JP2023006496A - Laminate film and molded body, and method for manufacturing the same - Google Patents

Abstract

Kind Code: A1 A laminated film having antiviral and/or antibacterial properties, excellent moldability, and capable of forming a molded article having high hardness is provided. A transparent supporting substrate, an uncured hard coat layer formed on at least one surface of the transparent supporting substrate, and an uncured first layer formed on the uncured hard coat layer. a functional layer, wherein the uncured hard coat layer contains an active energy ray-curable hard coat layer-forming composition, and the uncured first functional layer is an active energy ray-curable first function A laminated film comprising a layer-forming composition, wherein the first functional layer-forming composition contains inorganic particles having at least one of antiviral properties and antibacterial properties, and the stretch ratio at 160°C is 50% or more. [Selection drawing] Fig. 1

Description

The present invention relates to laminated films and moldings, and methods for producing them.

Due to the recent heightened awareness of hygiene, it is required to apply antibacterial or antiviral finishing to articles that come into contact with people. For example, Patent Literature 1 proposes a transparent film having an antibacterial layer, which is used for touch panels and the like. Patent Literature 2 proposes a sheet to which an antiviral agent is applied for use as a shrink film.

JP-A-9-316369 WO2016/084774

Antiviral and/or antibacterial properties are also required, for example, in display protectors. Display protectors also require high hardness. A laminated film for forming a protective material may sometimes be required to have moldability capable of being molded into a three-dimensional shape.

An object of the present invention is to provide a laminated film that has antiviral and/or antibacterial properties, is excellent in moldability, and provides a molded article having high hardness.

In order to solve the above problems, the present invention provides the following aspects.
[1]
a transparent support substrate;
an uncured hard coat layer formed on at least one surface of the transparent supporting substrate;
an uncured first functional layer formed on the uncured hard coat layer;
The transparent supporting substrate and the uncured hard coat layer are adjacent to each other,
The uncured hard coat layer contains an active energy ray-curable hard coat layer-forming composition,
The uncured first functional layer contains an active energy ray-curable first functional layer-forming composition,
The first functional layer-forming composition contains inorganic particles having at least one of antiviral and antibacterial properties,
A laminated film having a stretch ratio of 50% or more at 160°C.

[2]
The laminated film according to [1] above, wherein the hardness measured by a nanoindentation method from the uncured first functional layer side is 0.05 GPa or more and 0.5 GPa or less.

[3]
The laminated film according to [1] or [2] above, wherein the laminated film irradiated with an active energy ray having an integrated light amount of 2000 mJ/cm ² has a pencil hardness measured from the first functional layer side of 2H or more. .

[4]
The laminated film according to any one of [1] to [3] above, which has a haze value of 2% or less.

[5]
The laminated film according to any one of [1] to [3] above, wherein the uncured first functional layer has a thickness of 15 nm or more and 1 μm or less.

[6]
The inorganic particles have at least antiviral properties,
The laminated film according to any one of the above [1] to [5], wherein the laminated film irradiated with active energy rays having an integrated light amount of 2000 mJ/cm ² has an antiviral activity value of 2.0 or more.

[7]
The hard coat layer-forming composition comprises a first layer-forming component,
The first layer-forming component includes a first reactive component having two or more polymerizable functional groups in one molecule,
Any one of the above [1] to [6], wherein the first reactive component includes at least one of a first oligomer having a weight average molecular weight of 10,000 or less and a first monomer having a weight average molecular weight of 10,000 or less. laminated film.

[8]
The laminated film according to [7] above, wherein the first reactive component further contains a first polymer having a weight average molecular weight of more than 10,000.

[9]
[7] or [ 8].

[10]
The laminated film according to any one of [1] to [9] above, wherein the luminous reflectance including specular light measured from the uncured first functional layer side is 4% or less.

[11]
The laminated film according to any one of [1] to [10] above, wherein the first functional layer-forming composition further comprises first low refractive particles that reduce the refractive index of the uncured first functional layer. .

[12]
An uncured second functional layer is further provided between the uncured hard coat layer and the uncured first functional layer,
The laminated film according to [11] above, wherein the uncured second functional layer contains high refractive particles that increase the refractive index of the uncured second functional layer.

[13]
An uncured third functional layer is further provided between the uncured hard coat layer and the uncured first functional layer,
The laminated film according to any one of [1] to [12] above, wherein the uncured third functional layer contains second low refractive particles that lower the refractive index of the uncured third functional layer.

[14]
An uncured second functional layer is further provided between the uncured hard coat layer and the uncured third functional layer,
The laminated film according to [13] above, wherein the uncured second functional layer contains high refractive particles that increase the refractive index of the uncured second functional layer.

[15]
Any one of the above [1] to [14], further comprising another supporting substrate disposed on the surface of the uncured first functional layer opposite to the uncured hard coat layer. Laminated film as described.

[16]
A molded article comprising the cured laminated film according to any one of [1] to [15] above.

[17]
The hard coat layer is arranged on one main surface of the transparent supporting substrate,
The formed body according to [16] above, further comprising a decorative layer disposed on the other main surface of the transparent supporting base material.

[18]
The hard coat layer is arranged on one main surface of the transparent supporting substrate,
The molded article according to [16] or [17] above, further comprising a molded resin layer disposed on the other main surface of the transparent support base.

