AFM (Atomic Force Microscope). A laminated film in which 1) is 1 nm or more and 20 nm or less, and the macro surface roughness (Ra-2) determined by a three-dimensional surface roughness meter is 1 nm or more and 50 nm or less.
[II] The laminated film according to [I], wherein the resin layer contained in the surface layer has a macro surface roughness (Ra-2) determined by a three-dimensional surface roughness meter of 5 nm or more and 50 nm or less.
[III] The ratio (Ra-2 / Ra-1) of the micro surface roughness (Ra-1) of the resin layer having the surface layer to the macro surface roughness (Ra-2) is 3 or more and 30 or less. The laminated film according to I] or [II].
[IV] The resin layer on the surface layer contains particles, and the particle abundance ratio in the range from the surface of the resin layer to the position of 10% of the thickness of the resin layer when the cross section of the resin layer in the thickness direction is observed ( P-1) is one of [I] to [III], which is larger than the particle abundance ratio (P-2) in the range from the resin layer surface to the position of 40% to 60% of the resin layer thickness. The laminated film described.
[V] The particle abundance ratio (P-1) in the range from the resin layer surface to the position of 10% of the resin layer thickness, and the range from the resin layer surface to the position of 40% to 60% of the resin layer thickness. The laminated film according to [IV], wherein the ratio (P-1 / P-2) of the particle abundance ratio (P-2) in the above is 1.1 or more and 5.0 or less.
[VI] The laminated film according to [IV] or [V], wherein the thickness (t) of the resin layer on the surface layer is 100 nm or more and 5000 nm or less.
[VII] The average particle size (d) of the particles contained in the resin layer on the surface layer is 1 nm or more and 100 nm or less, and the ratio (t) of the thickness (t) of the resin layer to the average particle size (d) of the particles is (t). The laminated film according to [VI], wherein / (d) is 2 or more and 1000 or less.
[VIII] The laminated film according to any one of [I] to [VII], wherein the polyester layer and the resin layer are directly laminated.
[IX] A coating liquid containing a polyfunctional acrylic resin and particles is applied to at least one surface of the polyester film before the crystal orientation is completed, and then the polyester film is stretched in at least one axial direction and heat-treated on the polyester film. The method for producing a laminated film according to any one of [I] to [VIII], which comprises the step of completing the crystal orientation of the polyester film.

The laminated film of the present invention is excellent in transparency, scratch resistance, and blocking resistance, can improve the transportability during the film processing process, and can suppress scratches on the film.

Hereinafter, the laminated film of the present invention will be described in detail.
The present invention is a laminated film having a polyester layer and a resin layer, in which a surface layer on at least one side is a resin layer, and the resin layer having the surface layer is determined by AFM (Atomic Force Microscope). A laminated film having a micro surface roughness (Ra-1) of 1 nm or more and 20 nm or less, and a macro surface roughness (Ra-2) obtained by a three-dimensional surface roughness meter of 1 nm or more and 50 nm or less.

The micro surface roughness in the present invention represents the roughness of the surface of the resin layer measured in a region of 10 μm × 10 μm using an AFM (Atomic Force Microscope) manufactured by BRUKER. This micro surface roughness is a property that affects the transparency and scratch resistance of the resin layer. Details of the measurement method will be described later.

When the micro surface roughness of the resin layer on the surface layer of the laminated film is 1 nm or more and 20 nm or less, the resin layer does not have large irregularities that scatter light, so that the transparency of the laminated film can be improved. it can. Further, since the resin layer is less likely to be caught, scratch resistance can be improved. More preferably, it is 1 nm or more and 15 nm or less. As a method of setting the micro surface roughness of the resin layer to 1 nm or more and 20 nm or less, a curable resin made of an acrylic resin having excellent fluidity is applied on a polyester layer having a micro surface roughness of 1 nm or more and 20 nm or less and cured. There are a method of forming a resin layer by allowing the resin layer to be formed, and a method of applying a curable resin made of an acrylic resin containing nanoparticles having an average particle diameter of 100 nm or less and curing the resin layer. Among these, a method of applying a curable resin made of an acrylic resin containing nanoparticles and having excellent fluidity and curing the resin is preferable from the viewpoint of excellent transparency.

The macro surface roughness in the present invention represents the roughness of the resin layer surface measured in a region of 400 μm × 900 μm using a three-dimensional roughness meter manufactured by Kosaka Laboratory. This macro surface roughness is a property that affects the anti-blocking property and transparency of the resin layer. Details of the measurement method will be described later.

When the macro surface roughness of the resin layer on the surface layer of the laminated film is in the region of 1 nm or more and 50 nm or less, the surface of the resin layer has a gentle uneven structure, so that the antiblocking property and transparency of the laminated film can be improved. it can. It is preferably 5 nm or more and 50 nm or less, and more preferably 5 nm or more and 30 nm or less. As a method of setting the macro surface roughness to 1 nm or more and 50 nm or less, a resin layer is formed by using a curable resin made of an acrylic resin, and the resin layer contains particles having an average particle diameter larger than the thickness of the resin layer. Method or after applying a curable resin made of acrylic resin, a mold having an uneven shape is transferred to a coating film in which the acrylic resin is still uncured, and then the acrylic resin is cured to form a resin layer. There are a so-called nanoimprint method, a method of applying a curable resin made of an acrylic resin, and then applying a stretching treatment to the resin layer in a state where the acrylic resin is not yet cured to give fine stretching unevenness. Among these, after applying a curable resin made of acrylic resin, the resin layer is stretched while the acrylic resin is still uncured to form a gentle uneven structure on the surface of the resin layer due to fine stretching unevenness. The method is preferable because it has excellent anti-blocking properties. Further, since it has a gentle uneven structure, it is preferable because it can suppress light scattering and is excellent in transparency.

Further, in the laminated film of the present invention, the ratio (Ra-2 / Ra-1) of the micro surface roughness (Ra-1) of the resin layer having the surface layer to the macro surface roughness (Ra-2) is 3 or more. When it is 30 or less, the anti-blocking property is improved, which is preferable. It is preferably 5 or more and 25 or less, and more preferably 5 or more and less than 10. The ratio (Ra-2 / Ra-1) of the micro surface roughness (Ra-1) to the macro surface roughness (Ra-2) is achieved by adjusting the average particle size of the particles contained in the resin layer. be able to. Specifically, when the average particle size of the particles contained in the resin layer is increased, both the micro surface roughness (Ra-1) and the macro surface roughness (Ra-2) tend to increase. In particular, since the macro surface roughness (Ra-2) is the surface roughness in a wide field of view, when the average particle diameter of the particles contained in the resin layer is increased, the surface roughness is higher than that of the micro surface roughness (Ra-1). The numbers tend to be higher.

Further, in the laminated film of the present invention, the resin layer on the surface layer contains particles, and the range from the surface of the resin layer to the position of 10% of the thickness of the resin layer when observing the cross section of the resin layer in the thickness direction is observed. The particle abundance ratio (P-1) in the above is preferably larger than the particle abundance ratio (P-2) in the range from the position of 40% to the position of 60% of the resin layer thickness from the surface of the resin layer. By making (P-1) larger than (P-2), scratch resistance can be improved. When the ratio (P-1 / P-2) of (P-1) and (P-2) is 1.1 or more and 5.0 or less, scratch resistance is particularly improved, which is preferable. More preferably, it is 1.1 or more and 2.0 or less. As a method of making (P-1) larger than (P-2), a method of using particles having a small specific gravity as particles to be contained in the resin layer, or a method of modifying a low surface energy component such as fluorine or silicone is used. There is a method of arranging the particles on the air side by using the particles.

Further, in the laminated film of the present invention, when the thickness (t) of the resin layer on the surface layer is 100 nm or more, the influence of curing inhibition of the surface layer of the resin layer can be suppressed and scratch resistance is excellent, which is preferable. The upper limit of the thickness of the resin layer is not limited, but is preferably 5000 nm or less in terms of transparency and productivity. Further, it is more preferably 300 nm or more and 3000 nm, and further preferably 500 nm or more and 1500 nm.
Further, in the laminated film of the present invention, the average particle size (d) of the particles contained in the resin layer on the surface layer is 1 nm or more and 100 nm or less, and the thickness (t) of the resin layer and the average particle size of the nanoparticles ( When the ratio (t) / (d) to d) is 2 or more and 1000 or less, the diffusion of light by the particles is suppressed and the transparency of the laminated film is improved, which is preferable. More preferably, it is 2 or more and 100 or less. The above range can be achieved by designing the film thickness of the resin layer and the average particle size of the particles contained in the resin layer.

[acrylic resin]
In the laminated film of the present invention, the resin layer on the surface layer preferably contains an acrylic resin. In particular, it is preferable to contain an acrylic resin (A) and / or an acrylic resin (F) and / or an acrylic resin (G) described later. By using the acrylic resin (A) and / or the acrylic resin (F) and / or the acrylic resin (G), the hardness of the surface of the resin layer can be improved while maintaining the transparency. As a result, it is possible to improve the scratch resistance of the laminated film.

The acrylic resin (A) in the present invention is a cured composition composed of a monomer component (a) having an acryloyl group in the molecule. Among these, the monomer component (a) is preferably a polyfunctional acrylate having three or more acrylic loyl groups in the molecule. The polyfunctional acrylate is a monomer or oligomer having 3 (more preferably 4, more preferably 5 or more) (meth) acryloyl groups in one molecule. Examples of such a composition include compounds in which a polyhydric alcohol having three or more alcoholic hydroxyl groups in one molecule is an esterified product of three or more (meth) acrylic acids. it can.

Specific examples include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, and dipentaerythritol tetra (meth) acrylate. Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylpropantri (meth) acrylate, pentaerythritol triacrylate hexanemethylene diisosianto urethane polymer and the like can be used. These monomers can be used alone or in admixture of two or more. In addition, commercially available polyfunctional acrylic compositions include Mitsubishi Rayon Co., Ltd .; (trade name "Diabeam" (registered trademark) series, etc.), Nagase Sangyo Co., Ltd .; (trade name "Denacol" (registered trademark) series). , Shin-Nakamura Co., Ltd .; (trade name "NK ester" series, etc.), Dainippon Ink and Chemicals Co., Ltd .; (trade name "UNIDIC" (registered trademark), etc.), Toa Synthetic Chemical Industry Co., Ltd .; ("Aronix" "(Registered trademark) series, etc.), Nippon Yushi Co., Ltd .; (" Blemmer "(registered trademark) series, etc.), Nippon Kayaku Co., Ltd .; (Product name" KAYARAD "(registered trademark) series, etc.), Kyoeisha Chemical Co., Ltd. ; (Product name "Light ester" series, etc.) can be mentioned, and these products can be used.

