JP2019048447A - Laminate film and manufacturing method therefor - Google Patents

Abstract

To provide a laminate polyester film excellent in transparency, scratch resistance and slipperiness.SOLUTION: There is provided a laminate film having a thermoplastic resin layer and a resin layer (X), in which at least one side surface later is the resin layer (X), the resin layer (X) on the surface layer contains particles (M) of at least one kind of element selected from Si, Al, Ti, Zr, Fe and at least one kind of crosslinking agent selected from a melamine compound, an oxazoline compound, a carbodiimide compound, an isocyanate compound and an epoxy compound, ten point average toughness (Rz) by a three dimensional roughness meter of a surface of the resin layer (X) on the surface layer is 50 to 500 nm and maximum particle diameter φ (μm) of the particle (M) contained in the resin layer (X) is smaller than film thickness d (μm) of the resin layer (X).SELECTED DRAWING: None

Description

  The present invention relates to a laminated film having a thermoplastic resin layer and a resin layer (X).

  Thermoplastic resin films, particularly biaxially oriented polyester films, have excellent mechanical properties, electrical properties, dimensional stability, transparency, chemical resistance and the like, and thus many of magnetic recording materials, packaging materials, etc. It is widely used in applications. In particular, in recent years, it is used for various optical films including display member applications such as touch panels, liquid crystal display panels (LCDs), plasma display panels (PDPs), organic electroluminescence (organic EL) and the like.

  In these optical films, a layer having different refractive index (hereinafter referred to as an optical adjustment layer) is laminated on a polyester film, and then a conductive layer is often provided to be used as a conductive film. Here, in general, when laminating an optical adjustment layer, after a functional coating agent is applied and cured on a base film wound in a roll, so-called roll to roll Processing is applied in the form of In addition, the conductive layer is formed by forming an inorganic film on a roll film by sputtering in a vacuum environment.

  Therefore, in such applications, a laminated film in which a scratch resistant layer is laminated on a polyester film is used in order to prevent damage during transport of the film roll.

  As this laminated | multilayer film, the hard coat film which laminated | stacked the layer which consists of ultraviolet-ray (UV) curable resin as a scratch-resistant layer is used. When it is used for optical applications, it is required to make the surface of the resin layer smooth in order to improve the transparency, since transparency is required, but when the surface of the resin layer is made smooth, it becomes a film roll. Blocking (sticking) occurs. Therefore, in recent years, a laminated film having blocking resistance is required.

  In addition to scratch resistance, the laminated film used for optical applications is also required to have adhesion to a substrate when stored not only under normal temperature but also under high temperature and high humidity, transparency, etc. . For example, visibility and design are required for laminated films used for optical applications. In particular, in the case of a biaxially oriented polyester film, since the base material contains an oligomer, the oligomer may be deposited on the surface layer when stored in a high temperature and high humidity environment, and the transparency may be deteriorated.

With respect to this requirement, Patent Document 1 proposes a method of reducing the contact area of the hard coat film and laminating the coating containing particles larger than the coat film thickness to exhibit antiblocking properties. Moreover, in patent document 2, the method of obtaining the laminated film which is excellent in anti-glare property and abrasion resistance is proposed by laminating | stacking the coating film containing an acryl particle smaller than a coat film thickness.
Patent Document 3 proposes a method of suppressing the deterioration of transparency in a high temperature and high humidity environment by reducing the amount of oligomers of a polyester film as a base material.

JP 2014-228833 A JP, 2011-186287, A JP 2003-191413

  However, in the method described in Patent Document 1, since the particle diameter of the particles present in the coat layer is large, light scattering occurs, and there is a problem that the transparency is impaired. Also in the method described in Patent Document 2, since the particle diameter of the acrylic particles present in the coating layer having a film thickness of 6 to 8 μm is as large as about 2 to 5 μm, this is a region where light scattering occurs. There is a problem with transparency in optical applications where high transparency is required. Further, although the method described in Patent Document 3 has a certain effect of suppressing the precipitation of the oligomer, the effect is not sufficient, and the effect can not be obtained in a high temperature and high humidity environment.

  Therefore, it is an object of the present invention to solve the above-mentioned drawbacks and to provide a laminated film which is excellent in transparency, scratch resistance, moisture heat resistance transparency, and heat resistance transparency (oligomer block property).

In order to solve the above-mentioned subject, a layered film of the present invention has the following composition.
(1) A laminated film having a thermoplastic resin layer and a resin layer (X), wherein the surface layer on at least one side is a resin layer (X), and the resin layer (X) on the surface layer is Si, Al, Ti And particles containing at least one element selected from Zr and Fe, and at least one crosslinking agent selected from melamine compounds, oxazoline compounds, carbodiimide compounds, isocyanate compounds, epoxy compounds, and the surface layer The ten-point average roughness (Rz) by the three-dimensional roughness meter of the resin layer (X) surface is 50 to 500 nm, and the maximum particle diameter φ of the particles (M) having an element contained in the resin layer (X) A laminated film in which (μm) is smaller than the film thickness d (μm) of the resin layer (X).
(2) The laminated film according to (1), wherein the haze of the laminated film is 0.2% or less.
(3) The laminated film as described in (1) or (2) whose particle content of the said thermoplastic resin layer is 0.1 weight% or less.
(4) The content of particles (M) having an element of the resin layer (X) in the surface layer is 20 to 60% by weight with respect to the entire resin layer (X) (1) to (3) The laminated film as described in.
(5) The resin layer (X) is a layer formed by applying a coating composition (x) containing an acrylic resin (A) to a thermoplastic resin layer, followed by heating, and the acrylic resin (A) The laminated film in any one of (1)-(4) whose Tg of 0-60 degreeC.
(6) The resin layer (X) comprises particles (M-1) having at least one element selected from the group consisting of Si, Al, Ti, Zr, Se and Fe, and Si, Any of (1) to (5) containing particles (M-2) containing an element different from the elements of the particles (M-1) selected from Al, Ti, Zr, Se and Fe The laminated film as described in.
(7) When the particle diameter of the particles (M) contained in the resin layer (X) is the particle diameter on the horizontal axis and the existence ratio of the particles on the vertical axis, the particle diameter is in the range of 10 to 100 nm, The laminated film in any one of (1)-(6) which has one or more maximal value in each of the range of diameter 200-600 nm.
(8) A laminated film having a thermoplastic resin layer and a resin layer (X), wherein the surface layer on at least one side is a resin layer (X), and the resin layer (X) on the surface layer is Si, Al, Ti And particles containing at least one element selected from Zr and Fe (M) and at least one crosslinking agent selected from a melamine compound, an oxazoline compound, a carbodiimide compound, an isocyanate compound, and an epoxy compound,
When the spectral reflectance spectrum is measured in the wavelength range of 400 to 800 nm from the resin layer (X) side and the wavelength (nm) is plotted on the horizontal axis and the reflectance (%) on the vertical axis, in the wavelength 400 to 800 nm range There are 4 or more and 14 or less extrema,
There are two or more extreme values in the wavelength range of 500 to 600 nm, and two or more extreme values in at least one of the wavelength range of 400 to 500 nm and the wavelength range of 600 to 800 nm,
The largest value of the amplitude intensity (the difference between the spectral reflectances of two adjacent extreme values) in the wavelength region of 500 to 600 nm corresponds to the amplitude intensity at two wavelengths of 400 to 500 nm or 600 to 800 nm (two adjacent poles). The laminated film in any one of (1)-(7) which is 0.5 times or more and less than 2 times with respect to the largest value of the spectral reflectance difference which a value has.
(9) The method for producing a laminated film according to any one of (1) to (7), wherein at least one side of the thermoplastic resin layer is selected from Si, Al, Ti, Zr, Se, Fe Coating composition (x) containing particles (M) having one kind of element and at least one kind of crosslinking agent selected from melamine, oxazoline, carbodiimide, isocyanate, epoxy compound is applied, and then said coating composition The manufacturing method of the laminated | multilayer film which extend | stretch the thermoplastic resin layer by which (x) was apply | coated at least uniaxial direction, and then heat-process.

  The laminated film of the present invention is excellent in transparency, scratch resistance and moisture-heat resistance, and imparts scratching property while maintaining excellent transparency even after heat treatment during film processing and wet heat treatment. Can.

The extremum calculated from the reflection spectrum of the laminated film and the amplitude intensity are schematically shown.

Hereinafter, the laminated film of the present invention will be described in detail.
The present invention is a laminated film having a thermoplastic resin layer and a resin layer (X), wherein the surface layer on at least one side is a resin layer (X), and the resin layer (X) on the surface layer is Si, Al, A particle (M) having at least one element selected from Ti, Zr, and Fe, and at least one crosslinking agent selected from a melamine compound, an oxazoline compound, a carbodiimide compound, an isocyanate compound, and an epoxy compound The maximum particle diameter φ (μm) of the particles (M) contained in the resin layer (X) is 50 to 500 nm and the thickness of the resin layer (X) is ten-point average roughness (Rz) measured by the original roughness meter It is a laminated film smaller than d (μm).

  The ten-point average roughness (Rz) by the three-dimensional roughness meter in the present invention is measured by using a three-dimensional roughness meter manufactured by Kosaka Laboratory for an area of 400 μm × 900 μm on the surface of the resin layer (X). The ten-point average roughness (Rz) of the resin layer (X) is meant. When the ten-point average roughness (Rz) of the surface of the resin layer (X) is 50 to 500 nm, a film excellent in moisture heat resistance and transparency is obtained.

The method for setting the ten-point average roughness (Rz) of the surface of the resin layer (X) to the above range is not particularly limited, but the particles are contained in the resin layer (X), and the particle diameter and particle content And a method of stretching the resin layer in a state where the binder resin constituting the resin layer is not yet cured and then thermally curing it to form a smooth asperity.
Among the above methods, the resin layer (X) contains particles (M) having a number average particle diameter of 200 to 600 nm, preferably 200 to 400 nm, and the binder resin is stretched to the resin layer in a still uncured state. After the treatment, the method of heat treatment can make the ten-point average roughness (Rz) 50 to 500 nm while developing the scratch resistance of the resin layer (X), and the resin layer and the opposite surface Because the number of times of rubbing is reduced, the moisture and heat resistance is improved, which is preferable.

  Furthermore, it is preferable that it is a composition (MA) which has an acrylic resin (A) in part or all of the surface of particle | grains (M). By having the acrylic resin (A), the particles (M) in the resin layer can be nano-dispersed, and while maintaining the transparency of the resin layer, the force is applied to the particles when the resin layer is applied. It can be dispersed and has excellent transparency and scratch resistance. Furthermore, since the particles are densely present, precipitation of low molecular weight substances at the time of heating and wet heat treatment can be suppressed, and heat resistant transparency and moisture heat resistant transparency are preferable.

  Examples of the method of covalent bonding or noncovalent bonding (physical adsorption) of the particles (M) and the acrylic resin (A) include a method in which the particles (M) described later are surface-treated with the acrylic resin (A).

The acrylic resin (A) in the present invention, the monomer unit (a ₁₎ represented by the formula (1), a monomer unit represented by formula (2) (a _2), is expressed by equation (3) it is preferably a resin having a monomer unit (a ₃₎ that.

(In formula (1), R ₁ represents a hydrogen atom or a methyl group, and n represents an integer of 9 or more and 34 or less).

(In formula (2), the R ₂ group represents a hydrogen atom or a methyl group, and the R ₄ group represents a group containing two or more saturated carbocyclic rings).

(In formula (3), the R ₃ group represents a hydrogen atom or a methyl group. Further, the R ₅ group is a hydroxyl group, a carboxyl group, a tertiary amino group, a quaternary ammonium base, a sulfonic acid group, or phosphoric acid Represents a group)
In the present application, the ratio of particle diameter (φ) thickness (d) (particle diameter (φ) / thickness (d)) is preferably 0.3 or more and 0.6 or less. By setting it in this range, the ten-point average roughness (Rz) of the resin layer (X) becomes 50 to 500 nm, and the scratch resistance of the resin layer (X) is expressed, and both transparency and moisture-heat resistance transparency are achieved. can do. In order to set it as the said range, it can achieve by containing less than 3 parts of particle | grains (M2) which have local maximum in 200-600 nm range in a resin layer (X).

  In the laminate film of the present invention, the content of particles (M) of the resin layer (X) is 10 to 60% by weight with respect to the entire resin layer (X), a specific element is contained in the resin layer. Since the hardness of a resin layer improves and it is excellent in scratch resistance by being filled with the particle which it has, it is preferable. The content of particles (M) having a specific element is preferably 20 to 50% by weight, more preferably 30 to 50% by weight.