[19]
a step of applying an active energy ray-curable hard coat layer-forming composition onto one surface of a transparent supporting substrate to form an uncured hard coat layer;
a step of applying an active energy ray-curable composition for forming a first functional layer onto one surface of another supporting substrate to form an uncured first functional layer;
The surface of the uncured hard coat layer opposite to the transparent supporting substrate and the surface of the uncured first functional layer opposite to the other supporting substrate are laminated to form a laminated film. and a lamination step to obtain,
The first functional layer-forming composition contains inorganic particles having at least one of antiviral and antibacterial properties,
A method for producing a laminated film, wherein the laminated film has a stretch ratio of 50% or more at 160°C.

[20]
A method for producing a molded article, comprising a curing step of irradiating the laminated film according to any one of the above [1] to [15] with an active energy ray having an accumulated light amount of 200 mJ/cm ² or more.

[21]
In the laminated film, the uncured hard coat layer is arranged on one main surface of the transparent supporting substrate,
The method for producing a molded article according to [20] above, wherein a decorative layer is disposed on the other main surface of the transparent supporting base material.

[22]
In the laminated film, the uncured hard coat layer is arranged on one main surface of the transparent supporting substrate,
The method for producing a molded article according to [20] or [21] above, further comprising an injection molding step of placing the laminated film in a mold and injecting a molding resin toward the transparent supporting substrate. .

[23]
The mold imparts a three-dimensional shape to the laminated film,
The method for producing a molded article according to [22] above, further comprising a preforming step of molding the laminated film into a shape along the three-dimensional shape before the injection molding step.

INDUSTRIAL APPLICABILITY According to the present invention, a laminated film and molded article having antiviral and/or antibacterial properties, excellent moldability, and high hardness can be obtained, and methods for producing the same are provided. can do.

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows typically the laminated|multilayer film which concerns on one Embodiment of this invention. FIG. 3 is a cross-sectional view schematically showing a laminated film according to another embodiment of the invention; FIG. 4 is a cross-sectional view schematically showing a laminated film according to still another embodiment of the present invention; 1 is a cross-sectional view schematically showing a molded body according to one embodiment of the present invention; FIG. 1 is a flow chart showing a method for manufacturing a laminated film according to one embodiment of the invention. It is a schematic diagram explaining a lamination process in a manufacturing method of a lamination film concerning one embodiment of the present invention. 1 is a flow chart showing a method for manufacturing a molded body according to an embodiment of the present invention; 4 is a flow chart showing a method for manufacturing a molded body according to another embodiment of the present invention;

As a protective material for a display having a three-dimensional shape, conventionally, a laminated film called a pre-cured type is used. In a pre-cured laminated film, each layer is already cured at the time it is subjected to preforming prior to injection molding into a three-dimensional shape. Therefore, the laminated film cannot conform to a deep three-dimensional shape, and cracks or whitening may occur in the laminated film.

In order to allow the pre-cured laminated film to conform to a deep three-dimensional mold, it is conceivable to lower the crosslink density of the laminated film and increase the stretchability after curing. However, when the crosslink density is low, it is difficult to obtain sufficient mechanical properties and chemical resistance.

In order to allow the laminated film to conform to a deep three-dimensional mold while increasing the cross-linking density of the molded article as the final product, the laminated film may be cured after preforming. From such a point of view, a laminated film having an uncured layer was conceived.

A. Laminated Film The laminated film according to the present embodiment comprises a transparent supporting substrate, an uncured hard coat layer formed on at least one surface of the transparent supporting substrate, and an uncured hard coat layer formed on the and an uncured first functional layer. That is, the laminated film according to this embodiment is an after-cure type. In the after-cured laminated film, the hard coat layer and the first functional layer are not completely cured and are uncured.

"Uncured" refers to a state of not being completely cured. The hard coat layer and the first functional layer contained in the laminated film may be in a semi-cured state or completely uncured.

For example, when an active energy ray-curable composition is irradiated with an active energy ray of 150 mJ/cm ² or less, a completely uncured (uncured) layer is obtained. When the composition is irradiated with an active energy ray of 5 mJ/cm ² or more and 150 mJ/cm ² or less, it can be said that the composition is in a semi-cured state. The integrated light amount of the active energy ray for preventing complete curing is not limited to this, and is appropriately set depending on the composition of the composition and the like.

A composition irradiated with an active energy ray of 2000 mJ/cm ² is generally said to be completely cured. A hard coat layer, a first functional layer, and the like in a molded article according to this embodiment, which will be described later, are also completely cured. That is, the physical properties of the composition irradiated with an active energy ray of 2000 mJ/cm ² can be regarded as the physical properties of the hard coat layer, the first functional layer, etc. of the molded product.

Each physical property of the laminated film may be measured using the laminated film immediately before being subjected to the curing step after being heat-treated in an atmosphere of 150° C. or higher and 190° C. or lower for 30 seconds or more and 60 seconds or less. The above physical properties may also be measured using a dried laminated film. Each physical property of the laminated film (molding) after curing may be measured using the laminated film cured after being heat-treated under the above conditions.