In the present invention, it is preferable to use the acrylic resin (A) obtained by using the acrylic monomer component having an amide bond as the acrylic resin (A) because the scratch resistance is particularly improved. The present inventors presume that the reason for this is as follows. When the acrylic monomer component having an acryloyl group is cured in the presence of oxygen atoms in the atmosphere, the radical polymerization reaction of the acryloyl group may be inhibited by the oxygen atoms in the atmosphere, and as a result, the reaction may be inhibited. Curing may not be sufficient and scratch resistance may be poor. When the acrylic monomer component containing an acryloyl group has an amide bond, the oxygen atom in the atmosphere interacts with the highly polar amide bond, so that the inhibition of curing of the radical polymerization reaction of the acryloyl group by oxygen in the atmosphere is suppressed. As a result, it is estimated that the acrylic resin is cured and the scratch resistance is particularly improved. Examples of the acrylic monomer component having an amide bond include compounds having a structure represented by the following (Formula 1).

The acrylic resin (F) in the present invention is a resin having a monomer unit (f ₃ ) represented by (formula 2).

((Formula 2), R ₃ radicals represents a hydrogen atom or a methyl group. Also, R ₅ groups are hydroxyl, carboxyl, tertiary amino groups, quaternary ammonium salt, a sulfonic acid group or a phosphoric acid Represents a group.)













R ₅ groups in (Equation 2), a hydroxyl group, a carboxyl group, a tertiary amino group, quaternary ammonium group, sulfonic acid group, a phosphoric acid group, the use of an acrylic resin having both no monomer units, acrylic resin Is not preferable because the compatibility of the acrylic resin (F) with the aqueous solvent is insufficient and the acrylic resin (F) is non-uniformly present in the resin composition, resulting in poor scratch resistance in a part of the resin layer.

Further, as the inorganic particles (B) described later aggregate or settle, or the inorganic particles (B) aggregate in the drying step, the pressure on the resin layer when scraped is locally increased, resulting in a resin. Layers may be destroyed, leading to scratches.

Further, since such an agglomerate is larger than the wavelength of visible light, it may not be possible to obtain a laminated film having good transparency. In order for the acrylic resin (F) in the present invention to have the monomer unit (f ₃ ) represented by the following (formula 2), the (meth) acrylate monoma (f ₃ ') represented by (formula 3) It is necessary to polymerize using the above as a raw material.

The following compounds are exemplified as the (meth) acrylate monomer (f ₃ ') represented by (formula 3).

Examples of the (meth) acrylate monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2,3-dihydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and polyethylene. Examples thereof include a monoesterified product of a polyhydric alcohol such as glycol mono (meth) acrylate and (meth) acrylic acid, or a compound obtained by ring-opening polymerization of ε-caprorapton on the monoesterified product, and in particular, 2-hydroxyethyl ( Meta) acrylate and 2-hydroxypropyl (meth) acrylate are preferable.

Examples of the (meth) acrylate monomer having a carboxyl group include α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, fumaric acid, and maleic acid, or hydroxyalkyl (meth) acrylates and acid anhydrides. Acrylic acid and methacrylic acid are particularly preferable.

Examples of the tertiary amino group-containing monomer include N, N-, such as N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, and the like. N, N-dialkylamino such as dialkylaminoalkyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide Examples thereof include alkyl (meth) acrylamide, and N, N-dimethylaminoethyl (meth) acrylate is particularly preferable.

The quaternary ammonium base-containing monomer is preferably one obtained by allowing a quaternary agent such as epihalohydrin, benzyl halide, or alkyl halide to act on the tertiary amino group-containing monomer, and specifically, 2- (methacryloyloxy). ) Ethyltrimethylammonium chloride, 2- (methacryloyloxy) ethyltrimethylammonium bromide, 2- (methacryolioxy) ethyltrimethylammonium dimethyl phosphate and other (meth) acryloyloxyalkyltrialkylammonium salts, methacryloylaminopropyltrimethylammonium chloride, methacryloyl (Meta) acryloylaminoalkyltrialkylammonium salts such as aminopropyltrimethylammonium bromide, tetraalkyl (meth) acrylates such as tetrabutylammonium (meth) acrylate, trialkylbenzylammonium (meth 9) such as trimethylbenzylammonium (meth) acrylate Examples thereof include acrylate, and 2- (methacryloyloxy) ethyltrimethylammonium chloride is particularly preferable.

Examples of the sulfonic acid group-containing monomer include (meth) acrylamide-alkanesulfonic acid such as butylacrylamide sulfonic acid and 2-acrylamide-2-methylpropanesulfonic acid, and sulfoalkyl (meth) such as 2-sulfoethyl (meth) acrylate. Examples thereof include acrylate, and 2-sulfoethyl (meth) acrylate is particularly preferable.

Examples of the phosphoric acid group-containing acrylic monomer include acid phosphooxyethyl (meth) acrylate, and acid phosphooxyethyl (meth) acrylate is particularly preferable.
Among this, particularly an acrylic resin (F), wherein a resin having a monomer unit represented by formula (2) (f _3), that R ₅ groups in (Equation 2), a hydroxyl group, a carboxyl group It is preferable in that it has a higher adsorption force with the inorganic particles (B) described later, can form a stronger film, and has improved scratch resistance. As a method of using the acrylic resin (F) to make the macro surface roughness 1 nm or more and 50 nm or less, a method of giving fine stretching unevenness by applying a stretching treatment to the resin layer while the acrylic resin is still uncured. At this time, it is important that the thickness of the resin layer is 300 nm or more. By setting the thickness as described above, fine stretching unevenness develops an appropriate height, and anti-blocking property can be improved.

In the present invention, the content of the acrylic resin in the resin layer is preferably 10 to 90% by weight, and the scratch resistance of the resin layer can be improved by setting the content in this range.
In particular, when the acrylic resin (A) is used as the acrylic resin, the content of the acrylic resin (A) is more preferably 40% by weight or more and 90% by weight or less with respect to the entire resin layer, and is preferably in the resin layer. The content of the acrylic resin (A) in the above is preferably 40% by weight or more and 80% by weight or less, and more preferably 45% by weight or more and 70% by weight or less.
When the acrylic resin (F) is used as the acrylic resin, the content of the acrylic resin (F) in the resin layer is preferably 20% by weight or more and 80% by weight or less with respect to the entire resin layer, which is more preferable. Is 40% by weight or more and 80% by weight or less, more preferably 45% by weight or more and 70% by weight or less.
In the present invention, the content in the resin layer represents the content in the solid content ([(mass of resin composition) − (mass of solvent)]) of the resin composition forming the resin layer.

[Inorganic particles]
In the laminated film of the present invention, it is preferable that the resin layer on the surface layer contains inorganic particles (B). Examples of the inorganic particles (B) include fine particles such as silicon oxide (silica), titanium oxide, aluminum oxide, zinc oxide, tin oxide, and zirconium oxide. Among these, fine particles of silicon oxide (silica), titanium oxide, aluminum oxide, zinc oxide, tin oxide, and zirconium oxide are preferable. One of these may be used alone, or two or more thereof may be used in combination.
Further, the inorganic particles (B) of the present invention are a composition (B-2) formed by binding the inorganic particles (B-1) and a resin component containing an acryloyl group, or the inorganic particles (B-1). It is preferable that the composition (B-3) has an acrylic resin (G) on a part or all of the surface of the above. The bond referred to here may be a covalent bond or a non-covalent bond (physical adsorption).

As an example of the resin composition (B-2) in which the inorganic particles (B-1) and the resin component containing an acryloyl group are bonded, the inorganic particles (B-1) and the resin component containing an acryloyl group are bonded (surface). It can be mentioned that it is modified). By binding the inorganic particles (B-1) and the resin component containing an acryloyl group, it is possible to suppress the removal of the inorganic particles when a force is applied to the resin layer, and it is possible to improve the scratch resistance.

As a specific method for binding the inorganic particles (B-1) and the resin component containing an acryloyl group, the resin component containing an acryloyl group is a resin component having a silanol group or a resin component that produces a silanol group by hydrolysis. Is preferable.

Next, the resin component containing an acryloyl group contained in the resin composition (B-2) containing the inorganic particles (B) will be described. The resin component containing an acryloyl group is a compound having an acryloyl group and a hydrolyzable silyl group. The hydrolyzable silyl group is one that reacts with water to form a silanol group, and for example, silicon has one or more methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group and the like. It refers to a group in which an alkoxy group, an aryloxy group, an acetoxy group, an amino group, or a halogen primitive is bonded.

The particles formed by binding the inorganic particles (B-1) and the resin component containing an acryloyl group are obtained by mixing the resin component (B-2) containing an acryloyl group having a hydrolyzable silyl group with the inorganic particles (B-1). It can be obtained by hydrolyzing and combining the two. Since the particles thus obtained react with the acrylic resin (A), the inorganic particles are less likely to fall off when the resin layer is rubbed, so that the scratch resistance becomes excellent.

The ratio of the resin component containing the inorganic particles (B-1) and the acryloyl group contained in the resin composition (B-2) containing the inorganic particles (B) is the resin containing the inorganic particles (B-1) and the acryloyl group. When the component is 100 parts by weight, the resin component (B-2) containing an acryloyl group is preferably 0.1 part by weight or more and 50 parts by weight or less. Within this range, scratch resistance, transparency, and anti-blocking property can be achieved at the same time without the inorganic particles falling off. If the resin component containing an acryloyl group exceeds 50 parts by weight, the density of the inorganic particles contained in the resin layer may decrease, and the scratch resistance may deteriorate.

Further, the composition (B-3) having an acrylic resin (G) on a part or all of the surface of the inorganic particles (B-1) of the present invention is a part or all of the surface of the inorganic particles (B-1). In addition, it is preferable that the particles have the acrylic resin (G) described above.
The acrylic resin (G) referred to here is a resin having a monomer unit (g ₁ ) represented by (formula 4) and a monomer unit (g ₂ ) represented by (formula 5).

(In (Equation 4), _one R group represents a hydrogen atom or a methyl group, and n represents an integer of 9 or more and 34 or less).

((Formula 5), R ₂ radical represents a hydrogen atom or a methyl group. Also, R ₄ groups represent two or more group containing saturated carbocyclic ring.).

Here, the acrylic resin (G) in the present invention is preferably a resin having a monomer unit (g ₁ ) represented by (Formula 4). Since the acrylic resin (G) has the monomer unit (g ₁ ) represented by (Equation 4), the surface energy of the resin layer is lowered, so that the friction coefficient applied to the resin layer when the scratch treatment is applied is small. Therefore, scratch resistance can be improved.