In the laminated film of the present invention, when the spectral reflection spectrum is measured in the wavelength range of 400 to 800 nm from the resin layer (X) side, and the wavelength (nm) is plotted on the horizontal axis and the reflectance (%) on the vertical axis, There are 4 or more and 14 or less extreme values in the wavelength range of 400 to 800 nm,
There are two or more extreme values in the wavelength range of 500 to 600 nm, and two or more extreme values in at least one of the wavelength range of 400 to 500 nm and the wavelength range of 600 to 800 nm,
The largest value of the amplitude intensity (the difference between the spectral reflectances of two adjacent extreme values) in the wavelength region of 500 to 600 nm corresponds to the amplitude intensity at two wavelengths of 400 to 500 nm or 600 to 800 nm (two adjacent poles). It is preferable that it is 0.5 times or more and less than 2 times the largest value of the spectral reflectance difference).
When the spectral reflection spectrum is in the above range, the amplitude intensity of each wavelength region becomes an appropriate range, amplification of amplitude due to light interference can be suppressed, and interference unevenness of the laminated film when viewed visually is reduced. be able to.

  Although the method to make a spectral reflection spectrum the said range is not specifically limited, For example, it can achieve by adjusting the refractive index and thickness of a resin layer (X) suitably. Specifically, the refractive index of the resin layer (X) is preferably in the range of 1.58 to 1.75, and more preferably in the range of 1.59 to 1.64. The thickness of the resin layer (X) is preferably 0.3 to less than 5 μm, more preferably 0.5 to less than 1.5 μm, and still more preferably 0.5 to 1.0 μm.

Specifically, titanium oxide (TiO ₂ ) particles and aluminum oxide (Al ₂ O ₃ ) particles are used as particles (M1) having a specific element having a particle diameter of 10 to 100 nm, and specific particles having a particle diameter of 200 to 600 nm are used. When silica particles are used as the particles (M2) having an element, moisture-heat-resistance transparency can be imparted while suppressing interference unevenness of the resin layer (X), which is preferable.

Furthermore, a titanium oxide (TiO ₂ ) particle, which is a particle (M1) having a specific element with a particle diameter of 10 to 100 nm, and a part or all of the surface of aluminum oxide (Al ₂ O ₃ ) particle, an acrylic resin (A) It is preferable that it is a composition (MA) which has. By having the acrylic resin (A), the particles (M1) having a specific element in the resin layer can be nano-dispersed, and while maintaining the transparency of the resin layer, when a force is applied to the resin layer The force can be dispersed into the particles. As a result, it is possible to improve the scratch resistance of the laminated film.

  Moreover, the laminated film of this invention can suppress the influence of hardening inhibition of a resin layer surface layer as the thickness of a resin layer is less than 0.3-5 micrometers, and since it is excellent in scratch resistance, it is preferable. The upper limit of the thickness of the resin layer is not limited, but is preferably 5 μm or less in terms of transparency and productivity. In addition, more preferably 0.3 μm or more and less than 2 μm, further preferably 0.5 μm or more and less than 1.5 μm.

  The laminated film of the present invention preferably has an internal haze of 0.2% or less. By setting the internal haze within the above range, a film having good transparency can be obtained.

[Particles having a specific element (M)]
The laminated film of the present invention needs to contain particles (M) having at least one element selected from Si, Al, Ti, Zr, Se, Fe in the resin layer (X) in the surface layer. It is.

As particles (M) having such a specific element, oxide particles of at least one element selected from Si, Al, Ti, Zr, Se and Fe are preferable, and silicon dioxide (silica) Examples include (SiO ₂ ), aluminum oxide (Al ₂ O ₃ ), titanium dioxide (TiO ₂ ), zirconium dioxide (ZrO ₂ ), selenium dioxide (SeO ₂ ), iron oxide (Fe ₂ O ₃ ) particles, and the like.
Among these, titanium oxide (TiO ₂ ) and aluminum oxide (Al ₂ O ₃ ) particles are preferable because they have excellent transparency in terms of matching with the refractive index. The content of the particles (M) having a specific element in the resin layer (X) is preferably 20 to 60% by weight based on the entire resin layer (X). Furthermore, aluminum oxide particles are more preferable because they are excellent in scratch resistance and resistance to heat and transparency.

  Further, in the present invention, it is preferable that the resin layer (X) contain particles (M) having at least two elements selected from Si, Al, Ti, Zr, Se, and Fe. When containing particles (M) having at least two elements, one particle may contain particles (M) containing two or more of the above elements, and one particle may be contained in one particle. A plurality of particles (M) containing one of the elements described above may be contained. Among them, particles (M-1) having at least one element selected from Si, Al, Ti, Zr, Se, Fe, and particles (M-1), Si, Al, Ti, Zr, Se, Fe It is preferable to contain the particle | grain (M-2) containing an element different from the element which has to the said particle | grain (M-1) chosen from these. In particular, when the particle diameter of the particles contained in the resin layer (X) is measured by the measurement method described later, and the particle diameter is plotted on the horizontal axis and the abundance ratio of the particles is plotted on the vertical axis, If particles (M) having a specific element are contained so as to have maximum values in each of the 600 nm range, the ten-point average roughness can be improved with the amount of particles added that does not impair transparency, and the initial stage It is preferable because it is possible to achieve both transparency and moisture-and-heat transparency. In order to obtain a resin layer (X) having a maximum value in the above range, it has particles (M1) having a specific element with an average particle diameter of 10 to 100 nm and a specific element having an average particle diameter of 200 to 600 nm The inclusion of particles (M2) is mentioned.

  In particular, in the laminated film of the present invention, the content of the particles (M1) having a specific element having an average particle diameter of 10 to 100 nm of the resin layer (X) is 20% by weight based on the entire resin layer (X) As described above, the content of the particles (M2) having a specific element having an average particle diameter of 200 to 600 nm which is less than 60% by weight is 0.01% by weight or more based on the entire resin layer (X). When the amount is less than 0% by weight, the pressure applied to the resin layer (X) is reduced, precipitation of low molecular weight substances contained in the film substrate and the resin layer (X) is suppressed, and moisture heat resistance is excellent. .

  In addition, the laminated film of the present invention is resistant to heating when the particles (M1) having a specific element with an average particle diameter of 10 to 100 nm are contained in an amount of 20% by weight or more and less than 60% by weight based on the entire resin layer (X). It is preferable because of its excellent transparency. In particular, aluminum oxide particles excellent in heat resistance are more preferable. By setting it as the said range, the physical distance required in order for the low molecular-weight thing contained in laminated | multilayer film to move to surface layer becomes large by presence of particle | grains in a resin layer, and it is excellent in heat-resistant transparency. Furthermore, when the resin layer (X) contains at least one crosslinking agent selected from melamine compounds, oxazoline compounds, carbodiimide compounds, isocyanate compounds, and epoxy compounds, the resin layer (X) has a dense crosslinked structure, The energy required when the low molecular weight substance contained in the laminated film tends to precipitate on the surface layer is large, so it is difficult to precipitate on the surface layer, and the heat-resistant transparency is excellent.

Furthermore, in the present invention, titanium oxide (TiO ₂ ) particles and aluminum oxide (Al ₂ O ₃ ) particles are used as particles (M1) having a specific element having an average particle diameter of 10 to 100 nm, and have an average particle diameter of 200 to 600 nm. When silica particles are used as the particles (M2) having a specific element, moisture-heat-resistance transparency can be imparted while suppressing interference unevenness of the resin layer (X), which is preferable.

  In addition, particles (M) having a specific element used in the laminated film of the present invention are compositions (MA) having an acrylic resin (A) on part or all of the surface of particles (M) having a specific element Is preferred. The bonding referred to here may be covalent bonding or non-covalent bonding (physical adsorption).

In addition, a composition (MA) having an acrylic resin (A) on part or all of the surface of particles (M) having a specific element of the present invention is a part of the surface of particles (M) having a specific element It is preferable that it is a particle | grain which has the acrylic resin (A) mentioned above in all or.
By having the acrylic resin (A) on the surface of the particles (M) having a specific element, aggregation of the particles (M) having a specific element in the drying process can be suppressed and transparency and scratch resistance can be improved. It becomes.

  The method of producing the particles (M) having a specific element is not particularly limited, but a method of surface treating particles (M) having a specific element with an acrylic resin (A) can be mentioned. Specifically, the following methods (i) to (iv) are exemplified. In the present invention, the surface treatment refers to a treatment in which the acrylic resin (A) is adsorbed and adhered to all or part of the surface of the particles (M) having a specific element.

  (I) A method in which a mixture in which particles (M) having a specific element and an acrylic resin (A) are mixed in advance is added to a solvent and then dispersed.

  (Ii) A method in which particles (M) having a specific element and an acrylic resin (A) are sequentially added and dispersed in a solvent.

  (Iii) A method in which particles (M) having a specific element and an acrylic resin (A) are dispersed in advance in a solvent, and the obtained dispersion is mixed.

  (Iv) A method of dispersing particles (M) having a specific element in a solvent, and then adding an acrylic resin (A) to the obtained dispersion.

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

  Further, as an apparatus for dispersing, a dissolver, a high speed mixer, a homomixer, a meider, a ball mill, a roll mill, a sand mill, a paint shaker, an SC mill, an annular mill, a pin mill, etc. can be used.

  Moreover, as a dispersion | distribution method, using the said apparatus, a rotating shaft is rotated by 5-15 m / s of circumferential speeds. The rotation time is 5 to 10 hours.

  In addition, it is more preferable to use dispersion beads such as glass beads at the time of dispersion, in order to enhance the 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, and the like can be performed.

  The presence or absence of adsorption / adhesion of the acrylic resin (A) on all or part of the surface of the particles (M) having a specific element can be confirmed by the following analysis method. A measurement object (for example, a composition (MA-1) having an acrylic resin (A-1) on a part or all of the surface of particles (M1) having a specific element) Centrifugation was performed by Kikusui Co., Ltd .: CS150NX (rotation speed: 30,000 rpm, separation time: 30 minutes), and particles adsorbed on the surface of particles (M1) having a particular element (and particles (M1) having a particular element After precipitation of the acrylic resin (A-1)), the supernatant is removed and the precipitate is concentrated to dryness. The concentrated and dried precipitate is analyzed by X-ray photoelectron spectroscopy (XPS) to confirm the presence or absence of the acrylic resin (A) on the surface of the particles (M1) having a specific element. It was confirmed that the acrylic resin (A-1) is present in an amount of 1% by mass or more on the surface of the particles (M) having a specific element with respect to a total of 100% by mass of the particles (M) having a specific element In this case, the acrylic resin (A-1) is adsorbed and adhered to the surface of the particles (M) having a specific element.

Here, the particle diameter of the particles (M) having a specific element will be described. Here, the particle size refers to the particle size obtained by a scanning electron microscope (SEM).
Using a microtome, small pieces cut in a direction perpendicular to the surface of the laminated film were formed, and the cross section was magnified and observed at 100,000 times using a scanning transmission electron microscope (SEM). From the cross-sectional photograph, the particle size distribution of particles present in the film was determined using an image analysis software Image-Pro Plus (Nippon Roper). Cross-sectional pictures are selected from different measurement fields of view, the diameters (equivalent circle diameters) of 200 or more particles arbitrarily selected from the cross-sectional pictures are measured, and the horizontal axis is the particle size, and the vertical axis is the particle abundance ratio The obtained volume based particle size distribution was obtained. In the volume-based particle size distribution described above, the particle diameter that carries the horizontal axis is the class at every 10 nm interval starting from 0 nm, and the abundance ratio of particles that carry the vertical axis is the formula “existence ratio = corresponding particle diameter It is represented by “total volume of detected particles / total volume of all detected particles”. The particle size of the peak top showing the maximum is read from the chart of the abundance ratio of particles obtained as described above.
Further, the maximum particle size in the present application refers to the particle size of the peak top showing the largest maximum of the particle size among the maximum values of the particle abundance ratio chart obtained above.