Since each layer of the laminated film is in an uncured state, the occurrence of cracks and whitening in the process of molding into a three-dimensional shape (typically preform and injection molding) is suppressed. When no cracks or whitening is visually observed when the laminated film is formed into a three-dimensional shape, it can be said that the laminated film has excellent conformability to the three-dimensional shape and has high moldability. A laminated film having a draw ratio of 50% or more at 160° C. has high moldability.

During preforming, the laminate film is stretched. In the case of using an after-cured laminated film, the uncured laminated film is stretched, and the stretched film is not excessively stretched after curing. Therefore, each layer can be formed from a layer-forming composition that increases the crosslink density. That is, it is possible to increase the hardness of the laminated film after curing, and it is easy to obtain sufficient mechanical properties and chemical resistance.

Since both the hard coat layer and the first functional layer are uncured, the adhesion between the layers is high. Furthermore, by heat-treating the laminated film, the unevenness of the surface of each layer can be leveled. Thereby, a laminated film having high smoothness can be obtained. A molded article obtained from such a laminated film exhibits excellent wear resistance and maintains good visibility for a long period of time. Furthermore, since haze caused by surface irregularities is suppressed, the appearance is good.

The uncured hard coat layer and the transparent supporting substrate are adjacent to each other. This increases the hardness (particularly, pencil hardness) of the molded product. If, for example, an adhesive layer is interposed between the uncured hard coat layer and the transparent supporting substrate, the hardness of the molded product tends to be low. Furthermore, since the hard coat layer is uncured, the composition for forming the adhesive layer and the composition for forming the hard coat layer may be mixed when forming the adhesive layer. In addition, the number of production steps increases.

(stretch ratio)
The stretch ratio E160 at ₁₆₀ °C of the laminated film according to this embodiment is 50% or more. Thereby, the laminated film is sufficiently stretched at a molding temperature of 150° C. or higher and 190° C. or lower. Therefore, the laminated film can follow a complicated three-dimensional shape without cracks. In particular, damage to the laminated film is suppressed in the preforming process. Therefore, it is possible to obtain a molded article having the functions of the hard coat layer and the first functional layer and having a complicated three-dimensional shape. The laminated film is molded into a three-dimensional shape by preforming, injection molding, or the like, depending on the required physical properties, shape, and the like.

The stretch ratio _E160 of the laminated film is preferably 60% or more, more preferably 70% or more. The elongation E ₁₆₀ of the laminate film may be less than 400%, may be less than 350%, may be less than 300%. The stretch ratio at 160° C. of the molded product obtained by curing the laminated film is less than 15%, and may be 5% or less.

The elongation ratio E ₁₆₀ can be measured, for example, as follows.
A tensile tester with a chuck-to-chuck distance of 150 mm and an evaluation sample cut into a length of 200 mm and a width of 10 mm are prepared. The evaluation sample is stretched 10% in the long side direction under the conditions of a tensile force of 5.0 Kgf and a tensile speed of 300 mm/min in an atmosphere of 160°C. The presence or absence of cracks in the stretched evaluation sample is visually checked.

If no cracks occur, a new sample is cut out and stretched up to 20% in the long side direction. Similarly, the presence or absence of cracks is visually checked. This procedure is repeated while increasing the stretch ratio by 10%, and the stretch ratio at which cracks are first observed is taken as the stretch ratio E ₁₆₀ of the laminated film.

(indentation hardness)
The hardness H _BC by the nanoindentation method measured from the first functional layer side of the laminated film is preferably 0.05 GPa or more in terms of easily suppressing damage. When the hardness H _BC is 0.05 GPa or more, defects such as dents and damages during slit formation and cutting, dents due to foreign matter mixed when laminating a plurality of laminated films, squeegee marks, and suction marks are suppressed. , it becomes easy to improve the yield.

The hardness H _BC is preferably 0.5 GPa or less from the viewpoint of easily improving the adhesion between the uncured first functional layer and other layers (eg, uncured hard coat layer, second functional layer, etc.). In this case, when the uncured hard coat layer and the uncured first functional layer are laminated, it is easy to prevent air from entering between the layers (air entrapment). Specifically, the hardness _HBC is preferably 0.05 GPa or more and 0.5 GPa or less. Hardness _HBC is more preferably 0.07 GPa or more. The hardness _HBC is more preferably 0.4 GPa or less.

The hardness H _AC measured by the nanoindentation method from the first functional layer side of the laminated film irradiated with an active energy ray having an accumulated light amount of 2000 mJ/cm ² is, for example, 0.25 GPa or more. In this case, the molding has sufficiently high hardness. The hardness H _AC is preferably 0.7 GPa or less. Specifically, the hardness _HAC is preferably 0.25 GPa or more and 0.7 GPa or less. The hardness H _AC is particularly preferably 0.3 GPa or more. The hardness H _AC may be 0.6 GPa or less. The hardness H _AC of the compact is greater than the hardness H _BC of the laminated film.

Hardnesses _HBC and _HAC are calculated based on values measured by a nanoindentation method from the first functional layer side of the laminated film or molded body. Hardnesses H _BC and H _AC are measured under conditions where the surface state of the first functional layer and the hardness of the transparent support substrate are unlikely to affect them. That is, the hardnesses H _BC and H _AC are measured by pushing an indenter into the hard coat layer from the first functional layer side. It can be said that the hardness HBC and _{HAC reflect} the hardness of the uncured or cured hard coat layer. For example, the hardness H _BC and H _AC are measured within 1000 nm or more from the surface of the first functional layer.