Further, in (Formula 4), when an acrylic resin having a monomer unit in which n is less than 9 is used, the dispersibility of the inorganic particles (B) in an aqueous solvent (details of the aqueous solvent will be described later) is unstable. It becomes. When an acrylic resin having a monomer unit in which n is less than 9 in (Formula 4) is used, the inorganic particles (B) may aggregate or settle in the resin composition, or the inorganic particles (B) may aggregate in the drying step. Sometimes. As a result, the transparency of the laminated film may be impaired or the scratch property may be inferior. On the other hand, the acrylic resin having a monomer unit in which n exceeds 34 in (Formula 4) has extremely low solubility in an aqueous solvent, so that the acrylic resin tends to aggregate in the aqueous solvent. Since such aggregates are larger than the wavelength of visible light, it may not be possible to obtain a laminated film having good transparency.

In order for the acrylic resin (G) in the present invention to have the monomer unit (g ₁ ) represented by (Formula 4), the (meth) acrylate monomer (g ₁ ') represented by the following (Formula 6) It is necessary to polymerize using the above as a raw material.

As the (meth) acrylate monomer (g ₁ '), a (meth) acrylate monomer in which n in (Formula 6) is represented by an integer of 9 or more and 34 or less is preferable, and more preferably 11 or more and 32 or less (meth). An acrylate monomer, more preferably 13 or more and 30 or less (meth) acrylate monomer.

The (meth) acrylate monomer (g ₁ ') is not particularly limited as long as it is a (meth) acrylate monomer in which n in (Formula 6) is 9 or more and 34 or less, but specifically, decyl (meth) acrylate and dodecyl (meth) Meta) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, 1-methyltridecyl (meth) acrylate, hexadecyl (meth) acrylate, octadecyl (meth) acrylate, eikosyl (meth) acrylate, docosyl (meth) acrylate, Examples thereof include tetracosyl (meth) acrylate and tridecyl (meth) acrylate, and dodecyl (meth) acrylate and tridecyl (meth) acrylate are particularly preferable. These may be used alone or in admixture of two or more.

Further, the acrylic resin (G) in the present invention is preferably a resin having a monomer unit (g ₂ ) represented by the above (formula 5). When the acrylic resin (G) has the monomer unit (g ₂ ) represented by (Equation 5), the resin layer becomes rigid due to the influence of the steric hindrance of the saturated carbon ring, and the scratch resistance can be improved. ..

Further, in (Formula 5), if an acrylic resin having a monomer unit containing only one saturated carbon ring is used, the function as a steric hindrance becomes insufficient, and the inorganic particles (B) are aggregated or aggregated in the resin composition. Inorganic particles (B) may settle or aggregate in the drying step.

Since such aggregates are larger than the wavelength of visible light, it may not be possible to obtain a laminated film having good transparency. In order for the acrylic resin (G) in the present invention to have the monomer unit (g ₂ ) represented by (formula 5), the (meth) acrylate monomer (g ₂ ') represented by the following (formula 7) It is necessary to polymerize using the above as a raw material.

The (meth) acrylate monomer (g ₂ ') represented by (Formula 7) has a crosslinked condensed ring type (two or more rings each share two atoms and have a bonded structure). , Spiro ring type (having a structure in which one carbon atom is shared and two cyclic structures are bonded) and various cyclic structures, specifically, compounds having bicyclo, tricyclo, tetracyclo group and the like can be exemplified. Among them, (meth) acrylate containing a bicyclo group is particularly preferable from the viewpoint of compatibility with the binder.

Examples of the (meth) acrylate containing a bicyclo group include isobonyl (meth) acrylate, bornyl (meth) acrylate, disiroclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, adamantyl (meth) acrylate, and dimethyladamantyl. Examples thereof include (meth) acrylate, and isovonyl (meth) acrylate is particularly preferable.
By having the acrylic resin (G) on the surface of the inorganic particles (B-1), the interfacial adhesion between the inorganic particles (B-1) and the acrylic resin (G) in the resin layer is strengthened, so that the scraping treatment can be performed. Particles are suppressed from falling off when applied, and it has excellent scratch resistance. Further, it is possible to suppress the aggregation of the inorganic particles (B) in the drying process and to set the micro surface roughness and the macro surface roughness of the resin layer within a predetermined range.

The method for producing the inorganic particles (B-1) is not particularly limited, and specific examples thereof include a method of surface-treating the inorganic particles (B-1) with an acrylic resin (G). Is exemplified by the following methods (i) to (iv). In the present invention, the surface treatment refers to a treatment of adsorbing and adsorbing the acrylic resin (G) on all or part of the surface of the inorganic particles (B-1).

(I) A method in which a mixture in which inorganic particles (B-1) and acrylic resin (F) are mixed in advance is added to a solvent and then dispersed.

(Ii) A method in which inorganic particles (B-1) and acrylic resin (G) are sequentially added and dispersed in a solvent.

(Iii) A method in which inorganic particles (B-1) and acrylic resin (G) are dispersed in advance in a solvent, and the obtained dispersion is mixed.

(Iv) A method in which inorganic particles (B-1) are dispersed in a solvent, and then an acrylic resin (G) is added to the obtained dispersion.

The desired effect can be obtained by any of these methods.

Further, as a device for performing dispersion, a dissolver, a high speed mixer, a homo mixer, a meador, a ball mill, a roll mill, a sand mill, a paint shaker, an SC mill, an annual type mill, a pin type mill and the like can be used.

Further, as a dispersion method, the rotation shaft is rotated at a peripheral speed of 5 to 15 m / s by using the above device. The rotation time is 5 to 10 hours.

Further, it is more preferable to use dispersed beads such as glass beads at the time of dispersion in terms of enhancing dispersibility. The bead diameter is preferably 0.05 to 0.5 mm, more preferably 0.08 to 0.5 mm, and particularly preferably 0.08 to 0.2 mm.

As a method of mixing and stirring, the container can be shaken by hand, a magnetic stirrer or a stirring blade can be used, ultrasonic irradiation, vibration dispersion, or the like can be performed.

The presence or absence of adsorption / adhesion of the acrylic resin (G) on all or part of the surface of the inorganic particles (B-1) can be confirmed by the following analysis method. The object to be measured (for example, the composition (B-3) containing the inorganic particles (B-1)) is centrifuged by a Hitachi desktop ultracentrifuge (manufactured by Hitachi Koki Co., Ltd .: CS150NX) (rotation speed 3,). After sedimenting the inorganic particles (B-1) (and the acrylic resin (G) adsorbed on the surface of the inorganic particles (B-1)) at 0000 rpm, separation time 30 minutes), the supernatant liquid is removed to remove the sediment. Concentrate and dry. The concentrated and dried sediment is analyzed by X-ray photoelectron spectroscopy (XPS) to confirm the presence or absence of acrylic resin (F) on the surface of the inorganic particles (B-1). When it is confirmed that 1% by mass or more of the acrylic resin (G) is present on the surface of the inorganic particles (B-1) with respect to 100% by mass of the total of the inorganic particles (B-1), the inorganic particles (B-1) are present. It is assumed that the acrylic resin (G) is adsorbed and adhered to the surface of -1).

Here, the number average particle diameter of the inorganic particles (B-1) will be described. Here, the number average particle diameter means a particle diameter determined by a transmission electron microscope (TEM). The magnification is set to 500,000 times, and the outer diameter of the 10 particles existing on the screen is the number average particle diameter obtained by measuring a total of 100 particles in 10 fields of view. Here, the outer diameter represents the maximum diameter of the particle (that is, the major diameter of the particle and indicates the longest diameter in the particle), and similarly, in the case of a particle having a cavity inside, the maximum diameter of the particle is used. Represent.

When the number average particle diameter of the inorganic particles (B) is smaller than 1 nm, the van der Waals force between the particles increases, and as a result of the particles agglutinating, light scattering may occur and the transparency may decrease. On the other hand, when the number average particle diameter of the inorganic particles (B) is larger than 100 nm, from the viewpoint of transparency, there is a possibility that the light becomes a starting point for scattering and the transparency deteriorates. In addition, the filling of the inorganic particles in the coating film may not proceed sufficiently, and the scratch resistance may decrease. Therefore, the inorganic particles (B) preferably have a number average particle diameter of 5 nm or more and 100 nm or less. It is preferably 10 nm or more and 80 nm or less, and more preferably 20 nm or more and 60 nm or less.

In the present invention, the inorganic particles (B) contained in the resin layer (X) are preferably in the range of 10 to 50 parts by weight, more preferably in the range of 15 to 50 parts by weight, based on 100 parts by weight of the acrylic resin (A). Is more preferable. Within the above range, both transparency and scratch resistance can be achieved.
Further, in the present invention, the amount of the inorganic particles (B) contained in the resin layer (X) is preferably in the range of 50 to 200 parts by weight with respect to a total of 100 parts by weight of the acrylic resin (F) and the acrylic resin (G). More preferably, the range is 100 to 200 parts by weight. Within the above range, both transparency and scratch resistance can be achieved.

[Polyester layer]
In the laminated film of the present invention, a polyester layer used as a base material layer (hereinafter, the polyester layer used as a base material layer may be referred to as a polyester film) will be described. First, polyester is a general term for polymers having an ester bond in the main chain, and is ethylene terephthalate, propylene terephthalate, ethylene-2,6-naphthalate, butylene terephthalate, propylene-2,6-naphthalate, ethylene-α, β. Those having at least one constituent selected from −bis (2-chlorophenoxy) ethane-4,4′-dicarboxylate and the like can be preferably used.

The polyester film using the polyester is preferably biaxially oriented. The biaxially oriented polyester film is generally a polyester sheet or film in an unstretched state, which is stretched about 2.5 to 5 times in the longitudinal direction and the width direction orthogonal to the longitudinal direction, respectively, and then heat-treated to crystallize. Orientation is completed and shows a biaxial orientation pattern by wide-angle X-ray diffraction. When the polyester film is biaxially oriented, thermal stability, particularly dimensional stability and mechanical strength, is sufficient, and flatness is also good.

In addition, various additives such as antioxidants, heat-resistant stabilizers, weather-resistant stabilizers, ultraviolet absorbers, organic lubricants, pigments, dyes, organic or inorganic fine particles, fillers, and antistatic agents are contained in the polyester film. Agents, nucleating agents and the like may be added to such an extent that the characteristics are not deteriorated.

The thickness of the polyester film is not particularly limited and is appropriately selected depending on the application and type, but is usually preferably 10 to 500 μm, more preferably 15 to 250 μm from the viewpoint of mechanical strength, handleability and the like. Most preferably, it is 20 to 100 μm. Further, the polyester film may be a composite film obtained by co-extrusion, or may be a film obtained by laminating the obtained films by various methods.