When the particle diameter of the particles (M) having a specific element is smaller than 1 nm, the van der Waals force between the particles is increased, and as a result of aggregation of the particles, light scattering occurs and transparency is lowered. is there. On the other hand, when the particle diameter of the particles (M) having the specific element is larger than 100 nm, from the viewpoint of transparency, light may be a source of light scattering, and the transparency may be deteriorated. In addition, the loading of particles having a specific element in the coating may not proceed sufficiently, and the scratch resistance may be reduced. Therefore, the particles (M1) having a specific element contained in an amount of 20% by weight or more in the resin layer preferably have a particle diameter of 5 nm or more and 100 nm or less. Preferably they are 20 nm or more and 80 nm or less, more preferably 30 nm or more and 80 nm or less.
Furthermore, when particles (M2) having a specific element having a maximum value in the range of 200 to 600 nm are included in the resin layer, the ten-point average roughness (Rz) falls within a predetermined range, which is preferable.
In the present invention, the ratio of the thickness (nm) of the resin layer to the particle diameter (nm) of the particles (M) having the specific element is the maximum of the particles (M) having the specific element contained in the resin layer (X) The particle diameter 粒子 (μm) needs to be smaller than the film thickness d (μm) of the resin layer (X).
The maximum particle diameter φ of the particles (M) having a specific element is smaller than the film thickness d (μm) of the resin layer (X), thereby achieving both scratch resistance, initial transparency, and moisture heat resistance transparency. Is possible.

[Binder resin]
In the laminated film of the present invention, the resin layer containing particles (M) having a specific element in the surface layer preferably contains an acrylic resin (A). By using the acrylic resin (A), the particles (M) having a specific element in the resin layer can be nano-dispersed, and while maintaining the transparency of the resin layer, when a force is applied to the resin layer The force can be dispersed into the particles. As a result, it is possible to improve the scratch resistance of the laminated film.

The acrylic resin (A) in the present invention, the monomer unit (a ₁₎ represented by the formula (1), a monomer unit represented by formula (2) (a _2), is expressed by equation (3) it is preferably a resin having a monomer unit (a ₃₎ that.

(In formula (1), R ₁ represents a hydrogen atom or a methyl group, and n represents an integer of 9 or more and 34 or less).

(In formula (2), the R ₂ group represents a hydrogen atom or a methyl group, and the R ₄ group represents a group containing two or more saturated carbocyclic rings).

(In formula (3), the R ₃ group represents a hydrogen atom or a methyl group. Further, the R ₅ group is a hydroxyl group, a carboxyl group, a tertiary amino group, a quaternary ammonium base, a sulfonic acid group, or phosphoric acid Represents a group)
Here, the acrylic resin (A) in the present invention is preferably a resin having a monomer unit (f ₁ ) represented by the formula (1).

  In Formula (1), when an acrylic resin having a monomer unit in which n is less than 9 is used, the dispersibility of particles (M) having a specific element in an aqueous solvent (the details of the aqueous solvent will be described later) is It becomes unstable. When an acrylic resin having a monomer unit in which n is less than 9 in the formula (1) is used, particles (M) having a specific element in the resin composition may aggregate or precipitate, or particles having a specific element in the drying step (M) may aggregate. As a result, the transparency of the laminated film may be impaired. On the other hand, since the acrylic resin having a monomer unit in which n is more than 34 in the formula (1) has extremely low solubility in the aqueous solvent, aggregation of the acrylic resin is likely to occur 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 with good transparency, or interference spots after coating film lamination may be poor.

In order for the acrylic resin (A) in the present invention to have a monomer unit (a ₁ ) represented by the formula (1), a (meth) acrylate monomer (a ₁ ′) represented by the following formula (4) It is necessary to polymerize using as a raw material.

The (meth) acrylate monomer (a ₁ ′) is preferably a (meth) acrylate monomer in which n in the formula (4) is represented by an integer of 9 or more and 34 or less, more preferably 11 or more and 32 or less (meth) Acrylate monomers, more preferably 13 or more and 30 or less (meth) acrylate monomers.

The (meth) acrylate monomer (f ₁ ′) is not particularly limited as long as it is a (meth) acrylate monomer in which n in the formula (4) is 9 or more and 34 or less. Specifically, decyl (meth) acrylate, dodecyl ( Meta) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, 1-methyl tridecyl (meth) acrylate, hexadecyl (meth) acrylate, octadecyl (meth) acrylate, eicosyl (meth) acrylate, docosyl (meth) acrylate, Tetracosyl (meth) acrylate, triaconty (meth) acrylate and the like can be mentioned, and in particular dodecyl (meth) acrylate and tridecyl (meth) acrylate are preferable. One of these may be used alone, or a mixture of two or more may be used.

Moreover, it is important that the acrylic resin (A) in the present invention is a resin having the monomer unit (a ₂ ) represented by the above formula (2).

  In the formula (2), when an acrylic resin having a monomer unit containing only one saturated carbon ring is used, the function as a steric hindrance becomes insufficient and particles (M) having a specific element in the resin composition become There may be aggregation or sedimentation, or aggregation of particles (M) having a specific element in the drying step.

Such an aggregate may be unable to obtain a laminated film with good transparency because it is larger than the wavelength of visible light. In order for the acrylic resin (A) in the present invention to have a monomer unit (a ₂ ) represented by the formula (2), a (meth) acrylate monomer (a ′) represented by the following formula (5) It is necessary to use as a raw material and to polymerize.

As the (meth) acrylate monomer (a ₂ ′) represented by the formula (5), a crosslinked fused cyclic type (having a structure in which two or more rings share two elements each and are bonded) And compounds having various cyclic structures such as spirocyclic (having a structure in which two carbon structures are linked by sharing one carbon element), specifically, bicyclo, tricyclo, tetracyclo groups and the like. Among them, particularly from the viewpoint of the compatibility with the binder, a (meth) acrylate containing a bicyclo group is preferable.

  Examples of the bicyclo group-containing (meth) acrylates include isobonyl (meth) acrylate, bornyl (meth) acrylate, disilocropentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, adamantyl (meth) acrylate and dimethyladamantyl. Examples thereof include (meth) acrylates, and in particular, isobonyl (meth) acrylate is preferable.

Further, the acrylic resin (A) in the invention is preferably a resin having a monomer unit represented by the formula ₍₃₎ (a 3).

When an acrylic resin having a monomer unit in which the R ₅ group in the formula (3) has neither a hydroxyl group, a carboxyl group, a tertiary amino group, a quaternary ammonium group, a sulfonic acid group nor a phosphoric acid group is used, an acrylic resin In the resin composition, the acrylic resin may precipitate, and particles (M) having a specific element may aggregate or precipitate in the resin composition, or the specific element in the drying step. The particles (M) may have aggregation.

Such an aggregate may be unable to obtain a laminated film with good transparency because it is larger than the wavelength of visible light. In order for the acrylic resin (A) in the present invention to have a monomer unit (a ₃ ) represented by the formula (3), the (meth) acrylate monomer (a ₃ ′) represented by the formula (6) is used as a raw material It is necessary to use and polymerize.

The following compounds are exemplified as represented by the formula (6) (meth) acrylate monomer (a ₃ ').

  As a (meth) acrylate monomer having a hydroxyl group, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2,3-dihydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene Examples thereof include monoesters of polyhydric alcohols such as glycol mono (meth) acrylate and (meth) acrylic acid, and compounds obtained by ring-opening polymerization of ε-caprolaptone to the monoesters, and 2-hydroxyethyl (especially Meta) acrylate and 2-hydroxypropyl (meth) acrylate are preferred.

  As a (meth) acrylate monomer having a carboxyl group, α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, fumaric acid, and maleic acid, or hydroxyalkyl (meth) acrylate and acid anhydride And half-esterified products of the above, and acrylic acid and methacrylic acid are particularly preferable.

  Examples of tertiary amino group-containing monomers include N, N- such as N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, etc. N, N-dialkylamino such as dialkylaminoalkyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide and the like Alkyl (meth) acrylamide etc. is mentioned, Especially, N, N- dimethylaminoethyl (meth) acrylate is preferable.

  As the quaternary ammonium base-containing monomer, those obtained by reacting the above-mentioned tertiary amino group-containing monomer with a quaternizing agent such as epihalohydrin, benzyl halide and alkyl halide are preferable, and specifically, 2- (methacryloyloxy) ) (Meth) acryloyloxyalkyl trialkyl ammonium salts such as ethyl trimethyl ammonium chloride, 2- (methacryloyloxy) ethyl trimethyl ammonium bromide, 2- (methacryloyloxy) ethyl trimethyl ammonium dimethyl phosphate, methacryloyl aminopropyl trimethyl ammonium chloride, methacryloyl (Meth) acryloylaminoalkyltrialkylammonium salts such as aminopropyltrimethylammonium bromide, tetrabutylane Tetra (meth) acrylates such as bromide (meth) acrylate, and tri-alkyl benzyl ammonium (meth) acrylates such as trimethylbenzylammonium (meth) acrylate. In particular 2- (methacryloyloxy) ethyl trimethyl ammonium chloride are preferred.

  Examples of the sulfonic acid group-containing monomer include (meth) acrylamide-alkanesulfonic acid such as butyl acrylamide sulfonic acid and 2-acrylamido-2-methylpropane sulfonic acid, or sulfoalkyl (meth) such as 2-sulfoethyl (meth) acrylate Acrylate and the like are mentioned, and 2-sulfoethyl (meth) acrylate is particularly preferable.

  As a phosphoric acid group containing acrylic monomer, acid phospho oxyethyl (meth) acrylate etc. are mentioned, Especially acid phospho oxyethyl (meth) acrylate is preferable.

Among these, in particular, the acrylic resin (A) is a resin having a monomer unit (a ₃ ) represented by the formula (3), and the R ₅ group in the formula (3) is a hydroxyl group or a carboxyl group And particles (M) having a specific element to be described later, which is high in adsorptive power and preferable in that a stronger film can be formed.

In the present invention, the content of the acrylic resin (A) in the resin layer is preferably 5 to 50% by weight, and by setting the content in this range, particles (M) having a specific element and the acrylic resin (A) Can be strengthened, and the scratch resistance of the resin layer can be improved.
In particular, the content of the acrylic resin (A) is more preferably 20% by weight or more and 70% by weight or less based on the entire resin layer, and the content of the acrylic resin (A) in the resin layer is 20% % Or more and 60% by weight or less is preferable, and 20% or more and 50% by weight or less is more preferable.

  In addition, in this invention, content in a resin layer represents content in solid content ([(mass of a resin composition)-(mass of a solvent)]) of the resin composition which forms a resin layer.

[Base layer]
The laminated film of the present invention has a thermoplastic resin layer and a resin layer (X) (hereinafter, the thermoplastic resin layer may be referred to as a base material layer). The thermoplastic resin used as the substrate layer is not particularly limited, but is preferably a layer containing polyester as a main component (hereinafter, a layer containing polyester as a main component used as a substrate layer is referred to as a polyester film There is a case). In the present invention, the main component means a component capable of suppressing 50% by weight or more with respect to the entire resin constituting the layer.

  In the present invention, the content of particles in the base layer is preferably 0.1% by weight or less based on the entire base layer. By setting the content of the particles in the above range, the internal haze can be 0.2% or less, and a laminated film excellent in transparency can be obtained.

  Hereinafter, polyester used for the base material layer of the laminated film of this invention is 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 Preferred are at least one component selected from -bis (2-chlorophenoxy) ethane-4,4'-dicarboxylate and the like.

  It is preferable that the polyester film using the said polyester is biaxially oriented. In general, a biaxially oriented polyester film is stretched by about 2.5 to 5 times each in an unstretched polyester sheet or film in the longitudinal direction and in the width direction orthogonal to the longitudinal direction, and then heat-treated to form crystals. An orientation is completed, which indicates a pattern of biaxial orientation in wide-angle X-ray diffraction. When the polyester film is biaxially oriented, the thermal stability, particularly the dimensional stability and the mechanical strength, is sufficient, and the planarity is also good.

  In the polyester film, various additives such as antioxidants, heat stabilizers, weather stabilizers, ultraviolet absorbers, organic lubricants, pigments, dyes, organic or inorganic fine particles, fillers, antistatic agents An agent, a nucleating agent, etc. may be added to such an extent that the characteristic is not deteriorated.

  The thickness of the polyester film is not particularly limited and may be appropriately selected depending on the application and type, but is preferably 10 to 500 μm, more preferably 15 to 250 μm, in terms of mechanical strength, handling properties, etc. , Most preferably 20 to 100 μm. The polyester film may be a composite film by co-extrusion, or may be a film obtained by laminating the obtained films by various methods.

[Method of producing resin layer (X)]
Examples of the method for producing the resin layer of the laminated film of the present invention will be shown below, 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. Accordingly, the scope of the present invention should not be construed as limited by the following examples.