The hardness by the nanoindentation method is determined by, for example, Continuous Stiffness Measurement using a nanoindentation device. In continuous stiffness measurements, the sample is subjected to a microload (alternating current (AC) load) in addition to a quasi-static test load (direct current (DC) load). This causes the force applied to the sample to oscillate minutely. The stiffness with respect to depth is calculated from the vibration component of the resulting displacement and the phase difference between the displacement and the load. As a result, a continuous profile of hardness can be obtained with respect to depth.

As a nanoindentation device, NANOMECHANICS, INC. can be used. Continuous stiffness measurement methods include, for example, those described in Advanced Dynamic E and H.; NMT method can be used. iMicro dedicated software can be used to calculate load and stiffness. The sample is loaded with an indenter until a maximum load of 50 mN is reached. As the indenter, for example, a Verkovich type diamond indenter is used. Appropriate values are set for the Poisson's ratio, load, etc. of the object to be measured (uncured or cured hard coat layer and first functional layer) for measurement and stiffness calculation.

After the hardness H _BC is measured by the nanoindentation method, if there is no impression left on the surface of the first functional layer that matches the shape of the indenter used, the measured hardness H _BC is judged to be inaccurate. can. It is believed that the above phenomenon occurs because the uncured hard coat layer is excessively soft. In other words, the measured hardness is strongly influenced by the transparent supporting substrate rather than by the uncured hard coat layer. In the above case the hardness H _BC may be considered to be less than 0.05 GPa.

(Pencil hardness)
A molded article having high hardness can be obtained by the laminated film according to the present embodiment. For example, the laminated film irradiated with an active energy ray having an integrated light amount of 2000 mJ/cm ² has a pencil hardness of 2H or more measured from the first functional layer side. Pencil hardness is measured according to JIS K5600-5-4 (1999), scratch hardness (pencil method).

(Haze value)
The laminated film according to this embodiment has a low haze value in spite of containing the antiviral/antibacterial inorganic particles. For example, the laminated film has a haze value of 2.0% or less. Thereby, a molded article having high transparency can be obtained. The laminated film according to this embodiment is suitable as a protective material for displays. A haze value is measured according to JIS K7136. The haze value is more preferably 1.0% or less, still more preferably 0.5% or less, and particularly preferably 0.3% or less.

(Antiviral activity value)
The laminated film and molded article according to this embodiment exhibit excellent antiviral and/or antibacterial properties. For example, the antiviral activity value of a laminated film irradiated with an active energy ray with an integrated light intensity of 2000 mJ/cm ² is 2.0 or more. In this case, it can be said that the laminated film and molded article have sufficiently high antiviral properties.

Antiviral activity values are measured according to ISO 21702 "Determination of antiviral activity of plastics and other non-porous surfaces". However, in the present specification, bacteriophage Q-beta is used as the test virus. Bacteriophage Qβ is easy to handle and inexpensive.

A molded article obtained by stretching and then curing the laminated film according to the present embodiment also exhibits excellent antiviral and/or antibacterial properties.

(luminous reflectance)
It is desirable that the laminated film has antireflection performance. For example, the luminous reflectance including specularly reflected light in the wavelength range of 380 nm or more and 780 nm or less measured from the first functional layer side of the laminated film is preferably 4.0% or less. In this case, the molded article obtained by curing the laminated film also has excellent antireflection properties. Therefore, the molded article has little reflection due to external light, and the molded article can have good display characteristics and good visibility. The luminous reflectance of the molded body can be similarly 4.0% or less.

The luminous reflectance of the laminated film and molded article is preferably 3.0% or less, more preferably 2.5% or less, and particularly preferably 1.0% or less. The luminous reflectance of the laminated film and molded article may be 0.1% or more.

The luminous reflectance is obtained by measuring all reflected light including regular reflected light. That is, the luminous reflectance is measured by a so-called SCI (Specular Component Include) method. Since this method is not easily affected by the surface state of the object to be measured, the luminous reflectance of an uncured layer can be measured.

Specifically, the luminous reflectance of the laminated film can be measured by the following method.
A black paint (for example, CZ-805 BLACK manufactured by Nikko Bix Co., Ltd.) is applied to the surface of the transparent support substrate opposite to the uncured hard coat layer using a bar coater to a dry film thickness of 3 μm or more. It is applied so that it becomes 6 μm or less. After that, an evaluation sample M is prepared by leaving it to dry for 5 hours under a room temperature environment.

From the first functional layer side of the obtained evaluation sample M, using a spectral colorimeter (for example, SD7000 manufactured by Nippon Denshoku Industries Co., Ltd.), the luminous reflectance by the SCI method in the wavelength region of 380 nm or more and 780 nm or less was measured. Measure.

The luminous reflectance of the molded article can be measured as follows.
An evaluation sample N is prepared by irradiating the evaluation sample M prepared above with an active energy ray with an accumulated light amount of 200 mJ/cm ² or more (for example, an accumulated light amount of 2000 mJ/cm ² ). From the first functional layer side of the obtained evaluation sample N, the luminous reflectance is measured in the same manner as described above.