[Manufacturing method of resin layer]
An example of the method for producing the resin layer of the laminated film of the present invention is shown below, but the materials, amounts used, proportions, treatment contents, treatment procedures, etc. shown below may be appropriately changed as long as the gist of the present invention is not deviated. it can. Therefore, the scope of the present invention should not be construed as limited by the examples shown below.

When the resin layer of the present invention contains an acrylic resin selected from at least one of an acrylic resin (A) and / or an acrylic resin (F) and inorganic particles (B), the transparency and scratch resistance of the resin layer, It has excellent anti-blocking properties and is preferable.

Further, in the resin layer, if necessary, compounds other than (A), (F) and (B), for example, polymer resins such as polyester resin, acrylic resin and urethane resin, carbodiimide compounds and oxazoline compounds , Aziridine compounds, titanate-based coupling agents such as titanium chelate, and methylolated or alkyrylated melamine compounds may be contained. Further, various additives such as an organic lubricant, organic or inorganic fine particles, an antistatic agent and the like may be added to such an extent that the characteristics are not deteriorated.

In particular, as the compounds other than (A), (F) and (B), an oxazoline compound and / or a melamine compound are preferable, and a melamine compound is particularly preferable.

Examples of the melamine-based compound include melamine, a methylolated melamine derivative obtained by condensing melamine and formaldehyde, a compound obtained by reacting methylolated melamine with a lower alcohol to partially or completely etherify, and a mixture thereof. Can be used. Specifically, a compound having a triazine and a methylol group is particularly preferable. Further, the melamine compound may be a condensate composed of a monomer, a dimer or a multimer or more, or a mixture thereof. As the lower alcohol used for etherification, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butanol, isobutanol and the like can be used. The group has an imino group, a methylol group, or an alkoxymethyl group such as a methoxymethyl group or a butoxymethyl group in one molecule, and is an imino-based methylated melamine resin, a methylol-based melamine resin, or a methylol-based methyl. Chemical melamine resin, fully alkyl-type methylated melamine resin, etc. Of these, methylolated melamine resin is most preferable. Further, in order to promote the thermosetting of the melamine compound, an acidic catalyst such as p-toluenesulfonic acid may be used.

When such a melamine-based compound is used, not only the scratch resistance is improved by increasing the coating hardness due to the self-condensation of the melamine-based compound, but also the reaction between the hydroxyl group or carboxylic group contained in the acrylic resin and the melamine-based compound proceeds. , A stronger resin layer can be obtained, and a film having excellent scratch resistance can be obtained. Furthermore, due to the effect of suppressing the falling off of the inorganic particles (B) in the resin layer, it is possible to prevent scraping of the convex portion of the uneven structure required for exhibiting antiblocking property.

[Manufacturing method of laminated film]
The method for producing the laminated film of the present invention will be described below with an example, but the materials, amounts used, proportions, treatment contents, treatment procedures, etc. shown below may be appropriately changed without departing from the spirit of the present invention. it can. Therefore, the scope of the present invention should not be construed as limited by the examples shown below.

In the laminated film of the present invention, the acrylic monomer (a) constituting the acrylic resin (A) and the resin composition (b) containing the inorganic particles (B) are applied onto the polyester film, and the resin composition acts as a solvent. When it is contained, it can be obtained by forming a resin layer on the polyester film by drying the solvent.
When the acrylic monomer (f) constituting the acrylic resin (F) and the resin composition (b) containing the inorganic particles (B) are applied onto the polyester film, and the resin composition contains a solvent, It can be obtained by forming a resin layer on the polyester film by drying the solvent.

Further, in the present invention, when the resin composition contains a solvent, it is preferable to use an aqueous solvent as the solvent. This is because the use of an aqueous solvent can suppress rapid evaporation of the solvent in the drying step, can form a uniform composition layer, and is excellent in terms of environmental load.

Here, the aqueous solvent is soluble in water or water and alcohols such as methanol, ethanol, isopropyl alcohol and butanol, ketones such as acetone and methyl ethyl ketone, and glycols such as ethylene glycol, diethylene glycol and propylene glycol. Refers to a mixture of organic solvents that are in an arbitrary ratio.

Further, in the present invention, when an aqueous solvent is used, it contains an acrylic monomer (a) constituting the acrylic resin (A), an acrylic monomer (f) constituting the acrylic resin (F), and inorganic particles (B). It is preferable to apply a water-based coating agent containing the resin composition (b). By applying this as a water-based coating agent, the water dispersant or emulsifier is arranged on the surface layer of the coating film when the solvent is dry, as compared with the organic solvent-based coating agent. This is because the inhibition of curing is suppressed, and even if the thickness of the resin layer is thin, the scratch resistance is excellent.

As a method for water-based coating of the acrylic monomer (a) constituting the acrylic resin (A) and the resin composition (b) containing the inorganic particles (B), the acrylic constituting the acrylic resin (A) is used. Examples thereof include a method of impregnating a resin composition (b) containing a monomer (a) and an inorganic particle (B) with a hydrophilic group such as a carboxylic acid or a sulfonic acid, and a method of emulsifying with an emulsifier.

The method of applying the resin composition to the polyester film is preferably an in-line coating method. The in-line coating method is a method of coating in the process of manufacturing a polyester film. Specifically, it refers to a method in which a polyester resin is applied at an arbitrary stage from melt extrusion to biaxial stretching and then heat treatment and winding, and is usually obtained by melt extrusion and quenching, which is substantially non-existent. A crystalline unstretched (unaligned) polyester film (A film), then a uniaxially stretched (uniaxially oriented) polyester film (B film) stretched in the longitudinal direction, or a biaxially stretched film in the width direction before heat treatment. It is applied to any film of stretched (biaxially oriented) polyester film (C film).

In the present invention, the resin composition is applied to the polyester film of any of the above A film and B film before the crystal orientation is completed, and then the polyester film is stretched in the uniaxial direction or the biaxial direction to obtain a solvent. It is preferable to adopt a method of performing heat treatment at a temperature higher than the boiling point to complete the crystal orientation of the polyester film and providing a resin layer. According to this method, the formation of the polyester film and the coating and drying of the resin composition (that is, the formation of the resin layer) can be performed at the same time, which is advantageous in terms of manufacturing cost. In addition, it is easy to make the thickness of the resin layer thinner in order to perform stretching after coating.

Among them, a method in which a resin composition is applied to a film (B film) uniaxially stretched in the longitudinal direction, then stretched in the width direction, and heat-treated is excellent. Compared to the method of biaxial stretching after coating on an unstretched film, the stretching step is one less, so that defects and cracks in the composition layer are less likely to occur due to stretching, and a composition layer having excellent transparency and smoothness can be obtained. This is because it can be formed.

Further, by providing the resin layer by the in-line coating method, the resin layer can be stretched before the resin layer is completely cured, and a gentle uneven structure can be easily formed. Further, the uneven structure can form a more remarkable uneven structure when the thickness of the resin layer is 300 nm or more. As a result, the anti-blocking property of the film can be exhibited without forming large protrusions on the resin layer. This gentle uneven structure means that the macro surface roughness measured using a three-dimensional roughness meter manufactured by Kosaka Research Institute is 5 to 50 nm.

In the present invention, the resin layer is preferably provided by the in-line coating method because of the various advantages described above. Here, as a method for applying the resin composition to the polyester film, any known application method such as a bar coating method, a reverse coating method, a gravure coating method, a die coating method, or a blade coating method can be used.

Therefore, the best method for forming a resin layer in the present invention is a method in which a resin composition using an aqueous solvent is applied onto a polyester film by an in-line coating method, dried, and heat-treated. A more preferable method is to in-line coat the resin composition on the B film after uniaxial stretching. In the method for producing a laminated film of the present invention, drying can be carried out in a temperature range of 80 to 130 ° C. in order to complete the removal of the solvent of the resin composition. Further, the heat treatment can be carried out in a temperature range of 160 to 240 ° C. in order to complete the crystal orientation of the polyester film and the thermosetting of the resin composition to complete the formation of the resin layer.

Next, the method for producing the laminated film of the present invention will be described by taking as an example a case where a polyethylene terephthalate (hereinafter referred to as PET) film is used as the polyester film, but the present invention is not limited thereto. First, the PET pellets are sufficiently vacuum-dried, then supplied to an extruder, melt-extruded into a sheet at about 280 ° C., and cooled and solidified to prepare an unstretched (unoriented) PET film (A film). This film is stretched 2.5 to 5.0 times in the longitudinal direction with a roll heated to 80 to 120 ° C. to obtain a uniaxially oriented PET film (B film). The resin composition of the present invention prepared to a predetermined concentration is applied to one side of this B film.

At this time, the coated surface of the PET film may be subjected to surface treatment such as corona discharge treatment before coating. By performing a surface treatment such as a corona discharge treatment, the wettability of the resin composition to the PET film is improved, the resin composition is prevented from being repelled, and a resin layer having a uniform coating thickness can be formed. After coating, the end portion of the PET film is gripped with a clip and led to a heat treatment zone (preheating zone) at 80 to 130 ° C., and the solvent of the resin composition is dried. After drying, it is stretched 1.1 to 5.0 times in the width direction. Subsequently, the mixture is led to a heat treatment zone (heat fixing zone) at 160 to 240 ° C. and heat-treated for 1 to 30 seconds to complete the crystal orientation.

In this heat treatment step (heat fixing step), a relaxation treatment of 3 to 15% may be performed in the width direction or the longitudinal direction, if necessary. The laminated film thus obtained becomes a laminated film having excellent transparency, scratch resistance, and anti-blocking property.

In the laminated film of the present invention, an intermediate layer may be provided between the resin layer and the polyester layer, but when the intermediate layer is provided, the film in which the intermediate layers are laminated may be wound up or thereafter according to the present invention. The film may be scratched in the process of providing the resin layer. Therefore, in the present invention, it is preferable that the resin layer and the polyester layer are directly laminated.

[Measurement method of characteristics and evaluation method of effect]
The method for measuring the characteristics and the method for evaluating the effect in the present invention are as follows.

(1) Haze (transparency)
The haze is measured in a normal state (23 ° C., relative humidity 50%) after leaving the laminated film sample for 40 hours, and then using a turbidity meter "NDH5000" manufactured by Nippon Denshoku Kogyo Co., Ltd., JIS K 7136 "Transparent". The method was based on "How to find the haze of materials" (2000 edition). The measurement was performed by irradiating light from the surface side on which the resin layers of the sample were laminated. As the sample, 10 square samples having a side of 50 mm were prepared, and the average value measured 10 times in total was taken as the haze value of the sample.
In addition, transparency was evaluated on a 4-point scale based on the haze value. X is a practically problematic level, Δ is a practical level, and A and S are good.
S: 0.6% or less A: More than 0.6% and 1.0% or less B: More than 1.0% and 2.0% or less C: More than 2.0%.