  When the resin layer of the present invention contains particles (M) having a specific element and an acrylic resin (A), it is preferable because the resin layer is excellent in transparency, scratch resistance and slipperiness.

In a particularly preferred embodiment of the present invention, the resin layer (X) preferably contains particles (M) having a specific element having two or more different particle diameters, and specifically, an average particle diameter of 10 to 10 As particles (M1) having a specific element of 100 nm, titanium oxide (TiO ₂ ) particles and aluminum oxide (Al ₂ O ₃ ) particles are used, and as particles (M2) having a specific element having an average particle diameter of 200 to 600 nm The method of using a silica particle is mentioned.
Furthermore, in the particles (M) having the specific element, a monomer unit (a ₁ ) represented by the formula (1) and a monomer unit (a) represented by the formula (2) on part or all of the surface ₂ ) and the composition (MA) having an acrylic resin (A) having a monomer unit (a ₃ ) represented by the formula (3) are excellent in transparency and scratch resistance.
In addition, the thickness (d) of the resin layer is 0.5 μm or more and less than 1.5 μm, and the average particle diameter of particles (M2) having a specific element with an average particle diameter of 200 to 600 nm is appropriately selected. When the ratio of the thickness (d) (particle diameter (φ) / thickness (d)) is 0.3 or more and 0.6 or less, the transparency, the heat resistant transparency, and the moisture resistant heat transparency can be compatible.

  In the resin layer, if necessary, particles (M) having a specific element, compounds other than acrylic resin (A), for example, polymer resins such as polyester resin, acrylic resin, urethane resin, aziridine The compound may contain a titanate coupling agent such as titanium chelate. In addition, various additives, for example, organic lubricants, organic or inorganic fine particles, antistatic agents, etc. may be added to the extent that they do not deteriorate the characteristics.

  In the present invention, at least one cross-linking agent selected from melamine compounds, oxazoline compounds, carbodiimide compounds, isocyanate compounds, and epoxy compounds is required as the other compound (C) other than the particles (M) having a specific element There is. By using this crosslinking agent, the scratch resistance due to the curing of the resin layer (X) can be improved.

  Examples of melamine compounds include melamine, methylolated melamine derivatives obtained by condensing melamine and formaldehyde, compounds obtained by reacting lower alcohols with methylolated melamine to partially or completely etherify, and mixtures thereof, etc. It can be used. Specifically, compounds having triazine and methylol groups are particularly preferable. The melamine compound in the present invention refers to a component derived from the melamine compound when the melamine compound to be described next forms a crosslinked structure with an acrylic resin (A), an oxazoline compound, or a carbodiimide compound, an isocyanate compound, an epoxy compound or the like. Means Moreover, as a melamine type compound, any may be sufficient as the condensate which consists of a monomer and a multimer more than a dimer, and these mixtures may be sufficient. As lower alcohols used for etherification, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butanol, isobutanol etc. can be used. As the group, imino group, methylol group or alkoxymethyl group such as methoxymethyl group or butoxymethyl group is contained in one molecule, and imino group methylated melamine resin, methylol group melamine resin, methylol group methyl Melamine resins and fully alkylated methylated melamine resins. Among them, methylolated melamine resin is most preferable. Furthermore, an acidic catalyst such as p-toluenesulfonic acid may be used to accelerate the thermal curing of the melamine compound.

  When such a melamine compound is used, not only the improvement of the scratch resistance due to the increase in coating film hardness due to the self condensation of the melamine compound is observed, but also the reaction of the hydroxyl group and the carboxylic group contained in the acrylic resin progresses with the melamine compound. A stronger resin layer can be obtained, and a film excellent in scratch resistance can be obtained. Furthermore, low molecular weight substances such as oligomers contained in the laminated film can suppress surface deposition under a moist heat environment, and can exhibit wet heat resistance transparency.

  When an oxazoline compound or an oxazoline compound forms a crosslinked structure with an acrylic resin (A), a melamine compound, an isocyanate compound, or a carbodiimide compound etc. which are described next, an oxazoline compound means the component derived from an oxazoline compound. The oxazoline compound is not particularly limited as long as it has an oxazoline group as a functional group in the compound, but it contains at least one or more monomers containing an oxazoline group, and at least one other compound. What consists of an oxazoline group containing copolymer obtained by copolymerizing a monomer is preferable.

  As a monomer containing an oxazoline group, 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline and the like can be used, and mixtures of one or more of these can also be used. Among them, 2-isopropenyl-2-oxazoline is preferable because it is industrially available.

  The at least one other monomer used for the oxazoline group-containing monomer in the oxazoline compound is not particularly limited as long as it is a monomer which can be copolymerized with the oxazoline group-containing monomer. Acrylic acid esters or methacrylates such as methyl methacrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, acrylic acid, Unsaturated carboxylic acids such as methacrylic acid, itaconic acid and maleic acid, unsaturated nitriles such as acrylonitrile and methacrylonitrile, acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacryl Unsaturated amides such as imido, vinyl esters such as vinyl acetate and vinyl propionate, vinyl ethers such as methyl vinyl ether and ethyl vinyl ether, olefins such as ethylene and propylene, vinyl chloride, vinylidene chloride, vinyl fluoride and the like Halogen-.alpha.,. Beta.-unsaturated monomers, .alpha.,. Beta.-unsaturated aromatic monomers such as styrene, .alpha.-methylstyrene and the like can be used, and mixtures of one or more of these can be used. You can also.

  The carbodiimide compound in the present invention refers to a component derived from the carbodiimide compound when the carbodiimide compound described below or the carbodiimide compound forms a crosslinked structure with the acrylic resin (A), the melamine compound, the isocyanate compound, or the oxazoline compound, etc. means. The carbodiimide compound is not particularly limited as long as it has a carbodiimide group as a functional group in the compound or one or more cyanamide groups in the molecule in a tautomeric relationship.

  A well-known technique can be applied to manufacture of a carbodiimide compound, Generally, a carbodiimide compound is obtained by polycondensing a diisocyanate compound in catalyst presence. As a diisocyanate compound which is a starting material of the carbodiimide compound, aromatic, aliphatic or alicyclic diisocyanate can be used. Specifically, tolylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, cyclohexane diisocyanate , Isophorone diisocyanate, dicyclohexyl diisocyanate and the like can be used.

The isocyanate compound in the present invention is derived from the isocyanate compound when the isocyanate compound described below or the isocyanate compound forms a crosslinked structure with the acrylic resin (A), the melamine compound, the epoxy compound, the oxazoline compound, or the carbodiimide compound, etc. Mean ingredients that
As the isocyanate compound, for example, tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, metaxylylene diisocyanate, hexamethylene-1,6-diisocyanate, 1,6-diisocyanate hexane, an adduct of tolylene diisocyanate and hexanetriol, Adduct of tolylene diisocyanate and trimethylolpropane, polyol-modified diphenylmethane-4,4'-diisocyanate, carbodiimide-modified diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, 1,5-naphthalene diisocyanate, 3,3'-bitrylene- By using 4,4 'diisocyanate, 3,3'dimethyldiphenylmethane-4,4'-diisocyanate, metaphenylene diisocyanate etc. Can. In particular, it is preferable to use a polymer type isocyanate compound having a plurality of isocyanate groups at the terminal or side chain of a polymer such as polyester resin or acrylic resin, because the toughness of the resin layer (X) is enhanced. Can.

  Furthermore, when applying to the in-line coating method mentioned later, it is preferable that an isocyanate compound is a water dispersion. In particular, in view of the pot life of the coating agent, a blocked isocyanate compound having an isocyanate group masked by a blocking agent is particularly preferable. As a crosslinking reaction of the blocking agent, there is known a system in which the blocking agent is volatilized by the heat of the drying step after coating to expose the isocyanate group to cause the crosslinking reaction. The isocyanate group may be a monofunctional type or a multifunctional type, but the crosslink density of the layer (X) is improved by the block type polyisocyanate compound of the multifunctional type, and the wet heat of the printed layer or the hard coat layer is obtained. It is preferable because of excellent adhesion.

  Examples of low molecular weight or high molecular compounds having two or more blocked isocyanate groups include tolylene diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate 3 mole adduct of trimethylolpropane, polyvinyl isocyanate, vinyl isocyanate copolymer, polyurethane-terminated diisocyanate Using a methyl ethyl ketone oxime block of tolylene diisocyanate, a sodium hyposulfite block of hexamethylene diisocyanate, a methyl ethyl ketone oxime block of polyurethane terminal diisocyanate, a phenol block to 3-mole adduct of trimethylolpropane with tolylene diisocyanate, etc. it can.

  The epoxy compound to be used in the present invention is derived from the epoxy compound when the epoxy compound described below or the epoxy compound forms a crosslinked structure with the acrylic resin (A), the melamine compound, the isocyanate compound, the oxazoline compound, or the carbodiimide compound. Mean ingredients that The epoxy compound is a compound having one or two or more epoxy groups in the molecule as a functional group in the compound, and the molecular weight is more preferably 1,000 or less in the molecule. Although the kind of epoxy compound is not specifically limited, For example, sorbitol polyglycidyl ether type, polyglycerol polyglycidyl ether type, diglycerol polyglycidyl ether type, polyethylene glycol diglycidyl ether type etc. can be used. For example, Nagase Chemtech Co., Ltd. epoxy compound “Denacol” (EX-611, EX-614B, EX-512, EX-521, EX-421, EX-313, EX-810, EX-830, EX-850, etc. ), Diepoxy-polyepoxy compounds (SR-EG, SR-8EG, SR-GLG, etc.) manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., epoxy compounds “EPICLON” EM-85-75W manufactured by Dainippon Ink Industries Co., Ltd., or CR- 5 L etc. can be used suitably, Especially, what has water solubility is preferable.

  The epoxy compound preferably has an epoxy equivalent weight (weight per epoxy equivalent: WPE) of 100 to 300 WPE in terms of reactivity, and the epoxy equivalent is more preferably 110 to 200 WPE.

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

In the laminated film of the present invention, when a resin composition containing particles (M) having a specific element and an acrylic resin (A) is applied onto a polyester film, and the resin composition contains a solvent, the solvent is used. It can be obtained by forming a resin layer on a polyester film by drying.
Also, a resin composition containing particles (M) having a specific element and an acrylic resin (A) is applied onto a polyester film, and when the resin composition contains a solvent, the solvent is dried, It can be obtained by forming a resin layer on a polyester film.

  In the present invention, when the solvent is contained in the resin composition, it is preferable to use an aqueous solvent as the solvent. By using an aqueous solvent, it is possible to suppress rapid evaporation of the solvent in the drying step, and not only to form a uniform composition layer, but also to be excellent in terms of environmental impact.

  Here, the aqueous solvent is water or soluble in water such as water and water, 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. And organic solvents which are mixed in any ratio.

  In the present invention, when an aqueous solvent is used, it is preferable to apply an aqueous coating agent containing a resin composition containing particles (M) having a specific element and an acrylic resin (A). This is because the water dispersing agent or the emulsifying agent is arranged on the surface of the coating film in the state where the solvent is dried by coating as a water-based coating agent, compared to the organic solvent-based coating agent. It is because hardening inhibition is suppressed and the thickness of the resin layer is excellent in scratch resistance even if it is a thin film.

  In addition, as a resin composition (a) containing the particle (M) which has a specific element, and the method of making an acrylic resin (A) into a water-based paint, the resin containing the particle (M) which has a specific element Examples of the method include a method in which a hydrophilic group such as a carboxylic acid or a sulfonic acid is contained in the composition (a) or the acrylic resin (A), or a method in which the resin is emulsified using an emulsifying agent.

  It is preferable that the coating method to the polyester film of a resin composition is an in-line coating method. The in-line coating method is a method of coating in the process of producing a polyester film. Specifically, it refers to a method of coating at any stage from melt extrusion of polyester resin to biaxial heat treatment, heat treatment and winding up, and usually, substantially non-molten after melt extrusion / quenching Unstretched (unoriented) polyester film in crystalline state (A film), then uniaxially stretched (uniaxially oriented) polyester film (B film) stretched in the longitudinal direction, or biaxially before heat treatment further stretched in the width direction 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 A film and the B film before the crystal orientation is completed, and then the polyester film is stretched uniaxially or biaxially to obtain a solvent. It is preferable to adopt a method of heat treatment at a temperature higher than the boiling point to complete the crystal orientation of the polyester film and to provide a resin layer. According to this method, it is possible to simultaneously perform the film formation of the polyester film and the coating and drying of the resin composition (that is, the formation of the resin layer), which is advantageous in terms of manufacturing cost. Moreover, 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 the resin composition is applied to a film uniaxially stretched in the longitudinal direction (B film) and then stretched in the width direction and heat-treated is excellent. After being applied to an unstretched film, compared to the method of biaxial stretching, there is one less stretching step, so it is difficult to generate defects or cracks in the composition layer due to stretching, and a composition layer excellent in transparency and smoothness It is because it can be formed.