The transparent support substrate and each layer are further described below.
[Transparent Supporting Substrate]
The transparent supporting substrate is not particularly limited as long as it is transparent. Being transparent specifically means that the total light transmittance is 40% or more. The total light transmittance of the transparent support substrate is preferably 90% or more. The total light transmittance can be measured by a method conforming to JIS K 7361-1. As the transparent supporting substrate, those known in the art can be used without particular limitation. The transparent supporting substrate may be colorless or colored.

The transparent supporting substrate is appropriately selected depending on the application. Examples of transparent supporting substrates include polycarbonate (PC) films, polyester films such as polyethylene terephthalate and polyethylene naphthalate; cellulose films such as diacetyl cellulose and triacetyl cellulose; acrylic films such as polymethyl methacrylate (PMMA); Styrene films such as acrylonitrile/styrene copolymers; olefin films such as polyvinyl chloride, polyethylene, polypropylene, polyolefins having a cyclic or norbornene structure, and ethylene/propylene copolymers; amide films such as nylons and aromatic polyamides. . The transparent supporting substrate is a film containing resin such as polyimide, polysulfone, polyethersulfone, polyetheretherketone, polyphenylene sulfide, polyvinyl alcohol, polyvinylidene chloride, polyvinyl butyral, polyarylate, polyoxymethylene, and epoxy resin. It may be a film comprising mixtures of these polymers.

The transparent support substrate may be a laminate of multiple films. The transparent support substrate may be, for example, a laminate of a film made of acrylic resin and a film made of polycarbonate resin.

The transparent support substrate may be optically anisotropic or isotropic. The magnitude of birefringence of the optically anisotropic transparent supporting substrate is not particularly limited. The retardation of the anisotropic transparent support substrate may be 1/4 of the wavelength (λ/4) or 1/2 of the wavelength (λ/2).

The thickness of the transparent supporting substrate is not particularly limited. The thickness of the transparent supporting substrate is, for example, 50 μm or more and 600 μm or less. In this case, it becomes easy to maintain the rigidity of the laminated film after stretching. In addition, warping of the laminated film and molded article is easily suppressed. Furthermore, since the transparent supporting substrate and the laminated film can be easily wound into a roll, roll-to-roll processing can be performed.

The thickness of the transparent supporting substrate is preferably 100 μm or more, more preferably 200 μm or more. The thickness of the transparent support substrate is preferably 500 μm or less, more preferably 450 μm or less, and particularly preferably 400 μm or less.

[Uncured first functional layer]
The uncured first functional layer is formed on the uncured hard coat layer. The first functional layer may be adjacent to the hard coat layer, or another functional layer to be described later may be interposed between the first functional layer and the hard coat layer.

The first functional layer contains inorganic particles having at least one of antiviral and antibacterial properties (hereinafter referred to as antiviral/antibacterial inorganic particles). The first functional layer exhibits at least one of antiviral and antibacterial properties.

The uncured first functional layer contains an active energy ray-curable first functional layer-forming composition (hereinafter sometimes referred to as composition F1). Composition F1 is cured by active energy rays. The hardness and/or stretch ratio of the first functional layer can be controlled by adjusting the integrated light quantity of the active energy ray. Composition F1 is preferably cured by the same type of active energy rays as the hard coat layer-forming composition. Active energy rays are ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. The composition F1 is particularly preferably an ultraviolet curable type.

The thickness of the uncured first functional layer is not particularly limited, and is appropriately set in consideration of the average particle size and content of the antiviral/antibacterial inorganic particles. The thickness of the uncured first functional layer may be about the same as the average particle size of the antiviral/antibacterial inorganic particles, or may be thinner than that. In particular, the thickness of the uncured first functional layer is preferably 15 nm or more and 1 μm or less. When the thickness of the uncured first functional layer is within the above range, the appearance of the laminated film is likely to be improved, and the haze value is likely to be suppressed. As will be described later, when the first functional layer also has an antireflection function, the thickness of the uncured first functional layer is preferably 50 nm or more, particularly preferably 60 nm or more. The thickness of the uncured first functional layer is preferably 500 nm or less, particularly preferably 200 nm or less.

The first functional layer is laminated on the uncured hard coat layer in an uncured state. Furthermore, as described above, the laminated film is subjected to various processing in an uncured state. Therefore, the first functional layer must have high hardness, low tackiness and resistance to contamination, suppression of damage and appearance change during processing, and the difference in heat shrinkability from other layers. Suppression of curling and the like are required. In particular, the first functional layer is required to have low tackiness, be resistant to contamination, and be resistant to damage during processing (for example, dents such as suction traces and squeegee traces in the decorating step).

These requirements can be met by controlling the hardness, rigidity, smoothness, tackiness, etc. of the uncured first functional layer. The physical properties of the uncured first functional layer can be adjusted by the thickness thereof, the composition of the composition for forming the first functional layer, and the like.

<<First functional layer forming composition>>
The first functional layer-forming composition (composition F1) includes, for example, a second layer-forming component together with antiviral/antimicrobial inorganic particles.

<Antiviral/antibacterial inorganic particles>
Since inorganic particles are used as the component having at least one of antiviral and antibacterial properties, the molded product has good pencil hardness and good appearance.