(2) Scratch resistance Steel wool (Bonster # 0000, manufactured by Nippon Steel Wool Co., Ltd.) was rubbed 10 times with a load of 200 g / cm ² and visually checked for scratches on the surface of the laminated film. Evaluation was carried out.
S: No scratches A: 1 to 5 scratches B: 6 to 10 scratches C: 11 or more scratches.

(3) Antiblocking property The resin layers of the laminated film were bonded to each other, pressurized with a load of 1 kg / cm2, and stored at room temperature for 24 hours. After that, the presence or absence of film blocking (sticking) when the laminated film was peeled off was visually confirmed, and the following evaluation was carried out.
A: No blocking B: Partially blocking C: Fully blocking (4) Adhesive Put 100 1mm ² crosscuts on the resin layer side of the laminated film, "Cellotape" (registered trademark) (manufactured by Nichiban Co., Ltd.) , CT405AP) was attached and pressed with a hand roller at a load of 1.5 kg / cm ² , and then rapidly peeled off from the laminated film in the 90 degree direction. Adhesiveness was evaluated on a 4-point scale based on the number of remaining lattices. The evaluation was performed using the average value performed 10 times. C is a practically problematic level, B is a practical level, and A and S are good.
S: 90 to 100 remaining A: 80 to 89 remaining B: 50 to 79 remaining C: 0 to less than 50 remaining.

(5) Number average particle size of particles contained in the resin layer The number average particle size of particles contained in the resin layer was determined by observing the cross-sectional structure of the laminated film with a transmission electron microscope (TEM). The magnification was set to 500,000 times, and the outer diameters of the 10 particles existing in the screen were measured for a total of 100 particles in 10 fields of view, and the average particle diameter was determined. If 10 particles do not exist on the screen, observe another part under the same conditions, measure the outer diameter of the particles existing on the screen, and measure the outer diameter of 100 particles in total. Was taken as the average value. Here, the outer diameter represents the maximum diameter of the particle (that is, the major diameter of the particle and indicates the longest diameter in the particle), and similarly, in the case of a particle having a cavity inside, the maximum diameter of the particle is used. Represent.

(6) Thickness of Resin Layer The thickness of the resin layer on the polyester film was measured by observing the cross section using a transmission electron microscope (TEM). As for the thickness of the resin layer, the thickness of the resin layer was read from an image taken by TEM at a magnification of 100,000 times. A total of 20 resin layer thicknesses were measured and used as an average value.

Sample preparation: RuO ₄ staining FIB method
SMI3200SE (manufactured by SIINT Co., Ltd.)
FB-2000A II Micro Swimming System (manufactured by Hitachi, Ltd.)
Strata400S (manufactured by FEI)
Observation device: High-resolution transmission electron microscope (Hitachi H9000UHR II)
Observation conditions: Acceleration voltage 300 kV
(7) Micro surface roughness (Ra-1)
In the ScanAsystAir mode of AFM (Atomic Force Microscope) "Dimension Icon ScanAsyst" manufactured by BRUKER, the surface of the laminated film on the resin layer side is measured in a measurement range of 10 μm × 10 μm, the number of measurement lines is 512, and the measurement rate is 1. The arithmetic average roughness (Ra) was calculated from the surface information obtained by measuring at 0 Hz by the method specified in JIS-B-0601-1994. Specifically, "NanoScop Analysis" is used as software, "3rd" of "Flatten Order" is selected, and swell processing is performed in three dimensions. After that, "Roughness" is selected, and the numerical value described in "Image Ra" on the screen is used as the arithmetic mean roughness. In addition, the measurement was performed 10 times in total, and the average value of a total of 8 data excluding the maximum value and the minimum value was obtained as the arithmetic average roughness (Ra) of the sample as the micro surface roughness (Ra-1).

(8) Macro surface roughness (Ra-2)
The surface on the resin layer side of the laminated film is measured by the stylus method using a three-dimensional surface roughness meter (ET-4000A, manufactured by Kosaka Laboratory) under the following conditions, and the obtained center line surface roughness (SRa) is determined. It was determined as the macro surface roughness (Ra-2).
For the measurement, the sampling location was changed, 10 samples were measured, and the average value of 8 points excluding the maximum value and the minimum value was adopted.
Needle diameter 0.5 (μmR)
Needle pressing pressure 100 (μN)
Vertical magnification 20000 (times)
Low frequency CUT OFF 200 (μm)
Wide area CUT OFF 0 (μm)
Measurement speed 100 (μm / s)
Measurement interval 1 (μm) in the X direction, 5 (μm) in the Y direction
Number of records 81 Hysteresis width 0.000 (μm)
Reference area 1 mm in the X direction and 0.4 mm in the Y direction.
(9) Particle abundance ratio For the cross-sectional TEM image (magnification 100,000 times) obtained by the method described in (6), use software (image processing software ImageJ / developer: American National Satellite Research Institute (NIH)). , The white balance was adjusted so that the brightest part and the darkest part fit in the 8-bit tone curve. Furthermore, the contrast was adjusted so that the black part (inorganic particles) could be clearly distinguished.

Next, in the obtained image, the ratio of the black portion in the range from the surface of the resin layer to the position of 10% of the thickness of the resin layer is the particle abundance ratio (P-1), and the position of 40% of the thickness of the resin layer from the surface of the resin layer. The ratio of the black portion in the range from to 60% was defined as the particle abundance ratio (P-2).

<Reference Example 1> An emulsion (EM-5) containing an acrylic monomer (a-1) constituting the acrylic resin (A) component.
In a flask equipped with a stirrer, 100 parts by weight of acrylic monomer (a-1) (dipentahexaacrylate (KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.)) and polyoxyethylene polycyclic phenyl ether sulfate as an emulsifier (Japanese emulsifier) 79 parts by weight of a 10% by weight aqueous solution of Newcol 707SF manufactured by Kao Corporation, 2.1 parts by weight of polyoxyethylene lauryl ether (Emulsifier 104P manufactured by Kao Corporation), and 128.9 parts by weight of ion-exchanged water were added and mixed by stirring. .. Then, while cooling in an ice bath, ultrasonic irradiation for 120 seconds was performed three times using an ultrasonic disperser (UH-600S manufactured by SMT) to obtain an emulsion.

Next, the above emulsion was miniaturized with a high-pressure homogenizer (Microfluitizer M110Y manufactured by Mizuho Kogyo Co., Ltd.) under a pressure of 70 MPa to obtain an acrylic monomer (a-1) -containing emulsion (EM-5). The solid content concentration of the emulsion (EM-5) is 30% by weight.

<Reference Example 2> Resin composition (b-2) containing inorganic particles (B)
While stirring 221 parts by weight of mercaptopropyltrimethoxysilane, 1 part by weight of dibutyltin dilaurylate, and 30 parts by weight of isophorone diisocyanate and 30 parts by weight of perfluoropolyetherdiol (FLOUROLINK D10H manufactured by Solvaisolexis) with respect to the solution consisting of methyl ethyl ketone. After dropping at 50 ° C. for 1 hour, the mixture was heated and stirred at 70 ° C. for 3 hours. To this, 549 parts by weight of a polyfunctional acrylate (“NK ester” A-TMM-3LM-N manufactured by Shin-Nakamura Chemical Co., Ltd.) was added dropwise at 30 ° C. for 1 hour, and then stirred at 60 ° C. for 10 hours. , Acryloyl group-containing particle modifier (b-1) is obtained.

Next, 50 parts by weight of the obtained acryloyl group-containing particle modifier (b-1), 50 parts by weight of a colloidal silica aqueous dispersion (Nissan Chemical "Snowtech OL" particle diameter 40 nm), 0.12 parts by weight of ion-exchanged water. , And 0.01 parts by weight of p-hydroxyphenyl monomethyl ether are stirred at 60 ° C. for 4 hours, 1.36 parts by weight of orthoatetate methyl ester is added, and the mixture is further heated and stirred at the same temperature for 1 hour. , A resin composition (b-2) containing an acryloyl group containing inorganic particles (B) was obtained.

<Reference Example 3> An emulsion (EM-1) containing an acrylic monomer (a-1) constituting an acrylic resin (A) component and a resin composition (b-2) containing inorganic particles (B).
A resin composition containing 80 parts by weight of acrylic monomer (a-1) (dipentahexaacrylate (KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.)) and an acryloyl group containing inorganic particles (B) in a flask equipped with a stirrer. (B-2) 20 parts by weight, 79 parts by weight of a 10% aqueous solution of polyoxyethylene polycyclic phenyl ether sulfate ester salt (Newcol 707SF manufactured by Nippon Emulsifier Co., Ltd.) as an emulsifier, and polyoxyethylene lauryl ether (manufactured by Kao Corporation). Emulgen 104P) 2.1 parts by weight was added, and 128.9 parts by weight of ion-exchanged water was added, and the mixture was stirred and mixed. Then, while cooling in an ice bath, ultrasonic irradiation for 120 seconds was performed three times using an ultrasonic disperser (UH-600S manufactured by SMT) to obtain an emulsion.

Next, the above emulsion is micronized under a pressure of 70 MPa with a high-pressure homogenizer (Microfluitizer M110Y manufactured by Mizuho Kogyo Co., Ltd.) to form an acrylic monomer (a-1) and inorganic particles (a-1) constituting the acrylic resin (A) component. An emulsion (EM-1) containing the resin composition (b-2) containing B) was obtained. The solid content concentration of the emulsion (EM-1) is 30% by weight.

<Reference Example 4> An emulsion (EM-2) containing an amide bond-containing acrylic monomer (a-2) constituting the acrylic resin (A) component and a resin composition (b-2) containing inorganic particles (B). )
In a flask equipped with a stirrer, 0.024 g of 2,6-di-t-butyl-p-cresol, 15 g of ethylene diol, and 12 g of 2.4-tolylene diisocyanate (“TORDY-100” manufactured by Mitsui Chemicals Polyurethane Co., Ltd.) And methyl ethyl ketone was charged, 0.080 g of dibutyltin dilaurylate was added, the temperature was raised to 60 ° C., and the mixture was heated for 1.5 hours. Next, the reaction mixture was cooled in a water bath, and 35 g of tetramethylolmethane triacrylate (“NK ester” A-TMM-3LM-N manufactured by Shin-Nakamura Chemical Co., Ltd.) was diluted with methyl ethyl ketone to a solid content concentration of 50% by mass. Was added. The temperature was raised to 60 ° C. and heated for 4 hours to obtain an acrylic monomer (a-2) represented by the general formula 1.
A resin containing 30 parts of dipentahexaacrylate (KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.), 50 parts by weight of the acrylic monomer (a-2) represented by the following formula 1, and inorganic particles (B) in a flask equipped with a stirrer. 20 parts by weight of the composition (b-2), 79 parts by weight of a 10% aqueous solution of polyoxyethylene polycyclic phenyl ether sulfate as an emulsifier (Newcol 707SF manufactured by Nippon Emulsifier Co., Ltd.), and polyoxyethylene lauryl ether (Kao Co., Ltd.) ) Emulsifier 104P) 2.1 parts by weight and 128.9 parts by weight of ion-exchanged water were added and mixed by stirring. Then, while cooling in an ice bath, ultrasonic irradiation for 120 seconds was performed three times using an ultrasonic disperser (UH-600S manufactured by SMT) to obtain an emulsion.