  Furthermore, by providing the resin layer by the in-line coating method, the resin layer is subjected to a stretching treatment to promote the surface alignment of the particles (M) having a specific element, and as a result, the scratch resistance of the resin layer Can be expressed.

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

  Therefore, the best method of forming a resin layer in the present invention is a method of forming a resin composition using an aqueous solvent by applying it on a polyester film using an in-line coating method, drying and heat treatment. More preferably, the resin composition is in-line coated 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. The heat treatment may be performed at a temperature of 160 to 240 ° C. in order to complete the crystal orientation of the polyester film and complete the thermal curing 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 using a polyethylene terephthalate (hereinafter, PET) film as a polyester film as an example, but the present invention is not limited thereto. First, PET pellets are sufficiently vacuum dried and then supplied to an extruder, melt extruded into a sheet at about 280 ° C., and solidified by cooling to prepare an unstretched (unoriented) PET film (A film). This film is stretched 2.5 to 5.0 times in the longitudinal direction by 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 coated on one side of this B film.

  At this time, surface treatment such as corona discharge treatment may be performed on the coated surface of the PET film before coating. By performing surface treatment such as corona discharge treatment, the wettability of the resin composition to the PET film can be improved, repelling of the resin composition can be prevented, and a resin layer having a uniform coating thickness can be formed. After application, the end of the PET film is gripped by a clip and led to a heat treatment zone (preheating zone) at 80 to 130 ° C. to dry the solvent of the resin composition. After drying, it is stretched 1.1 to 5.0 times in the width direction. Subsequently, it is conducted to a heat treatment zone (heat setting zone) at 160 to 240 ° C. to carry out a heat treatment for 1 to 30 seconds to complete crystal orientation.

  In the heat treatment step (heat setting step), a relaxation treatment of 3 to 15% may be performed in the width direction or the longitudinal direction as necessary. The laminated film thus obtained becomes a laminated film excellent in transparency, scratch resistance and antiblocking property.

  In the laminated film of the present invention, an intermediate layer may be provided between the resin layer and the thermoplastic resin layer, but in the case of providing the intermediate layer, the film on which the intermediate layer is laminated may be wound or In the process until the resin layer of the invention is provided, the film may be scratched. Therefore, in the present invention, it is preferable that the resin layer and the thermoplastic resin layer be directly laminated.

  The laminated film of the present invention is not limited to the constitution of the thermoplastic resin layer, and, for example, a single layer constitution consisting only of the A layer, a laminate constitution of the A layer / B layer, ie two kinds and two layers lamination constitution, A layer / B Layers / layers have a laminated structure, that is, two layers and three layers, and layers A / B / C have a layer structure, such as three layers and three layers.

  The lamination method of the thermoplastic resin layer in the laminated film of the present invention is not limited, and examples thereof include a lamination method by co-extrusion method, a lamination method by bonding, a method by combination thereof, etc. From the viewpoint of the properties and the production stability, it is preferable to employ a coextrusion method. In the case of forming a laminate, different resin configurations may be used in order to provide different functions to the respective layers. For example, in the case of a laminated structure of A layer / B layer / A layer, that is, a two-kind three-layer laminated structure, the B layer is composed of homopolyethylene terephthalate from the viewpoint of transparency And methods such as adding particles.

  Here, when particles for imparting lubricity are added to the layer A, the moisture resistance to heat transparency is excellent even if the particle diameter of the particles (M) of the resin layer (X) is small.

  In particular, in the present invention, when homopolyethylene terephthalate is used in layer B and a polyester resin containing slippery particles is used in layer A, the base film is compared with the case where a single-layer laminated film consisting only of layer A is used. When the film thickness is thickened, the film haze can be suppressed and the transparency is excellent, which is preferable.

  The slippery particles include inorganic particles or organic particles. Examples of the inorganic particles include oxide particles such as silica, alumina and zirconia, and metal compound particles such as calcium carbonate. Examples of the organic particles include crosslinked styrene particles, epoxy particles, polyphenylene sulfide particles, and polyamideimide particles. Among them, particles containing a styrene component (particularly, crosslinked styrene particles), calcium carbonate particles, and the like are particularly preferable from the viewpoint of controlling the refractive index and particle diameter.

[Method of measuring characteristic and method of evaluating effect]
The measuring method of the characteristic in this invention and the evaluation method of an effect are as follows.

(1) Maximum particle diameter Using a microtome, the cross section of the resin layer (X) is observed using a scanning electron microscope (SEM), and the cross section of the resin layer (X) is observed. Particle size distribution was determined using image analysis software Image-Pro Plus (Nippon Roper, Inc.). Cross-sectional pictures are selected from different measurement fields of view, the diameters (equivalent circle diameters) of 200 or more particles arbitrarily selected from the cross-sectional pictures are measured, and the horizontal axis is the particle size, and the vertical axis is the particle abundance ratio The obtained volume based particle size distribution was obtained. In the volume-based particle size distribution described above, the particle diameter that carries the horizontal axis is the class at every 10 nm interval starting from 0 nm, and the abundance ratio of particles that carry the vertical axis is the formula “existence ratio = corresponding particle diameter It is represented by “total volume of detected particles / total volume of all detected particles”. Among the local maximum values of the chart of the abundance ratio of particles obtained as described above, the particle diameter of the peak top showing the local maximum of the particle diameter was read.

Sample preparation: BIB method · Device name: EMICA TIC 3X made by Leica Microsystems
・ Type of beam: Ar
Processing conditions: 5.0 kV, 10 h
-After embedding the resin in resin, make a cross section by dry polishing, Ar ion milling with a processing device, sputter coating (platinum, 10 nm), and deposition of C (carbon) is carried out.

Observation device: field emission scanning electron microscope (Hitachi High-Technologies S4800)
Observation condition: Acceleration voltage 1.5kV
Observation magnification: 100000 times.

(2) Thickness of Resin Layer (1) Similarly to the above, the thickness of the resin layer was measured by observing the cross section of the resin layer (X) using a scanning electron microscope (SEM).

(3) Particle diameter (1) Similarly, the cross section of the resin layer (X) is observed using a scanning electron microscope (SEM), and the particle size distribution of the particles present in the film is image analysis software It asked using Image-Pro Plus (Nippon Roper Co., Ltd.). Cross-sectional pictures are selected from different measurement fields of view, the diameters (equivalent circle diameters) of 200 or more particles arbitrarily selected from the cross-sectional pictures are measured, and the horizontal axis is the particle size, and the vertical axis is the particle abundance ratio The obtained volume based particle size distribution was obtained. In the volume-based particle size distribution described above, the particle diameter that carries the horizontal axis is the class at every 10 nm interval starting from 0 nm, and the abundance ratio of particles that carry the vertical axis is the formula “existence ratio = corresponding particle diameter It is represented by “total volume of detected particles / total volume of all detected particles”. From the chart of the abundance ratio of particles obtained as described above, the particle size of the peak top showing the maximum was read.

(4) Using an element SEM (scanning electron microscope) of the particles contained in the resin layer, the surface of the resin layer is observed at a magnification of 100,000 times to obtain EDX for the particles contained in the resin layer on the polyester film. Elemental analysis by (energy dispersive X-ray spectroscopy) was performed to determine specific elements of interest.

  Measure the element detection with QUANTAX Flat QUAD System (model number Xflash 5060FQ) manufactured by Bruker AXS for particles having a specific element contained in the resin layer observed with a field emission type scanning electron microscope (model number S-4800) manufactured by Hitachi High-Technologies The element of the contained particles was determined.

(5) Haze (transparency)
The haze is measured in a normal state (23 ° C., relative humidity 50%) after leaving the laminated film sample for 40 hours, using a turbidity meter “NDH 5000” manufactured by Nippon Denshoku Kogyo Co., Ltd. JIS K 7136 “transparent The method is based on the method described in "How to Determine the Haze of Materials" (2000 version). In addition, it irradiated and measured light from the surface side in which the resin layer of the sample was laminated | stacked. The sample prepared 10 samples of the square of 50 mm of one side, and made the haze value of the sample the average value measured a total of 10 times once each and each.
Moreover, transparency evaluated four steps by haze value. C is a level which has a problem in practical use, A is a practical level, and S is good.
S: 1.0% or less A: more than 1.0% to 2.0% or less C: more than 2.0%.

(6) Moisture and heat resistance (Δ haze value)
The haze before the treatment and the haze after the treatment were measured for the change in appearance of the laminate film after the laminate film was treated under an environment of 85 ° C. and 85% RH for 500 hours, and the difference in haze (Δ haze) was measured. evaluated. Here, in the sample in which the resin layer (X) was formed only on one side of the laminated film, the side of the laminated film opposite to the resin layer was a non-woven fabric containing acetone (manufactured by Ozu Sangyo Co., Ltd., HIZEGASE NT-4) The resin was flushed with acetone, and then it was flushed with acetone and allowed to stand in the normal state for 40 hours for drying to remove the deposit on the surface of the laminated film opposite to the resin layer. Then, the haze value after wet heat processing was measured by the method as described in said clause (5), and the difference ((DELTA)) of the haze value of the resin layer single-sided before and behind heat processing was evaluated as (DELTA) haze value.
After processing the sample in which the resin layer was formed on both sides of the laminated film, the haze value after wet heat treatment was measured by the method described in (5), and the difference in haze value before and after heat treatment was halved (50%) The value was taken as the difference (Δ) of the haze value on one side of the resin layer, and this was evaluated as the Δ haze value.
S: ΔHaze less than 0.2% A: ΔHaze 0.2% or more and less than 0.5% B: ΔHaze 1.0% or more and less than 3.0% C: ΔHaze 3.0% or more (7 ) Heat resistant transparency (oligomer blockability) (Δ haze value)
The haze before the treatment and the haze after the treatment were respectively measured for the change in appearance of the laminate film after the laminate film was heat treated at 150 ° C. for 2 hours, and the difference in haze (Δ haze) was evaluated. Here, in the sample in which the resin layer (X) was formed only on one side of the laminated film, the side of the laminated film opposite to the resin layer was a non-woven fabric containing acetone (manufactured by Ozu Sangyo Co., Ltd., HIZEGASE NT-4) The resin was flushed with acetone, and then it was flushed with acetone and allowed to stand in the normal state for 40 hours for drying to remove the deposit on the surface of the laminated film opposite to the resin layer. Then, the haze value after heat processing was measured by the method as described in preceding clause (5), and the difference ((DELTA)) of the haze value of the resin layer single-sided before and behind heat processing was evaluated as delta haze value.

(8) Scratch resistance A steel wool (Bonstar # 0000, manufactured by Nippon Steel Wool Co., Ltd.) was rubbed back and forth for 10 cycles under a load of 200 g / cm ² to visually confirm the occurrence of scratches on the surface of the laminated film. Evaluation was carried out.
S: no scratch A: 1 to 5 scratches B: 6 to 10 scratches C: 11 or more scratches.

(9) Adhesiveness 100 crosscuts of 1 mm ² are put on the resin layer side of the laminated film, and "Sellotape" (registered trademark) (Nichiban Co., Ltd. product, CT405AP) is stuck, and 1.5 kg / cm with a hand roller. After pressing with a load of ² , the laminated film was rapidly peeled off in the direction of 90 degrees. The adhesion was evaluated in four steps according to the number of remaining grids. Evaluation was performed by the value of the average implemented 10 times. C is a level which has problems in practical use, B is a practical level, and those of A and S are considered good.
S: 90-100 residual A: 80-89 residual B: 50-79 residual C: 0-49 residual.

(10) Interference unevenness Attach a black glossy tape (Yamato Co., Ltd., vinyl tape No. 200-50-21: black) on the opposite side of the resin layer (X) of the laminated film so as not to trap air bubbles. I put it together.

  This sample is placed in a dark room 30 cm just under a three-wavelength fluorescent lamp (Panasonic Co., Ltd., three-wavelength type daylight white (F · L 15 EX-N 15 W)), and the degree of interference unevenness is observed visually while changing the viewing angle The following evaluations were made. The thing of A or more was made favorable.