Antiviral/antimicrobial inorganic particles include, for example, metal salts. A metal salt is formed from a metal ion and its counterion. Examples of metal species include Cu (copper), Zn (zinc), Ti (titanium), Pt (platinum), Ag (silver), Au (gold), Co (cobalt), and Ni (nickel). Examples of counter ions include sulfate ions, chloride ions, bromide ions, fluoride ions, iodide ions, hydroxide ions, nitrate ions, acetate ions, and oxide ions. These are used singly or in combination of two or more.

The antiviral/antibacterial inorganic particles may be composed of a particulate inorganic material and a metal or its ion carried on the particulate inorganic material. Examples of particulate inorganic substances include glass, silicon dioxide, titanium oxide, silicon particles, aluminum oxide, and zeolite. Examples of the supported metal include the metal species described above. The antiviral/antimicrobial inorganic particles may be metal processed into particles.

The average particle size of the antiviral/antibacterial inorganic particles is preferably 1 μm or less. As a result, deterioration in moldability and increase in haze are easily suppressed. The average particle size of the antiviral/antibacterial inorganic particles is more preferably 700 nm or less, particularly preferably 550 nm or less. The average particle size of the antiviral/antibacterial inorganic particles is preferably 5 nm or more, more preferably 10 nm or more.

The average particle size of the antiviral/antibacterial inorganic particles is the primary particle size, which is the 50% average particle size (D50) in the volume-based particle size distribution obtained by the laser diffraction/scattering method.

The content of the antiviral/antibacterial inorganic particles is, for example, 0.01 parts by mass or more and 60 parts by mass or less with respect to 100 parts by mass of the solid content of the composition F1. The content of the antiviral/antibacterial inorganic particles may be 1 part by mass or more, or 5 parts by mass or more, relative to 100 parts by mass of the solid content of the composition F1. The content of the antiviral/antibacterial inorganic particles may be 50 parts by mass or less, or 40 parts by mass or less, relative to 100 parts by mass of the solid content of the composition F1.

<Second layer forming component>
The second layer-forming component inhibits bleed-out of the antiviral/antimicrobial inorganic particles. Furthermore, the surface of the first functional layer can be smoothed by the second layer-forming component. This can further reduce the haze value. In addition, the second layer-forming component makes it difficult for the antiviral/antibacterial inorganic particles to fall off when the surface of the first functional layer is worn. As a result, the antiviral/antibacterial properties are likely to be maintained.

The second layer-forming component contains a second reactive component having two or more polymerizable functional groups in one molecule. The second reactive component comprises at least one selected from the group consisting of second monomers, second oligomers and second polymers. The weight average molecular weights of the second monomer and the second oligomer are 10,000 or less, and may be 9,000 or less. The weight average molecular weight of the second polymer is greater than 10,000 and may be 20,000 or more. The weight average molecular weight of the second polymer may be 100,000 or less.

The weight average molecular weight (Mw) can be calculated based on the molecular weight of standard polystyrene from the chromatogram measured by gel permeation chromatography.

The second reactive component preferably contains at least one of the second monomer and the second oligomer in terms of easily improving wear resistance. The total content of the second monomer and the second oligomer is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, relative to 100 parts by mass of the solid content of the composition F1. The total content of the second monomer and the second oligomer is preferably 60 parts by mass or less, more preferably 55 parts by mass or less, and particularly preferably 50 parts by mass or less, relative to 100 parts by mass of the solid content of the composition F1. In one aspect, the total content of the second monomer and the second oligomer is 5 parts by mass or more and 55 parts by mass or less with respect to 100 parts by mass of the solid content of the composition F1.

The acrylic equivalents of the second monomer and the second oligomer are not particularly limited. In terms of reactivity, the acrylic equivalent of the second monomer and second oligomer is 100 g/eq. 110 g/eq. The above is more preferable, and 115 g/eq. The above are particularly preferred. The acrylic equivalent of the second monomer and second oligomer is 200 g/eq. 180 g/eq. 160 g/eq. may be:

The content of the second polymer is, for example, 20 parts by mass or less with respect to 100 parts by mass of the solid content of the composition F1. The content of the second polymer is preferably 1 part by mass or more with respect to 100 parts by mass of the solid content of the composition F1. The content of the second polymer is preferably 15 parts by mass or less with respect to 100 parts by mass of the solid content of the composition F1.

The second reactive component preferably contains a (meth)acrylate compound from the viewpoint of adhesion to the transparent support substrate and hard coat layer and transparency. Examples of (meth)acrylate compounds include acrylic (meth)acrylate compounds such as acrylic (meth)acrylate monomers, acrylic (meth)acrylate oligomers and acrylic (meth)acrylate polymers; urethane (meth)acrylate monomers, urethane (meth) urethane (meth)acrylate compounds such as acrylate oligomers and urethane (meth)acrylate polymers; silicon (meth)acrylate compounds such as silicon (meth)acrylate monomers, silicon (meth)acrylate oligomers and silicon (meth)acrylate polymers. These are used singly or in combination of two or more. "(Meth)acrylate" represents acrylate and/or methacrylate.

Examples of (meth)acrylate monomers that are raw materials for (meth)acrylate compounds include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, ( 2-ethylhexyl meth)acrylate, acrylic acid, methacrylic acid, isostearyl (meth)acrylate, ethoxylated o-phenylphenol acrylate, methoxypolyethyleneglycol acrylate, methoxypolyethyleneglycol acrylate, phenoxypolyethyleneglycol acrylate, 2-acryloyloxyethyl Succinate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, ethylene glycol mono(meth)acrylate, propylene glycol mono(meth)acrylate, 2-hydroxy-3-methoxypropyl (meth)acrylate acrylates, dipentaerythritol hexaacrylate (DPHA), pentaerythritol (tri/tetra)acrylate (PETA), N-methylol(meth)acrylamide, N-hydroxy(meth)acrylamide.