Next, the above emulsion was miniaturized with a high-pressure homogenizer (Microfluitizer M110Y manufactured by Mizuho Kogyo Co., Ltd.) under a pressure of 70 MPa to obtain an acrylic monomer (a-3) -containing emulsion (EM-2). The solid content concentration of the emulsion (EM-2) is 30% by weight.
(Equation 1) Acrylic monomer (a-2)

<Reference Example 5> An emulsion (EM-3) containing an amide bond-containing acrylic monomer (a-3) constituting the acrylic resin (A) component and a resin composition (b-2) containing inorganic particles (B). )
In a flask equipped with a stirrer, 0.024 g of 2,6-di-t-butyl-p-cresol, 15 g of ethylenediol, and 3-isocyanatemethyl-3,5,5-trimethylcyclohexylisocyanate (Sumitomo Chemical Bayer Urethane Co., Ltd.) , 12 g of Death Module I) and methyl ethyl ketone were charged, 0.080 g of dibutyltin dilaurylate was added, the temperature was raised to 60 ° C., and the mixture was heated for 1.5 hours. Next, the reaction mixture was cooled in a water bath, and 35 g of tetramethylolmethane triacrylate (“NK ester” A-TMM-3LM-N manufactured by Shin-Nakamura Chemical Co., Ltd.) was diluted with methyl ethyl ketone to a solid content concentration of 50% by mass. Was added. The temperature was raised to 60 ° C. and heated for 4 hours to obtain the acrylic monomer (a-3) obtained by the formula 8.
Next, a resin composition containing 30 parts of dipentahexaacrylate (KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.), 50 parts by weight of acrylic monomer (a-3), and inorganic particles (B) in a flask equipped with a stirrer. b-2) 20 parts by weight, 79 parts by weight of a 10% aqueous solution of polyoxyethylene polycyclic phenyl ether sulfate ester salt (Newcol 707SF manufactured by Nippon Emulsifier Co., Ltd.) as an emulsifier, polyoxyethylene lauryl ether (Emulgen 104P manufactured by Kao Corporation) ) 2.1 parts by weight and 128.9 parts by weight of ion-exchanged water were added and mixed by stirring. Then, while cooling in an ice bath, ultrasonic irradiation for 120 seconds was performed three times using an ultrasonic disperser (UH-600S manufactured by SMT) to obtain an emulsion.

Next, the above emulsion was miniaturized with a high-pressure homogenizer (Microfluitizer M110Y manufactured by Mizuho Kogyo Co., Ltd.) under a pressure of 70 MPa to obtain an acrylic monomer (a-3) -containing emulsion (EM-3). The concentration of the emulsion (EM-3) is 30%.
(Equation 8) Acrylic monomer (a-3)

<Reference Example 6> An emulsion (EM-4) containing an amide bond-containing acrylic monomer (a-2) constituting the acrylic resin (A) component.
In a flask equipped with a stirrer, 30 parts by weight of dipentahexaacrylate (KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.), 50 parts by weight of the obtained acrylic monomer (a-2), and polyoxyethylene polycyclic phenyl ether sulfate as an emulsifier. 79 parts by weight of 10% by weight aqueous solution of ester salt (Newcol 707SF manufactured by Nippon Emulsifier Co., Ltd.), 2.1 parts by weight of polyoxyethylene lauryl ether (Emargen 104P manufactured by Kao Corporation), and 128.9 parts by weight of ion-exchanged water were added. And stirred and mixed. Then, while cooling in an ice bath, ultrasonic irradiation for 120 seconds was performed three times using an ultrasonic disperser (UH-600S manufactured by SMT) to obtain an emulsion.

Next, the above emulsion was miniaturized with a high-pressure homogenizer (Microfluitizer M110Y manufactured by Mizuho Kogyo Co., Ltd.) under a pressure of 70 MPa to obtain an acrylic monomer (a-2) -containing emulsion (EM-4).

<Reference Example 7> An emulsion (EM-6) containing an amide bond-containing acrylic monomer (a-2) constituting the acrylic resin (A) component and a resin composition (b-2) containing inorganic particles (B). )
A resin composition (b-) containing 30 parts of dipentahexaacrylate (KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.), 50 parts by weight of acrylic monomer (a-2), and inorganic particles (B) in a flask equipped with a stirrer. 2) 40 parts by weight, 79 parts by weight of a 10% by weight aqueous solution of polyoxyethylene polycyclic phenyl ether sulfate ester salt (Newcol 707SF manufactured by Nippon Emulsifier Co., Ltd.) as an emulsifier, polyoxyethylene lauryl ether (Emulgen 104P manufactured by Kao Co., Ltd.) 2.1 parts by weight and 128.9 parts by weight of ion-exchanged water were added and mixed by stirring. Then, while cooling in an ice bath, ultrasonic irradiation for 120 seconds was performed three times using an ultrasonic disperser (UH-600S manufactured by SMT) to obtain an emulsion.

Next, the above emulsion was miniaturized with a high-pressure homogenizer (Microfluitizer M110Y manufactured by Mizuho Kogyo Co., Ltd.) under a pressure of 70 MPa to obtain an acrylic monomer (a-2) -containing emulsion (EM-6). The solid content concentration of the emulsion (EM-6) is 30% by weight.
<Reference Example 8> Resin composition (b-3) containing inorganic particles (B)
50 parts by weight of acryloyl group-containing particle modifier (b-1), 50 parts by weight of silica particle aqueous dispersion (“Sicaster” 43-02-103 particle diameter 1000 nm manufactured by Micromod), 0.12 parts by weight of ion-exchanged water, and A mixed solution of 0.01 parts of p-hydroxyphenyl monomethyl ether is stirred at 60 ° C. for 4 hours, 1.36 parts of orthoatetate methyl ester is added, and the mixture is further heated and stirred at the same temperature for 1 hour to obtain inorganic particles (inorganic particles). A resin composition (b-3) containing B) was obtained.

<Reference Example 9> An emulsion (EM-7) containing an acrylic monomer (a-1) constituting an acrylic resin (A) component and a resin composition (b-3) containing inorganic particles (B).
A resin composition (b-3) containing 80 parts by weight of acrylic monomer (a-2) (dipentahexaacrylate (KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.)) and inorganic particles (B) in a flask equipped with a stirrer. ) 20 parts by weight, 79 parts by weight of a 10% by weight aqueous solution of polyoxyethylene polycyclic phenyl ether sulfate ester salt (Newcol 707SF manufactured by Japan Emulsifier) as an emulsifier, polyoxyethylene lauryl ether (Emargen 104P manufactured by Kao Co., Ltd.) 2 .1 part by weight and 128.9 parts by weight of ion-exchanged water were added and mixed by stirring. Then, while cooling in an ice bath, ultrasonic irradiation for 120 seconds was performed three times using an ultrasonic disperser (UH-600S manufactured by SMT) to obtain an emulsion.

Next, the above emulsion was miniaturized with a high-pressure homogenizer (Microfluitizer M110Y manufactured by Mizuho Kogyo Co., Ltd.) under a pressure of 70 MPa to obtain an acrylic monomer (a-2) -containing emulsion (EM-7). The solid content concentration of the emulsion (EM-7) is 30% by weight.
<Reference Example 10> Resin composition (b-4) containing inorganic particles (B)
50 parts by weight of acryloyl group-containing particle modifier (b-1), 50 parts by weight of silica particle aqueous dispersion (“Sicaster” 43-02-503 particle diameter 5000 nm manufactured by Micromod), 0.12 parts by weight of ion-exchanged water, and 0.01 parts by weight of p-hydroxyphenyl monomethyl ether is stirred at 60 ° C. for 4 hours, 1.36 parts of orthoatetate methyl ester is added, and the mixture is further heated and stirred at the same temperature for 1 hour to obtain inorganic particles. A resin composition (b-4) containing (B) was obtained.

<Reference Example 11> An emulsion (EM-8) containing an acrylic monomer (a-1) constituting an acrylic resin (A) component and a resin composition (b-4) containing inorganic particles (B).
A resin composition (b-4) containing 80 parts by weight of acrylic monomer (a-1) (dipentahexaacrylate (KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.)) and inorganic particles (B) in a flask equipped with a stirrer. ) 20 parts by weight, 79 parts by weight of a 10% aqueous solution of polyoxyethylene polycyclic phenyl ether sulfate ester salt (Newcol 707SF manufactured by Nippon Emulsifier Co., Ltd.) as an emulsifier, polyoxyethylene lauryl ether (Emargen 104P manufactured by Kao Co., Ltd.) 2. 1 part and 128.9 parts by weight of ion-exchanged water were added and mixed by stirring. Then, while cooling in an ice bath, ultrasonic irradiation for 120 seconds was performed three times using an ultrasonic disperser (UH-600S manufactured by SMT) to obtain an emulsion.

Next, the above emulsion was miniaturized with a high-pressure homogenizer (Microfluitizer M110Y manufactured by Mizuho Kogyo Co., Ltd.) under a pressure of 70 MPa to obtain an acrylic monomer (a-2) -containing emulsion (EM-8). The solid content concentration of the emulsion (EM-8) is 30% by weight.