S: Interference unevenness hardly visible A: Interference unevenness slightly visible C: Interference unevenness is strong (11) Ten-point average roughness (Rz)
The resin layer side surface of the laminated film was measured by a stylus method under the following conditions using a three-dimensional surface roughness tester (manufactured by Kosaka Laboratory, ET-4000A) to obtain a ten-point average roughness (SRz) . In addition, the measurement changed the sampling place, measured ten samples, and employ | adopted the average value of eight points except the maximum value and minimum value.
Needle diameter 0.5 (μmR)
Needle pressing pressure 100 (μN)
Vertical magnification 20000 (times)
Low pass CUT OFF 200 (μm)
Wide area CUT OFF 0 (μm)
Measuring speed 100 (μm / s)
Measurement interval X direction 1 (μm), Y direction 5 (μm)
Number of records: 81 Hysteresis width: 0.000 (μm)
Reference area 1 mm in X direction, 0.4 mm in Y direction.

(12) Internalize On the resin layer (X) side of the laminated film and on the side of the laminated film opposite to the resin layer (X), the following UV curable resin is cured using a bar coater. It applied uniformly so that thickness might be set to 2 micrometers, and the lamination film for internal haze measurement was created. Then, the haze was measured by the haze measuring method as described in (4) to the lamination film for internal haze measurement, and it was set as the inside haze of the lamination film.

・ UV curable resin: DIC "Unidic" V6841
・ Integrated irradiation intensity: 500mJ / cm ²
(13) Reflectance Spectrum A film sheet cut into an A4 cut size was divided into three in vertical and horizontal directions, and a total of nine points were used as measurement samples. The long side was taken as the longitudinal direction. Measurement of the spectral reflectance does not entrap air bubbles on the back side of the measurement surface (the resin layer) with a 50 mm wide black glossy tape (Yamato Co., Ltd., vinyl tape No. 200-50-21: black) After bonding the sample and the tape in the same longitudinal direction, they are cut into sample pieces of about 4 cm square, and have a wavelength of 400 to 800 nm at an incident angle of 5 ° in a spectrophotometer (UV2450 manufactured by Shimadzu Corporation) Spectral reflectance was measured in the range. The direction in which the sample was set in the measuring device was such that the longitudinal direction of the sample was in the front-back direction toward the front of the measuring device. Note for scaling the reflectance, Al ₂ O ₃ was used plate that comes as standard reflection plate.

<Reference Example 1> Emulsion (EM-1) containing a composition (MA-1) having an acrylic resin (A) on the surface of particles (M) having a specific element
100 parts by weight of isopropyl alcohol as a solvent was charged into a normal acrylic resin reaction vessel equipped with a stirrer, thermometer, and a reflux condenser, and heated and stirred, and kept at 100 ° C.
Among them, 40 parts by weight of eicosyl methacrylate of n = 19 as (meth) acrylate (a'-1), and 40 parts by weight of isobonyl methacrylate having 2 rings as (meth) acrylate (a'-2) A mixture consisting of 20 parts by weight of 2-hydroxyethyl acrylate was added dropwise over 3 hours as a (meth) acrylate (a'-3) having a part and other hydroxyl groups. After completion of the dropwise addition, the mixture was heated at 100 ° C. for 1 hour, and then an additional catalyst mixed solution consisting of 1 part by weight of t-butylperoxy-2-ethylhexaate was charged. Subsequently, after heating at 100 degreeC for 3 hours, it cooled and the acrylic resin (A-1) was obtained.

Particles (“NanoTek” Al ₂ O ₃ slurry (number average particle diameter 30 nm, manufactured by CI Kasei Co., Ltd.) having Al elements as particles (M) having specific elements) are used in an aqueous solvent, “NanoTek” Al ₂ O ₍₃ ) A slurry and the above acrylic resin (A-1) are added in order, dispersed by the following method, and containing a mixed composition (MA-1) of particles (M) having a specific element and an acrylic resin (A-1) To obtain an emulsion (EM-1) (Method of (ii) above).
The additive amount ratio (mass ratio) of the particles (M) having a specific element and the acrylic resin (A-1) was (M) / (A-1) = 40/20 (note that the mass ratio is the decimal point It is calculated by rounding off the first place). The dispersion process was performed using a homomixer, and was performed by rotating for 5 hours at a peripheral speed of 10 m / s. The mass ratio of the particles (M) to the acrylic resin (A) in the finally obtained composition (MA) was (A) / (B-1) = 40/20 (note that the mass The ratio is calculated by rounding the first decimal place).

  The obtained composition (MA-1) was centrifuged using a Hitachi tabletop ultracentrifuge (manufactured by Hitachi Koki Co., Ltd .: CS150NX) (rotation speed: 3000 rpm, separation time: 30 minutes), and specific element elements were removed. After precipitating particles (M) (and acrylic resin (A) adsorbed on the surface of particles (M) having a specific element element), the supernatant was removed and the precipitate was concentrated to dryness. As a result of analyzing the concentrated and dried precipitate by X-ray photoelectron spectroscopy (XPS), it was confirmed that the acrylic resin (A) was present on the surface of the particles (M) having a specific element. That is, the acrylic resin (A) is adsorbed and attached to the surface of the particles (M) having a specific element, and the obtained composition (MA) is on the surface of the particles (M) having a specific element It turned out that it corresponds to the particle | grains which have an acrylic resin (A).

<Reference Example 2> Emulsion (EM-2) containing a composition (MA-2) having an acrylic resin (A) on the surface of particles (M) having a specific element
The additive amount ratio (mass ratio) of the particles (M) having a specific element of Reference Example 1 and the acrylic resin (A) was set to (M) / (A) = 10/50 (note that the mass ratio is the decimal point number An emulsion (EM-2) containing a mixed composition (MA-2) of the particles (M) and the acrylic resin (A) was obtained by the same method as in Reference Example 1 except that the first place was rounded off. Obtained.

<Reference Example 3> Emulsion (EM-3) containing a composition (MA-3) having an acrylic resin (A) on the surface of particles (M) having a specific element
The additive amount ratio (mass ratio) of the particles (M) having a specific element of Reference Example 1 and the acrylic resin (A) was set to (M) / (A) = 60/10 (note that the mass ratio is the decimal point number An emulsion (EM-3) containing a mixed composition (MA-3) of particles (M) and an acrylic resin (A) was obtained by the same method as in Reference Example 1 except that the first place was rounded off. Obtained.

<Reference Example 4> Emulsion (EM-4) containing a composition (MA-4) having an acrylic resin (A) on the surface of particles (M) having a specific element
As a particle (M) having a specific element, a “NanoTek” TiO ₂ slurry containing Ti element (a particle (M in a manner similar to Reference Example 1 except that a number average particle diameter of 36 nm manufactured by CI Kasei Co., Ltd. was used) An emulsion (EM-4) containing a mixed composition (M-4A) of a) and an acrylic resin (A) was obtained.

Reference Example 5 Emulsion (EM-5) Containing Composition (MA-5) Having Acrylic Resin (A) on the Surface of Particle (M) Having a Specific Element
As a particle (M) having a specific element, Reference Example 1 and Comparative Example 1 were used except that “Snowtex (registered trademark)” OL colloidal silica slurry (number average particle diameter 40 nm manufactured by Nissan Chemical Industries, Ltd.) containing Si element was used. In the same manner, an emulsion (EM-5) containing a mixed composition (MA-5) of the particles (M) and the acrylic resin (A) was obtained.

Reference Example 6 Emulsion (EM-6) Containing Composition (MA-6) Having Acrylic Resin (A) on the Surface of Particle (M) Having a Specific Element
A particle is prepared in the same manner as in Example 1 except that “Nanouse (registered trademark)” ZR (number average particle diameter 90 nm manufactured by Nissan Chemical Industries, Ltd.) containing Zr element is used as particles (M) having a specific element. An emulsion (EM-6) containing a mixed composition (MA-6) of the particles (M) and the acrylic resin (A) was obtained.

Reference Example 7 Preparation of Acrylic Resin (A-7) Under a nitrogen gas atmosphere and at normal temperature (25 ° C.), 100 parts by weight of water and 1 weight of polyethylene glycol monomethacrylate (16 ethylene oxide repeating units) were contained in Container 1 Parts and 0.5 parts by weight of ammonium persulfate were charged, the temperature was raised to 70 ° C., and dissolved to obtain a solution 1 at 70 ° C. Next, under the normal temperature (25 ° C.), the following raw materials were added to the container 2 at the following ratio in a container 2 and stirred to obtain a solution 2.
Polyethylene glycol monomethacrylate (the repeating unit of ethylene oxide is 16) 5 molar parts Methyl methacrylate 62 molar parts Ethyl acrylate 30 molar parts Acrylic acid 2 molar parts N-methylol acrylamide 1 molar part and then 100 parts by weight To solution 2, 50 parts by weight of water was added to obtain solution 3. Under an atmosphere of nitrogen gas, Solution 1 was transferred to a reactor, and Solution 3 was continuously dripped into Solution 1 over 3 hours while maintaining the temperature of the solution in the reactor at 70 ° C. After completion of the dropwise addition, the mixture was further stirred at 85 ° C. for 2 hours, cooled to 25 ° C., and neutralized with aqueous ammonia to obtain an acrylic resin (A-7) emulsion.

Reference Example 8 Polymerization of Thermoplastic Polyester Resin (PET-A) An esterification reaction product which is a reaction product of terephthalic acid and ethylene glycol is stored in advance in a molten state at 255 ° C., and terephthalic acid and ethylene glycol are further added to terephthalic acid. The slurry is made to be a slurry so that the molar ratio of ethylene glycol to acid is 1.15, fixed amount is supplied while maintaining the temperature of the esterification reaction tank, and the esterification reaction is carried out while distilling water to obtain the esterification reaction product. The The obtained esterification reaction product is transferred to a polymerization reaction tank, and an ethylene glycol solution containing phosphoric acid and an ethylene glycol solution containing magnesium acetate tetrahydrate, an ethylene glycol solution containing antimony trioxide, and potassium hydroxide are contained. Separately, an alkali metal element, an alkaline earth metal element, and a phosphorus element are separately added to the polyester resin to be obtained so that the M / P is 2.8 and the antimony element is 60 ppm, and the ethylene glycol solution is subsequently added. The inside of the polymerization reaction vessel was gradually depressurized to be 0.13 kPa or less in 30 minutes, and at the same time, the temperature was gradually raised to 280 ° C. to carry out the polymerization reaction. Thereafter, the polycondensation reaction tank was returned to normal pressure with nitrogen gas, discharged in a strand shape into cold water from a die, pelletized into a cylindrical shape with an extrusion cutter, and precrystallized with a surface crystallization device to obtain a liquid phase polyester . Using the liquid phase polyester obtained here, solid state polymerization is performed at a temperature of 215 ° C. for 20 hours under a reduced pressure of 0.13 KPa by a rotary vacuum drying apparatus to obtain a thermoplastic polyester resin (PET-A). The The obtained polyester resin (PET-A) contained substantially no particles, had an inherent viscosity of 0.63, and a cyclic trimer content of 0.44% by mass.

<Reference Example 9> Polymerized PET-A of a thermoplastic polyester resin (PET-B) and calcium carbonate particles having an average particle diameter of 1 μm were mixed, and these mixtures were melt-kneaded to obtain master pellets. Here, the amount of particles was adjusted to 1% by mass.

<Reference Example 10> Polymerized PET-A of a thermoplastic polyester resin (PET-C) and crosslinked polystyrene particles having an average particle diameter of 0.3 μm were mixed, and the mixture was melt-kneaded to obtain master pellets. Here, the amount of particles was adjusted to 2% by mass.

<Reference Example 11> Polymerized PET-A of a thermoplastic polyester resin (PET-D) and crosslinked polystyrene particles having an average particle diameter of 0.8 μm were mixed, and these mixtures were melt-kneaded to obtain master pellets. Here, the amount of particles was adjusted to 1% by mass.

<Reference Example 12> Polymerized PET-A of a thermoplastic polyester resin (PET-E) and alumina particles having an average particle diameter of 0.1 μm were mixed, and the mixture was melt-kneaded to obtain a master pellet. Here, the amount of particles was adjusted to 2% by mass.

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

Example 1
First, Resin Composition 1 was prepared as follows.
<Resin composition>
The following emulsion was mixed with the aqueous solvent at a ratio described in the table to obtain a resin composition 1.