Acrylic (meth)acrylate oligomers or polymers include, for example, polymers of at least one of the above (meth)acrylate monomers.

The urethane (meth)acrylate monomer or oligomer can also be prepared by reacting, for example, a polycarbonate diol, a (meth)acrylate compound containing a hydroxyl group and an unsaturated double bond group in the molecule, and a polyisocyanate. can.

Urethane (meth)acrylate polymers include, for example, polymers of at least one of the above urethane (meth)acrylate monomers and oligomers.

A silicon (meth)acrylate compound is a (meth)acrylate compound having a siloxane bond. While not to be bound by any particular theory, the silicone (meth)acrylate compound enables improved leveling and reduced tackiness of the uncured hard coat layer.

The second layer-forming component may contain a non-reactive component having less than 2 polymerizable functional groups per molecule.

The second reactive component (typically, a (meth)acrylate compound) may contain a fluorine atom from the viewpoint of improving wear resistance and antifouling properties, lowering the refractive index, and the like. The second layer-forming component may contain a non-reactive component having less than 2 polymerizable functional groups per molecule.

The acid value of the second layer-forming component is preferably 15 mgKOH/g or less, more preferably 10 mgKOH/g or less, and particularly preferably 5 mgKOH/g or less. In this case, the curing reaction due to heating of the composition F1 is likely to be suppressed. Therefore, the laminated film can still maintain a high draw ratio in the process prior to irradiation with active energy rays, such as the preforming process and the injection molding process, and the occurrence of cracks is more likely to be suppressed. The acid number is the number of milligrams of potassium hydroxide (KOH) required to neutralize the free acid in 1 gram of non-volatiles of the second layer-forming component. The acid value is measured according to JIS K 5601-2-1: acid value (titration method).

<First low refractive particles>
Composition F1 may contain first low refractive particles that lower the refractive index of the first functional layer. This allows the first functional layer to exhibit an anti-reflection function along with antiviral and/or antibacterial properties. The refractive index of the cured first functional layer is, for example, 1.20 or more and 1.55 or less, may be 1.25 or more and 1.50 or less, or may be 1.30 or more and 1.45 or less. .

Examples of the first low refractive particles include hollow silica fine particles. The hollow silica fine particles can lower the refractive index while maintaining the strength of the first functional layer. Hollow silica fine particles are structures filled with gas and/or porous structures containing gas. The refractive index decreases in inverse proportion to the gas occupancy. Therefore, the hollow silica fine particles have a lower refractive index than the original refractive index of the silica fine particles. Examples of hollow silica fine particles include Sururia 4320 (manufactured by Nikki Shokubai Kasei Co., Ltd.).

Silica fine particles having a nanoporous structure formed inside and/or at least partly on the surface may be used as the first low refractive particles. The nanoporous structure is formed according to the form, structure, aggregation state, and dispersion state inside the coating film of the silica fine particles. Hollow acrylic fine particles may be used as the first low refractive particles.

The volume average particle diameter of the first low refractive particles is preferably 50 nm or more and 200 nm or less. The volume average particle size is the primary particle size.

The content of the first low refractive particles is preferably 35 parts by mass or more, more preferably 37.5 parts by mass or more, relative to 100 parts by mass of the solid content of the composition F1. The content of the first low refractive particles is preferably 75 parts by mass or less, more preferably 60 parts by mass or less, relative to 100 parts by mass of the solid content of the composition F1. Thereby, the cured first functional layer tends to exhibit excellent antireflection properties. The content of the first low refractive particles is, for example, 35 parts by mass or more and 75 parts by mass or less with respect to 100 parts by mass of the solid content of the composition F1.

<Inorganic oxide fine particles>
Composition F1 may contain inorganic oxide fine particles. The inorganic oxide fine particles suppress volumetric shrinkage of the uncured first functional layer, and facilitate an increase in rigidity. Therefore, change in the appearance of the uncured first functional layer during the manufacturing process is likely to be suppressed. Furthermore, appearance change and curling of the cured first functional layer are suppressed. In addition, the tackiness of the hardened first functional layer is reduced, and wear resistance tends to increase.

The content of the inorganic oxide fine particles is preferably 20 parts by mass or less, more preferably 18 parts by mass or less, and particularly preferably 15 parts by mass or less with respect to 100 parts by mass of the solid content of the composition F1. The content of the inorganic oxide fine particles is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, and particularly preferably 3 parts by mass or more, relative to 100 parts by mass of the solid content of the composition F1.

The inorganic oxide fine particles are not particularly limited. Examples of inorganic oxide fine particles include silica (SiO ₂ ) particles (excluding hollow particles), alumina particles, titania particles, tin oxide particles, antimony-doped tin oxide (ATO) particles, and zinc oxide particles. . The surface of the inorganic oxide fine particles may be modified with a functional group containing an unsaturated double bond. A (meth)acryloyl group is desirable as the functional group. Among these, silica particles and alumina particles are preferred from the viewpoint of cost and paint stability, and silica particles and alumina particles whose surfaces are modified with functional groups are particularly preferred. The form of the inorganic oxide fine particles may be a sol.