<Reference Example 12> An emulsion (EM-10) containing a composition (B-3) having an acrylic resin (G) on the surface of the inorganic particles (B) and an acrylic resin (F).
100 parts of isopropyl alcohol was charged as a solvent into a normal acrylic resin reaction tank equipped with a stirrer, a thermometer, and a reflux condenser, and the mixture was heated and stirred to maintain the temperature at 100 ° C.
In this, 50 parts of nonadecil methacrylate having n = 19 as (meth) acrylate (g'1) and 50 parts of isobonyl methacrylate having two rings as (meth) acrylate (g'2) for 3 hours. Dropped over. Then, after the completion of the dropping, the mixture was heated at 100 ° C. for 1 hour, and then an additional catalyst mixed solution consisting of 1 part of t-butylperoxy2 ethylhexaate was charged. Then, it was heated at 100 ° C. for 3 hours and then cooled to obtain an acrylic resin (G1).
Further, 100 parts of isopropyl alcohol was charged as a solvent into a normal acrylic resin reaction tank equipped with a stirrer, a thermometer, and a reflux condenser, and the mixture was heated and stirred to maintain the temperature at 100 ° C. As the (meth) acrylate (f'3) having a hydroxyl group, 40 parts of 2-hydroxyethyl acrylate, 20 parts of other (meth) ethyl acrylate, and 20 parts of methyl methacrylate were added dropwise thereto over 3 hours. Then, after the completion of the dropping, the mixture was heated at 100 ° C. for 1 hour, and then an additional catalyst mixed solution consisting of 1 part of t-butylperoxy2 ethylhexaate was charged. Then, it was heated at 100 ° C. for 3 hours and then cooled to obtain an acrylic resin (F-1).

Inorganic particles (B) (“NanoTek” Al ₂ O ₃ slurry (manufactured by CI Kasei Co., Ltd., number average particle diameter 30 nm)) and the above acrylic resin (G-1) are added in order to an aqueous solvent and dispersed by the following method. After that, acrylic resin (F1) was added to obtain an emulsion (EM-10) containing a mixed composition (B-3) of particles (B), acrylic resin (G), and acrylic resin (F). The method (ii) above.)
The addition amount ratio (mass ratio) of the inorganic particles (B), the acrylic resin (F1), and the acrylic resin (G-1) is (B) / (F-1) / (G-1) = 50/40/10. (The mass ratio was calculated by rounding off the first decimal place). The dispersion treatment was carried out by using a homomixer and rotating at a peripheral speed of 10 m / s for 5 hours. The mass ratio of the particles (B), the acrylic resin (F-1), and the acrylic resin (G) in the finally obtained composition (B-3) is (B) / (F-1) /. (G) = 50/50 (Note that the mass ratio was obtained by rounding off the first decimal place).

The obtained composition (B-3) was centrifuged by a Hitachi desktop ultracentrifuge (manufactured by Hitachi Koki Co., Ltd .: CS150NX) (rotation speed 3000 rpm, separation time 30 minutes), and the inorganic particles (B). (And the acrylic resin (F-1) adsorbed on the surface of the inorganic particles (B)) was precipitated, the supernatant was removed, and the precipitate was concentrated to dryness. As a result of analyzing the concentrated and dried sediment by X-ray photoelectron spectroscopy (XPS), it was confirmed that the acrylic resin (F-1) was present on the surface of the inorganic particles (B). That is, the acrylic resin (F-1) is adsorbed and adhered to the surface of the inorganic particles (B), and the obtained composition (B-3) is attached to the surface of the inorganic particles (B). It was found that it corresponds to a particle having -1).

<Reference Example 13> An emulsion (EM-11) containing a composition (B-3) having an acrylic resin (G) on the surface of the inorganic particles (B) and an acrylic resin (F).
The addition amount ratio (mass ratio) of the inorganic particles (B) and the acrylic resin (F-1) acrylic resin (G-1) is (B) / (F-1) / (G-1) = 32.5 /. An emulsion (EM-11) containing a mixed composition (B-3) of particles (B) and an acrylic resin (F-1) was obtained in the same manner as in Reference Example 12 set to 37.5 / 30.

<Reference Example 14> An emulsion (EM-12) containing a composition (B-3) having an acrylic resin (G) on the surface of inorganic particles (B-1) and an acrylic resin (F).
On the surface of the particles (B) in the same manner as in Reference Example 13 except that the inorganic particles (“NanoTek” TiO ₂ slurry (number average particle diameter 36 nm manufactured by CI Kasei Co., Ltd.) were used as the inorganic particles (B)). An emulsion (EM-12) containing a mixed composition (B-3) of a composition (B-3) having an acrylic resin (G) and an acrylic resin (F-1) was obtained.

The characteristics of the laminated films obtained in the following examples and comparative examples are shown in the table.

Hereinafter, Examples 2, 9 to 10 and 21 shall be read as Reference Examples 2, 9 to 10 and 21.
<Example 1>
First, the resin composition 1 was prepared as follows.
<Resin composition>
The above emulsion was mixed with an aqueous solvent at the ratio shown in the table to obtain a resin composition 1.

-Emulsion (EM-5) containing acrylic monomer (a-1) constituting the acrylic resin (A) component: 100 parts by weight-Inorganic particles (B) "Snow Tech OL" (colloidal) manufactured by Nissan Chemical Industry Co., Ltd. Silica, particle size 40 nm): 20 parts by weight ・ Emulsifier: Polyoxyethylene polycyclic phenyl ether sulfate ester salt (Newcol 707SF manufactured by Nippon Emulsifier Co., Ltd.): 7.9 parts by weight, polyoxyethylene lauryl ether (manufactured by Kao Co., Ltd.) Emulgen 104P) 2.1 parts by weight (The above emulsifier is associated with (EM-5))
<Laminated film>
Next, PET pellets (extreme viscosity 0.63 dl / g) containing substantially no particles were sufficiently vacuum-dried, supplied to an extruder, melted at 285 ° C., extruded into a sheet from a T-shaped mouthpiece, and statically generated. Using an electric cast method, the particles were wound around a mirror casting drum having a surface temperature of 25 ° C. and cooled and solidified. This unstretched film was heated to 90 ° C. and stretched 3.4 times in the longitudinal direction to obtain a uniaxially stretched film (B film).
Next, the resin composition 1 was applied to the corona discharge-treated surface of the uniaxially stretched film using a bar coat to a coating thickness of about 6 μm. Both ends of the uniaxially stretched film coated with the resin composition in the width direction are gripped with clips to lead to a preheating zone, and the ambient temperature is set to 75 ° C. Then, the ambient temperature is set to 110 ° C using a radiation heater, and then the ambient temperature. The temperature was 90 ° C., and the resin composition was dried to form a resin layer. The laminated film was continuously stretched 3.5 times in the width direction in a heating zone (stretching zone) at 120 ° C., and then heat-treated in a heat treatment zone (heat fixing zone) at 230 ° C. for 20 seconds to complete crystal orientation. Got In the obtained laminated film, the thickness of the PET film was 50 μm, and the thickness of the resin layer was 1000 nm.
The characteristics of the obtained laminated film are shown in the table.
It was excellent in transparency, scratch resistance, anti-blocking property, and adhesiveness.

<Example 2>
A laminated film was obtained in the same manner as in Example 1 except that the resin composition in the coating liquid was changed as follows. The characteristics of the obtained laminated film are shown in the table.

-Emulsion (EM-5) containing the acrylic monomer (a-1) constituting the acrylic resin (A) component: 100 parts by weight-Inorganic particles (B): "Spherica 140" (silica particles) manufactured by Catalysis Chemical Co., Ltd. , Particle size 140 nm): 20 parts by weight ・ Emulsifier: Polyoxyethylene polycyclic phenyl ether sulfate ester salt (Newcol 707SF manufactured by Nippon Emulsifier Co., Ltd.): 7.9 parts by weight, Polyoxyethylene lauryl ether (Emulsifier manufactured by Kao Co., Ltd.) 104P) 2.1 parts by weight (The emulsifier is associated with (EM-5))
<Example 3>
A laminated film was obtained in the same manner as in Example 1 except that the resin composition in the coating liquid was changed as follows.
The characteristics of the obtained laminated film are shown in the table.

-Emulsion (EM-5) containing the acrylic monomer (a-1) constituting the acrylic resin (A) component: 100 parts by weight-Inorganic particles (B) ("Sea Hoster KEW-50" manufactured by Nippon Catalyst Co., Ltd. ( Silica particles, particle size 500 nm)): 20 parts by weight ・ Emulsifier: Polyoxyethylene polycyclic phenyl ether sulfate ester salt (Newcol 707SF manufactured by Nippon Emulsifier Co., Ltd.): 7.9 parts by weight, polyoxyethylene lauryl ether (Kao Co., Ltd.) ) Emulgen 104P) 2.1 parts by weight (The above emulsifier is accompanied by (EM-5))
<Example 4>
A laminated film was obtained in the same manner as in Example 1 except that the resin composition in the coating liquid was changed as follows.
The characteristics of the obtained laminated film are shown in the table.

-Emulsion (EM-5) containing the acrylic monomer (a-1) constituting the acrylic resin (A) component: 100 parts by weight-Inorganic particles (B) (Nissan Chemical Industry Co., Ltd. "Snowtex O" ( Silica particles, particle size 10 nm)): 20 parts by weight ・ Emulsifier: Polyoxyethylene polycyclic phenyl ether sulfate ester salt (Newcol 707SF manufactured by Nippon Emulsifier Co., Ltd.): 7.9 parts by weight, polyoxyethylene lauryl ether (Kao Co., Ltd.) ) Emulgen 104P) 2.1 parts by weight (The above emulsifier is accompanied by (EM-5))
<Example 5>
A laminated film was obtained in the same manner as in Example 1 except that the resin composition in the coating liquid was changed as follows. The characteristics of the obtained laminated film are shown in the table.

-Emulsion (EM-1) containing the acrylic monomer (a-1) constituting the acrylic resin (A) component and the resin composition (b-2) containing the inorganic particles (B): 100 parts by weight-Emulsifier : Polyoxyethylene polycyclic phenyl ether sulfate ester salt (Newcol 707SF manufactured by Japan Emulsifier Co., Ltd.): 7.9 parts by weight, Polyoxyethylene lauryl ether (Emulsifier 104P manufactured by Kao Co., Ltd.) 2.1 parts by weight (The above emulsifier is , (Accompanied by (EM-1))
<Example 6>
A laminated film was obtained in the same manner as in Example 1 except that the resin composition in the coating liquid was changed as follows. The characteristics of the obtained laminated film are shown in the table.

Emulsion (EM-2) containing an amide bond-containing acrylic monomer (a-2) constituting an acrylic resin (A) component and a resin composition (b-2) containing inorganic particles (B): 100 weight. Parts ・ Emulsifier: Polyoxyethylene polycyclic phenyl ether sulfate ester salt (Newcol 707SF manufactured by Nippon Emulsifier Co., Ltd.): 7.9 parts by weight, Polyoxyethylene lauryl ether (Emargen 104P manufactured by Kao Co., Ltd.) 2.1 parts by weight ( The above emulsifier accompanies (EM-2))
<Example 7>
A laminated film was obtained in the same manner as in Example 1 except that the resin composition in the coating liquid was changed as follows. The characteristics of the obtained laminated film are shown in the table.