· Mixed composition of particles (M) having a specific element and acrylic resin (A-1) (MA-1): 60 parts by weight · Melamine-based compound ("Beckamine (registered trademark)" APM manufactured by DIC) 40 parts by weight -Particles having a specific element (M2) (manufactured by Nippon Shokuhin Co., Ltd. "Sea Hoster (registered trademark)" KEW 30) 0.1 parts by weight <Laminated film>
Then, after substantially vacuum drying PET pellets (intrinsic viscosity: 0.63 dl / g) substantially free of particles, they are fed to an extruder and melted at 285 ° C., extruded from a T-shaped nozzle into a sheet, The film was wound around a mirror surface casting drum having a surface temperature of 25 ° C. by using an electric application casting method to cool and solidify. The 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, a resin composition 1 was applied to a corona discharge treated surface of a uniaxially stretched film using a bar coat to a coating thickness of about 6 μm. Both ends in the width direction of the uniaxially stretched film coated with the resin composition are gripped by clips and led to the preheating zone to make the atmosphere temperature 75 ° C. Subsequently, the atmosphere temperature is made 110 ° C. using a radiation heater, and then the atmosphere temperature The resin composition was dried at 90 ° C. to form a resin layer. Subsequently, the laminate film is continuously stretched 3.5 times in the width direction in a heating zone (stretching zone) at 120 ° C., and subsequently heat treated for 20 seconds in a heat treatment zone (heat setting zone) at 230 ° C. I got In the obtained laminated film, the thickness of the PET film was 50 μm, and the thickness of the resin layer was 0.7 μm.
Properties and the like of the obtained laminated film are shown in the table.
It was excellent in transparency, scratch resistance, moisture heat resistance transparency, and interference unevenness.

Example 2
A laminated film was obtained in the same manner as in Example 1 except that the resin composition in the coating solution was changed as follows. Properties and the like of the obtained laminated film are shown in the table.
<Resin composition>
-60 parts by weight of a composition (MA-2) having an acrylic resin (A) on the surface of particles (M) having a specific element-Melamine-based compound ("Beckamine (registered trademark)" APM manufactured by DIC) 40 parts by weight 0.1 parts by weight of particles having a specific element (M2) (manufactured by Nippon Shokuhin Co., Ltd. “Sea Hoster (registered trademark)” KEW 30).

Example 3
A laminated film was obtained in the same manner as in Example 1 except that the resin composition in the coating solution was changed as follows. Properties and the like of the obtained laminated film are shown in the table.
<Resin composition>
· Composition having an acrylic resin (A) on the surface of particles (M) having a specific element (MA-3) 60 parts by weight · Melamine-based compound ("Beckamine (registered trademark)" APM manufactured by DIC) 40 parts by weight 0.1 parts by weight of particles having a specific element (M2) (manufactured by Nippon Shokuhin Co., Ltd. “Sea Hoster (registered trademark)” KEW 30).

Example 4
A laminated film was obtained in the same manner as in Example 1 except that the resin composition in the coating solution was changed as follows. Properties and the like of the obtained laminated film are shown in the table.
<Resin composition>
・ Composition (MA-4) having an acrylic resin (A) on the surface of particles (M) having a specific element (“NanoTek” TiO ₂ slurry (number average particle diameter 36 nm manufactured by CI Kasei Co., Ltd.) having Ti element) 60 parts by weight · Melamine compound ("Beckamine (registered trademark)" APM manufactured by DIC) 40 parts by weight · Particles having a specific element (M2) (manufactured by Nippon Shokuhin "Sea Hoster (registered trademark)" KEW 30) 0.1 parts by weight .

Example 5
A laminated film was obtained in the same manner as in Example 1 except that the resin composition in the coating solution was changed as follows. Properties and the like of the obtained laminated film are shown in the table.
<Resin composition>
-Acrylic resin (A) is applied to the surface of particles (M) having a specific element ("Snowtex (registered trademark)" OL colloidal silica slurry containing Si element (number average particle diameter 40 nm manufactured by Nissan Chemical Industries, Ltd.)) Composition (MA-5) 60 parts by weight · Melamine-based compound ("Beckamine (registered trademark)" APM manufactured by DIC) 40 parts by weight · Particles having a specific element (M2) (manufactured by Nippon Shokubai "Sea Hoster (registered trademark) "KEW 30) 0.1 parts by weight.

Example 6
A laminated film was obtained in the same manner as in Example 1 except that the resin composition in the coating solution was changed as follows. Properties and the like of the obtained laminated film are shown in the table.
<Resin composition>
· Composition having an acrylic resin (A) on the surface of particles (M) having a specific element (“Nanouse (registered trademark)” ZR (number average particle diameter 90 nm manufactured by Nissan Chemical Industries, Ltd. containing Zr element)) MA-6) 60 parts by weight · Melamine-based compound ("Beckamine (registered trademark)" APM manufactured by DIC) 40 parts by weight · Particles having a specific element (M2) (manufactured by Nippon Shokubai "Sea Hoster (registered trademark)" KEW 30) 0 .1 part by weight.

Example 7
A laminated film was obtained in the same manner as in Example 1 except that the resin composition in the coating solution was changed as follows. Properties and the like of the obtained laminated film are shown in the table.
<Resin composition>
The above emulsion was mixed with the aqueous solvent in the ratio described in the table.

・ Composition (MA) having an acrylic resin (A) on the surface of particles (M) having a specific element (“NanoTek” Al ₂ O ₃ slurry containing Al element (number average particle diameter 30 nm, manufactured by CI Kasei Co., Ltd.)) -1) 60 parts by weight-Oxazoline compound ("Epocross (registered trademark)" WS500, manufactured by Nippon Shokubai Co., Ltd.) 40 parts by weight-Particles having a specific element (M2) ("Sea Hoster (registered trademark)" KEW 30 manufactured by Nippon Shokubai) 0. 1 part by weight.

Example 8
A laminated film was obtained in the same manner as in Example 1 except that the resin composition in the coating solution was changed as follows. Properties and the like of the obtained laminated film are shown in the table.
<Resin composition>
The above emulsion was mixed with the aqueous solvent in the ratio described in the table.

・ Composition (MA) having an acrylic resin (A) on the surface of particles (M) having a specific element (“NanoTek” Al ₂ O ₃ slurry containing Al element (number average particle diameter 30 nm, manufactured by CI Kasei Co., Ltd.)) -1) 60 parts by weight carbodiimide compound (Nisshinbo Co., Ltd. "Carbodilite (registered trademark)" V02L2) 40 parts by weight Particles having a specific element (M2) (Nippon Shokuhin Co., Ltd. "Sea Hoster (registered trademark)" KEW 30) 0.1 Parts by weight.

Example 9
A laminated film was obtained in the same manner as in Example 1 except that the resin composition in the coating solution was changed as follows. Properties and the like of the obtained laminated film are shown in the table.
<Resin composition>
The above emulsion was mixed with the aqueous solvent in the ratio described in the table.

・ Composition (MA) having an acrylic resin (A) on the surface of particles (M) having a specific element (“NanoTek” Al ₂ O ₃ slurry containing Al element (number average particle diameter 30 nm, manufactured by CI Kasei Co., Ltd.)) -1) 60 parts by weight-Isocyanate compound ("Duranate (registered trademark)" WT 20-100) (Asahi Kasei Corporation) 40 parts by weight-Particles having a specific element (M2) (Nippon Shokuhin "" Shihoster (R) "KEW 30) 0 .1 part by weight.

Example 10
A laminated film was obtained in the same manner as in Example 1 except that the resin composition in the coating solution was changed as follows. Properties and the like of the obtained laminated film are shown in the table.
<Resin composition>
The above emulsion was mixed with the aqueous solvent in the ratio described in the table.

・ Composition (MA) having an acrylic resin (A) on the surface of particles (M) having a specific element (“NanoTek” Al ₂ O ₃ slurry containing Al element (number average particle diameter 30 nm, manufactured by CI Kasei Co., Ltd.)) -1) 60 parts by weight-Epoxy compound ("Denacol (registered trademark)" EX512, manufactured by Nagase Chemtech) 40 parts by weight-Particles having a specific element (M2) (manufactured by Nippon Shokuhin "" Sea Hoster (registered trademark) "KEW 30) 0 .1 part by weight.

Example 11
A laminated film was obtained in the same manner as in Example 1 except that the resin composition in the coating solution was changed as follows. Properties and the like of the obtained laminated film are shown in the table.
<Resin composition>
・ Composition (MA) having an acrylic resin (A) on the surface of particles (M) having a specific element (“NanoTek” Al ₂ O ₃ slurry containing Al element (number average particle diameter 30 nm, manufactured by CI Kasei Co., Ltd.)) -1) 60 parts by weight · Melamine-based compound ("Beckamine (registered trademark)" APM manufactured by DIC) 40 parts by weight · Particles having a specific element (M2) (manufactured by Nippon Shokubai "Sea Hoster (registered trademark)" KEW 30) 2 parts Department.

Example 12
A laminated film was obtained in the same manner as in Example 1 except that the resin composition in the coating solution was changed as follows. Properties and the like of the obtained laminated film are shown in the table.
<Resin composition>
・ Composition (MA) having an acrylic resin (A) on the surface of particles (M) having a specific element (“NanoTek” Al ₂ O ₃ slurry containing Al element (number average particle diameter 30 nm, manufactured by CI Kasei Co., Ltd.)) -1) 60 parts by weight · 40 parts by weight of a melamine compound ("Beckamine (registered trademark)" APM manufactured by DIC).

Example 13
A laminated film was obtained in the same manner as in Example 1 except that the resin composition in the coating solution was changed as follows. Properties and the like of the obtained laminated film are shown in the table.
<Resin composition>
・ Composition (MA) having an acrylic resin (A) on the surface of particles (M) having a specific element (“NanoTek” Al ₂ O ₃ slurry containing Al element (number average particle diameter 30 nm, manufactured by CI Kasei Co., Ltd.)) -1) 60 parts by weight · Melamine-based compound ("Beckamine (registered trademark)" APM manufactured by DIC) 40 parts by weight · Particles having a specific element (M2) (manufactured by Nippon Shokubai "Sea Hoster (registered trademark)" KEW 30) 0. 05 parts by weight.

Example 14
A laminated film was obtained in the same manner as in Example 1 except that the resin composition in the coating solution was changed as follows. Properties and the like of the obtained laminated film are shown in the table.
<Resin composition>
・ Particles having a specific element (M) (“NanoTek” Al ₂ O ₃ slurry containing Al element (number average particle size 30 nm, manufactured by CI Kasei Co., Ltd.)) 40 parts by weight • Acrylic resin (A-7) 20 parts by weight -Melamine based compound ("Beckamine (registered trademark)" APM manufactured by DIC) 40 parts by weight-Particles (M2) having a specific element (Nippon Shokuhin "Shester (registered trademark)" KEW 30) 0.05 parts by weight.

Examples 15 and 16
Resin Composition in Coating Liquid A laminated film was obtained in the same manner as in Example 1 except that the film thickness of the resin layer was changed to the conditions described in Table 2 by changing as follows. Properties and the like of the obtained laminated film are shown in the table.
<Resin composition>
・ Composition (MA) having an acrylic resin (A) on the surface of particles (M) having a specific element (“NanoTek” Al ₂ O ₃ slurry containing Al element (number average particle diameter 30 nm, manufactured by CI Kasei Co., Ltd.)) -1) 60 parts by weight · Melamine-based compound ("Beckamine (registered trademark)" APM manufactured by DIC) 40 parts by weight · Particles having a specific element (M2) (manufactured by Nippon Shokubai "Sea Hoster (registered trademark)" KEW 20) 0. 1 part by weight.

Examples 17 and 18
Resin Composition in Coating Liquid A laminated film was obtained in the same manner as in Example 1 except that the film thickness of the resin layer was changed to the conditions described in Table 2 by changing as follows. Properties and the like of the obtained laminated film are shown in the table.
<Resin composition>
・ Composition (MA) having an acrylic resin (A) on the surface of particles (M) having a specific element (“NanoTek” Al ₂ O ₃ slurry containing Al element (number average particle diameter 30 nm, manufactured by CI Kasei Co., Ltd.)) -1) 60 parts by weight · Melamine-based compound ("Beckamine (registered trademark)" APM manufactured by DIC) 40 parts by weight · Particles having a specific element (M2) (manufactured by Nippon Shokubai "Sea Hoster (registered trademark)" KEW 50) 0. 1 part by weight.

Example 19
Resin Composition in Coating Liquid A laminated film was obtained in the same manner as in Example 1 except that the film thickness of the resin layer was changed to the conditions described in Table 2 by changing as follows. Properties and the like of the obtained laminated film are shown in the table.
<Resin composition>
・ Composition (MA) having an acrylic resin (A) on the surface of particles (M) having a specific element (“NanoTek” Al ₂ O ₃ slurry containing Al element (number average particle diameter 30 nm, manufactured by CI Kasei Co., Ltd.)) -1) 60 parts by weight · Melamine-based compound ("Beckamine (registered trademark)" APM manufactured by DIC) 40 parts by weight Particles (M2) having a specific element ("Spherica (registered trademark)" 140 manufactured by JGC Co., Ltd.) ) 0.1 parts by weight.

Example 20
Resin Composition in Coating Liquid A laminated film was obtained in the same manner as in Example 1 except that the film thickness of the resin layer was changed to the conditions described in Table 2 by changing as follows. Properties and the like of the obtained laminated film are shown in the table.
<Resin composition>
・ Composition (MA) having an acrylic resin (A) on the surface of particles (M) having a specific element (“NanoTek” Al ₂ O ₃ slurry containing Al element (number average particle diameter 30 nm, manufactured by CI Kasei Co., Ltd.)) -1) 60 parts by weight · Melamine-based compound ("Beckamine (registered trademark)" APM manufactured by DIC) 40 parts by weight · Particles having a specific element (M2) (manufactured by Nippon Shokubai "Sea Hoster (registered trademark)" KEW 20) 0. 1 part by weight.

Examples 21 and 22
Resin Composition in Coating Liquid A laminated film was obtained in the same manner as in Example 1 except that the film thickness of the resin layer was changed to the conditions described in Table 2 by changing as follows. Properties and the like of the obtained laminated film are shown in the table.
<Resin composition>
・ Composition (MA) having an acrylic resin (A) on the surface of particles (M) having a specific element (“NanoTek” Al ₂ O ₃ slurry containing Al element (number average particle diameter 30 nm, manufactured by CI Kasei Co., Ltd.)) -1) 60 parts by weight · Melamine-based compound ("Beckamine (registered trademark)" APM manufactured by DIC) 40 parts by weight · Particles having a specific element (M2) (manufactured by Nippon Shokubai "Sea Hoster (registered trademark)" KEW 60) 0. 1 part by weight.

Example 23
A laminated film was obtained in the same manner as in Example 12 except that a PET pellet containing 0.1 wt% of silica particles having a particle diameter of 2 μm was used as the PET pellet. Properties and the like of the obtained laminated film are shown in the table.

Example 24
A laminated film was obtained in the same manner as in Example 23, except that the thickness of the PET film was changed to 188 μm. Properties and the like of the obtained seat layer film are shown in the table.

Example 25
As thermoplastic resin A, what was mixed so that it might become a mass ratio of PET-A: PET-C: PET-D = 89: 10: 1, and PET-A as thermoplastic resin B were used. The prepared thermoplastic resins A and B were sufficiently vacuum-dried and then fed to an extruder for melt extrusion at 285 ° C. While measuring with a gear pump so that the mass ratio of A / B is 2:48, after combining with A / B / A with pinol, push it out from a T-shaped nozzle into a sheet shape, and apply the electrostatic application casting method Using a mirror surface casting drum having a surface temperature of 20 ° C., it was cooled and solidified. The 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, a resin composition 1 was applied to a corona discharge treated surface of a uniaxially stretched film using a bar coat to a coating thickness of about 6 μm. Both ends in the width direction of the uniaxially stretched film coated with the resin composition are gripped by clips and led to the preheating zone to make the atmosphere temperature 75 ° C. Subsequently, the atmosphere temperature is made 110 ° C. using a radiation heater, and then the atmosphere temperature The resin composition was dried at 90 ° C. to form a resin layer. Subsequently, the laminate film is continuously stretched 3.5 times in the width direction in a heating zone (stretching zone) at 120 ° C., and subsequently heat treated for 20 seconds in a heat treatment zone (heat setting zone) at 230 ° C. I got In the obtained laminated film, the thickness of the PET film was 50 μm, and the thickness of the resin layer was 0.7 μm.

Example 26
A laminated film was obtained in the same manner as in Example 25 except that the thickness of the PET film was changed to 188 μm. Properties and the like of the obtained seat layer film are shown in the table.

Example 27
A laminated film was produced in the same manner as in Example 25 except that a thermoplastic resin A was used which was mixed so as to have a mass ratio of PET-A: PET-B = 90: 10 substantially containing no particles. I got Properties and the like of the obtained seat layer film are shown in the table.

Example 28
A laminated film is prepared in the same manner as in Example 25 except that a thermoplastic resin A is used which is mixed so as to have a mass ratio of PET-A: PET-E = 90: 10 substantially free of particles. I got Properties and the like of the obtained seat layer film are shown in the table.

Comparative Example 1
A laminated film was obtained in the same manner as in Example 1 except that the resin composition in the coating solution was changed as follows. Properties and the like of the obtained laminated film are shown in the table.

<Resin composition>
・ Composition (MA) having an acrylic resin (A) on the surface of particles (M) having a specific element (“NanoTek” Al ₂ O ₃ slurry containing Al element (number average particle diameter 30 nm, manufactured by CI Kasei Co., Ltd.)) -1) 60 parts by weight · Melamine-based compound ("Beckamine (registered trademark)" APM manufactured by DIC) 40 parts by weight · Particles having a specific element (M2) (manufactured by Nippon Shokubai "Sea Hoster (registered trademark)" KEW 50) 2 parts Department.

Comparative Example 2
A laminated film was obtained in the same manner as in Example 1 except that the resin composition in the coating solution was changed as follows. Properties and the like of the obtained laminated film are shown in the table.

<Resin composition>
-Inorganic particles (A) containing Si element ("Snowtex (registered trademark)" O colloidal silica slurry (number average particle diameter 5 nm manufactured by Nissan Chemical Industries, Ltd.)) 40 parts by weight-Acrylic resin (A-7) 20 weight Part-40 parts by weight of a melamine compound ("Beckamine (registered trademark)" APM manufactured by DIC).

Comparative Example 3
A laminated film was obtained in the same manner as in Example 1 except that the resin composition in the coating solution was changed as follows. Properties and the like of the obtained laminated film are shown in the table.

・ Composition (MA) having an acrylic resin (A) on the surface of particles (M) having a specific element (“NanoTek” Al ₂ O ₃ slurry containing Al element (number average particle diameter 30 nm, manufactured by CI Kasei Co., Ltd.)) -1) 100 parts by weight-Particles having a specific element (M2) (manufactured by Nippon Shokuhin Co., Ltd. "Sea Hoster (registered trademark)" KEW 30) 0.1 parts by weight.

Comparative Example 4
A laminated film was obtained in the same manner as in Example 6, except that the thickness of the resin layer (X) was changed from 0.7 μm to 0.1 μm. Properties and the like of the obtained laminated film are shown in the table.

Comparative Example 5
A laminated film was obtained in the same manner as in Example 1 except that the resin composition in the coating solution was changed as follows. Properties and the like of the obtained laminated film are shown in the table.
<Resin composition>
・ Particles having a specific element containing an Au element (not containing Si, Al, Ti, Zr, Fe) (A) (gold nanoparticles Au-WPP 08-C (Dainippon Paint Co., Ltd. number average particle diameter 10 nm) 40 parts by weight Acrylic resin (B-3) 20 parts by weight Melamine-based compound ("Beckamine (registered trademark)" APM manufactured by DIC) 40 parts by weight <Comparative Example 6>
A laminated film was obtained in the same manner as in Example 1 except that the resin composition in the coating solution was changed as follows. Properties and the like of the obtained laminated film are shown in the table.

<Resin composition>
・ Composition (MA) having an acrylic resin (A) on the surface of particles (M) having a specific element (“NanoTek” Al ₂ O ₃ slurry containing Al element (number average particle diameter 30 nm, manufactured by CI Kasei Co., Ltd.)) -1) 60 parts by weight · 40 parts by weight of melamine based compound ("Beckamine (registered trademark)" APM manufactured by DIC)

  The present invention is a laminated film excellent in transparency, scratch resistance, and transparency after storage in a high temperature and high humidity environment, and a hard coat film conventionally used for display applications and a hard coat film used for molded decoration applications It is available as

Claims (10)

It is a laminated film which has a thermoplastic resin layer and a resin layer (X), Comprising: The surface layer of at least one side is a resin layer (X),
A particle (M) having at least one element selected from Si, Al, Ti, Zr, Fe, and a resin layer (X) possessed on the surface layer, a melamine compound, an oxazoline compound, a carbodiimide compound, an isocyanate compound, an epoxy Containing at least one compound selected from the compounds,
The ten-point average roughness (Rz) by the three-dimensional roughness meter of the resin layer (X) surface in the surface layer is 50 to 500 nm, and of particles (M) having a specific element contained in the resin layer (X) A laminated film in which the maximum particle diameter φ (μm) is smaller than the film thickness d (μm) of the resin layer (X). The laminated film according to claim 1, wherein the internal haze of the laminated film is 0.2% or less. The laminated film according to claim 1 or 2, wherein the particle content of the thermoplastic resin layer is 0.1% by weight or less. The content of particles (M) having a specific element of the resin layer (X) contained in the surface layer is 20 to 60% by weight with respect to the entire resin layer (X). Laminated film. The resin layer (X) is a layer formed by applying a coating composition (x) containing an acrylic resin (A) to a thermoplastic resin layer and heating it, and the Tg of the acrylic resin (A) is It is 0-60 degreeC, The laminated film in any one of Claims 1-4. The resin layer (X) comprises particles (M-1) having at least one element selected from the group consisting of Si, Al, Ti, Zr, Se, and Fe, and Si, Al, and Ti. The laminated film according to any one of claims 1 to 5, which contains particles (M-2) containing an element different from the element contained in the particles (M-1) selected from the group consisting of Zr, Se, and Fe. . The average particle diameter of the particles (M) having a specific element contained in the resin layer (X) is in the range of 10 to 100 nm when the particle diameter is plotted on the horizontal axis and the abundance ratio of the particles is plotted on the vertical axis. The laminated film according to any one of claims 1 to 6, which has one or more maximum values in each of the particle diameter range of 200 to 600 nm. It is a laminated film which has a thermoplastic resin layer and a resin layer (X), Comprising: The surface layer of at least one side is a resin layer (X),
A particle (M) having at least one element selected from Si, Al, Ti, Zr, Fe, and a resin layer (X) possessed on the surface layer, a melamine compound, an oxazoline compound, a carbodiimide compound, an isocyanate compound, an epoxy Containing at least one crosslinker selected from compounds,
When the spectral reflectance spectrum is measured in the wavelength range of 400 to 800 nm from the resin layer (X) side and the wavelength (nm) is plotted on the horizontal axis and the reflectance (%) on the vertical axis, in the wavelength 400 to 800 nm range There are 4 or more and 14 or less extrema,
There are two or more extreme values in the wavelength range of 500 to 600 nm,
There are two or more extreme values in at least one region of a wavelength of 400 to 500 nm and a wavelength of 600 to 800 nm,
The largest value of the amplitude intensity (the difference between the spectral reflectances of two adjacent extreme values) in the wavelength region of 500 to 600 nm corresponds to the amplitude intensity at two wavelengths of 400 to 500 nm or 600 to 800 nm (two adjacent poles). The laminated film according to any one of claims 1 to 7, which is 0.5 times or more and less than 2 times the largest value of the spectral reflectance difference). Ratio (maximum particle diameter (φ) / film thickness (d)) of the maximum particle diameter φ (μm) of the particles (M) contained in the resin layer (X) and the film thickness d (μm) of the resin layer (X) The laminated film according to any one of claims 1 to 8, wherein) is 0.3 or more and 0.6 or less. The method for producing a laminated film according to any one of claims 1 to 9, wherein at least one element selected from Si, Al, Ti, Zr, Se, and Fe is provided on at least one side of the thermoplastic resin layer. Coating composition (x) containing particles (M) having at least one cross-linking agent selected from melamine, oxazoline, carbodiimide, isocyanate, epoxy compound is applied, and then the coating composition (x) is applied The manufacturing method of the laminated | multilayer film which extend | stretches the thermoplastic resin layer which was carried out at least uniaxial direction, and then heat-processes.

Images