Emulsion (EM-3) containing an amide bond-containing acrylic monomer (a-2) constituting an acrylic resin (A) component and a resin composition (b-2) containing inorganic particles (B): 100 weight. Parts ・ Emulsifier: Polyoxyethylene polycyclic phenyl ether sulfate ester salt (Newcol 707SF manufactured by Nippon Emulsifier Co., Ltd.): 7.9 parts by weight, Polyoxyethylene lauryl ether (Emargen 104P manufactured by Kao Co., Ltd.) 2.1 parts by weight ( The above emulsifier accompanies (EM-3))
<Example 8>
A laminated film was obtained in the same manner as in Example 1 except that the resin composition in the coating liquid was changed as follows. The characteristics of the obtained laminated film are shown in the table.

-Emulsion (EM-4) containing an amide bond-containing acrylic monomer (a-2) constituting the acrylic resin (A) component: 80 parts by weight-Inorganic particles (B) (Nissan Chemical Industry Co., Ltd. "Snowtech" OL "(colloidal silica, particle size 40 nm)): 20 parts by weight-Emulsifier: Polyoxyethylene polycyclic phenyl ether sulfate (Newcol 707SF manufactured by Japan Emulsifier Co., Ltd.): 7.9 parts by weight, polyoxyethylene lauryl ether ( Emulgen 104P manufactured by Kao Co., Ltd.) 2.1 parts by weight (The above emulsifier is accompanied by (EM-3))
<Examples 9 to 15>
A laminated film was obtained in the same manner as in Example 6 except that the film thickness of the resin layer was changed to the thickness shown in the table. The characteristics of the obtained laminated film are shown in the table.
<Example 16>
A laminated film was obtained in the same manner as in Example 6 except that the resin composition in the coating liquid was changed as follows. The characteristics of the obtained laminated film are shown in the table.
An emulsion (EM-6) containing an amide bond-containing acrylic monomer (a-2) constituting an acrylic resin (A) component and a resin composition (b-2) containing inorganic particles (B).
: 100 parts by weight ・ Emulsifier: Polyoxyethylene polycyclic phenyl ether sulfate ester salt (Neucor 707SF manufactured by Nippon Emulsifier Co., Ltd.): 7.9 parts by weight, polyoxyethylene lauryl ether (Emulsifier 104P manufactured by Kao Corporation) 2.1 Parts by weight (The above emulsifier is attached to (EM-2))

<Example 17>
A laminated film was obtained in the same manner as in Example 1 except that the resin composition in the coating liquid was changed as follows. The characteristics of the obtained laminated film are shown in the table.

Emulsion (EM-10) containing the composition (B-3) having the acrylic resin (G) on the surface of the inorganic particles (B) and the acrylic resin (F): 100 parts by weight <Example 18>
A laminated film was obtained in the same manner as in Example 1 except that the resin composition in the coating liquid was changed as follows. The characteristics of the obtained laminated film are shown in the table.

Emulsion (EM-11) containing a composition (B-3) having an acrylic resin (G) on the surface of the inorganic particles (B) and an acrylic resin (F): 100 parts by weight <Example 19>
A laminated film was obtained in the same manner as in Example 1 except that the resin composition in the coating liquid was changed as follows. The characteristics of the obtained laminated film are shown in the table.

Emulsion (EM-12) containing a composition (B-3) having an acrylic resin (G) on the surface of inorganic particles (B-1) and an acrylic resin (F): 100 parts by weight <Example 20>
A laminated film was obtained in the same manner as in Example 1 except that the resin composition in the coating liquid was changed as follows. The characteristics of the obtained laminated film are shown in the table.

-Emulsion (EM-11) containing a composition (B-3) having an acrylic resin (G) on the surface of the inorganic particles (B) and an acrylic resin (F): 80 parts by weight-Melamine compound "Beccamin" ( Registered trademark) APM (manufactured by Dainippon Ink Industry Co., Ltd.): 20 parts by weight


<Examples 21 and 22>
A laminated film was obtained in the same manner as in Example 17 except that the film thickness of the resin layer was changed to the thickness shown in the table. The characteristics of the obtained laminated film are shown in the table.

<Example 23>
A laminated film was obtained in the same manner as in Example 1 except that the resin composition in the coating liquid was changed as follows.
The characteristics of the obtained laminated film are shown in the table.

-Emulsion (EM-5) containing the acrylic monomer (a-1) constituting the acrylic resin (A) component: 100 parts by weight-Inorganic particles (B) (Nissan Chemical Industry Co., Ltd. "Snowtex O" ( Silica particles, particle size 10 nm)): 20 parts by weight ・ Emulsifier: Polyoxyethylene polycyclic phenyl ether sulfate ester salt (Newcol 707SF manufactured by Nippon Emulsifier Co., Ltd.): 7.9 parts by weight, polyoxyethylene lauryl ether (Kao Co., Ltd.) ) Emulgen 104P) 2.1 parts by weight (The above emulsifier is accompanied by (EM-5))
<Comparative example 1>
A laminated film was obtained in the same manner as in Example 1 except that the composition of the resin composition in the coating liquid was changed as shown in the table. The characteristics of the obtained laminated film are shown in the table.

-Emulsion (EM-5) containing acrylic monomer (a-1) constituting the acrylic resin (A) component: 100 parts by weight-Inorganic particles (B) (Nissan Chemical Industry Co., Ltd. "Snowtech OXS" ( Colloidal silica, particle size 5 nm)): 20 parts by weight ・ Emulsifier: Polyoxyethylene polycyclic phenyl ether sulfate ester salt (Newcol 707SF manufactured by Nippon Emulsifier Co., Ltd.): 7.9 parts by weight, polyoxyethylene lauryl ether (Kao Co., Ltd.) ) Emulgen 104P) 2.1 parts by weight (The above emulsifier is accompanied by (EM-5))
<Comparative example 2>
The resin composition used in Example 6 was applied to one side of a PET film having a thickness of 50 μm (“Lumilar (registered trademark)” U34 manufactured by Toray Industries, Inc.) so that the thickness after drying was 1000 nm, and a hot air oven was applied. After being dried at 100 ° C. for 2 minutes, it was dried again at 230 ° C. for 20 seconds to obtain a laminated film. The characteristics of the obtained laminated film are shown in the table.
<Comparative example 3>
A laminated film was obtained in the same manner as in Example 1 except that the resin composition in the liquid was changed as follows. The characteristics of the obtained laminated film are shown in the table.

-Emulsion (EM-7) containing the acrylic monomer (a-1) constituting the acrylic resin (A) component and the resin composition (b-3) containing the inorganic particles (B): 100 parts by weight-Emulsifier : Polyoxyethylene polycyclic phenyl ether sulfate ester salt (Newcol 707SF manufactured by Japan Emulsifier Co., Ltd.): 7.9 parts by weight, Polyoxyethylene lauryl ether (Emulsifier 104P manufactured by Kao Co., Ltd.) 2.1 parts by weight (The above emulsifier is , (Accompanied by (EM-7))
<Comparative example 4>
A laminated film was obtained in the same manner as in Example 1 except that the resin composition in the liquid was changed as follows. The characteristics of the obtained laminated film are shown in the table.

-Emulsion (EM-8) containing the acrylic monomer (a-1) constituting the acrylic resin (A) component and the resin composition (b-3) containing the inorganic particles (B): 100 parts by weight-Emulsifier : Polyoxyethylene polycyclic phenyl ether sulfate ester salt (Newcol 707SF manufactured by Japan Emulsifier Co., Ltd.): 7.9 parts by weight, Polyoxyethylene lauryl ether (Emulsifier 104P manufactured by Kao Co., Ltd.) 2.1 parts by weight (The above emulsifier is , (Accompanied by (EM-8))
<Comparative example 5>
A laminated film was obtained in the same manner as in Example 17 except that the film thickness of the resin layer was changed to the thickness shown in the table. The characteristics of the obtained laminated film are shown in the table.

The present invention is a laminated film having excellent transparency, scratch resistance, handling property, and anti-blocking property, and can be used as a hard coat film used for conventional display applications and a hard coat film used for molding decoration applications. ..

Claims (10)

A laminated film having a polyester layer and a resin layer, the surface layer on at least one side is a resin layer, the resin layer on the surface layer contains an acrylic resin, and the micro surface roughness (Ra) determined by AFM (Atomic Force Microscope). -1) is 1 nm or more and 20 nm or less, and the macro surface roughness (Ra-2) determined by the three-dimensional surface roughness meter is 1 nm or more and 50 nm or less.
The resin layer on the surface layer contains inorganic particles, and the particle abundance ratio (P-) in the range from the surface of the resin layer to the position of 10% of the thickness of the resin layer when observing the cross section of the resin layer in the thickness direction is observed. 1) is a laminated film having a larger particle abundance ratio (P-2) in the range from the surface of the resin layer to the position of 40% to 60% of the thickness of the resin layer. The laminated film according to claim 1, wherein the particles are a composition obtained by binding an inorganic particle and a resin component containing an acryloyl group, or a composition having an acrylic resin on a part or all of the surface of the inorganic particle. The laminated film according to claim 1 or 2, wherein the resin layer contained in the surface layer has a macro surface roughness (Ra-2) determined by a three-dimensional surface roughness meter of 5 nm or more and 50 nm or less. Claims 1 to 3, wherein the ratio (Ra-2 / Ra-1) of the micro surface roughness (Ra-1) and the macro surface roughness (Ra-2) of the resin layer contained in the surface layer is 3 or more and 30 or less. The laminated film according to any one of 3. Particle abundance ratio (P-1) in the range from the resin layer surface to the position of 10% of the resin layer thickness, and particle presence in the range from the resin layer surface to the position of 40% to 60% of the resin layer thickness. The laminated film according to any one of claims 1 to 4, wherein the ratio (P-1 / P-2) of the ratio (P-2) is 1.1 or more and 5.0 or less. The laminated film according to any one of claims 1 to 5, wherein the thickness (t) of the resin layer on the surface layer is 100 nm or more and 5000 nm or less. The average particle size (d) of the particles contained in the resin layer on the surface layer is 1 nm or more and 100 nm or less, and the ratio (t) / (d) of the thickness (t) of the resin layer to the average particle size (d) of the particles. The laminated film according to any one of claims 1 to 6, wherein) is 2 or more and 1000 or less. The laminated film according to any one of claims 1 to 7, wherein the polyester layer and the resin layer are directly laminated. The hard coat laminated film according to any one of claims 1 to 8, which is used for a display application or a molding decoration application. A coating liquid containing a polyfunctional acrylic resin and inorganic particles is applied to at least one surface of the polyester film before the crystal orientation is completed, then the polyester film is stretched at least in the uniaxial direction, and the polyester film is heat-treated. The method for producing a laminated film according to any one of claims 1 to 8, further comprising a step of completing the crystal orientation of the polyester film.