The average particle size of the inorganic oxide fine particles is not particularly limited. From the viewpoint of transparency and property stability of the composition, the average particle size of the inorganic oxide fine particles is preferably 5 nm or more and 100 nm or less. The average particle size of the inorganic oxide fine particles is a value measured using image processing software from a cross-sectional image obtained by an electron microscope. The average particle size of other particulate matter is also determined by a similar method.

<Photoinitiator>
Composition F1 preferably comprises a photoinitiator. Thereby, the polymerization of the active energy ray-curable resin component is facilitated.

Examples of photopolymerization initiators include alkylphenone-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, titanocene-based photopolymerization initiators, and oxime ester-based polymerization initiators.

The content of the photopolymerization initiator is preferably 0.01 parts by mass or more, more preferably 1 part by mass or more, and particularly preferably 3 parts by mass or more, relative to 100 parts by mass of the solid content of the composition F1. The content of the photopolymerization initiator is preferably 10 parts by mass or less, more preferably 7 parts by mass or less, and particularly preferably 5 parts by mass or less, relative to 100 parts by mass of the solid content of the composition F1.

<solvent>
Composition F1 may contain a solvent. The solvent is not particularly limited, and is appropriately selected in consideration of the components contained in the composition, the type of transparent support substrate, the coating method, and the like.

Examples of solvents include aromatic solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone, acetone, methyl isobutyl ketone and cyclohexanone; diethyl ether, isopropyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, Ether solvents such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, anisole, and phenetole; ester solvents such as ethyl acetate, butyl acetate, isopropyl acetate, and ethylene glycol diacetate; dimethylformamide, diethylformamide, N-methylpyrrolidone amide solvents such as; cellosolve solvents such as methyl cellosolve, ethyl cellosolve and butyl cellosolve; alcohol solvents such as methanol, ethanol, propanol, isopropyl alcohol, butanol and isobutyl alcohol; and halogen solvents such as dichloromethane and chloroform. These solvents are used singly or in combination of two or more. Among them, ester solvents, ether solvents, alcohol solvents and ketone solvents are preferred.

<others>
Composition F1 can contain various additives as needed. Additives include, for example, antistatic agents, plasticizers, surfactants, antioxidants, UV absorbers, surface conditioners, surface modifiers, leveling agents and light stabilizers.

The content of each additive is not particularly limited, and may be appropriately set according to the desired effect. The content of each additive may be, for example, 1 part by mass or more, 3 parts by mass or more, or 5 parts by mass or more with respect to 100 parts by mass of the solid content of the composition F1. The content of each additive may be 20 parts by mass or less, and may be 15 parts by mass or less with respect to 100 parts by mass of the solid content of the composition F1.

[Uncured hard coat layer]
An uncured hard coat layer is formed on at least one surface of the transparent supporting substrate. The uncured hard coat layer and the transparent supporting substrate are adjacent to each other.

The uncured hard coat layer contains an active energy ray-curable hard coat layer-forming composition (hereinafter sometimes referred to as composition HC). Composition HC is cured by active energy rays. The hardness and/or stretch ratio of the hard coat layer can be controlled by adjusting the cumulative amount of active energy rays. Active energy rays are ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. The composition HC is particularly preferably UV curable. Composition HC is preferably cured by the same kind of active energy rays as composition F1.

The thickness of the uncured hard coat layer is not particularly limited. The thickness of the uncured hard coat layer is, for example, 2 μm or more and 30 μm or less. When the uncured hard coat layer has such a thickness, warping after curing is easily suppressed. Also, a hard coat layer having excellent hard coat performance (for example, mechanical properties and chemical resistance) can be obtained.

The thickness of the uncured hard coat layer is more preferably 3 μm or more. The thickness of the uncured hard coat layer is more preferably 25 μm or less, particularly preferably 20 μm or less.

The hard coat layer is also laminated in an uncured state with the uncured first functional layer. Furthermore, the laminated film is subjected to various processing in an uncured state. Therefore, the uncured hard coat layer has high hardness, low tackiness, is resistant to contamination, and is resistant to damage and appearance change during processing (e.g., foaming and cracking in the preforming process). In addition, curling due to the difference in heat shrinkability from other layers is required to be suppressed.

These requirements can be met by controlling the hardness, rigidity, smoothness, tackiness, etc. of the uncured hard coat layer. The physical properties of the uncured hard coat layer can be adjusted by adjusting its thickness, the composition of the hard coat layer-forming composition, and the like.

<<Hard coat layer forming composition>>
The hardcoat layer-forming composition (composition HC) comprises a first layer-forming component.

<First layer forming component>
The first layer-forming component includes a first reactive component having two or more polymerizable functional groups in one molecule. Preferably, the first reactive component comprises at least one of a first monomer and a first oligomer. As a result, the cross-linking density of the first layer-forming component is increased, and the hardness of the cured hard coat layer is easily improved. The weight average molecular weights of the first monomer and the first oligomer are 10,000 or less, and may be 9,000 or less.

The total content of the first oligomer and the first monomer is preferably 25 parts by mass or more and 65 parts by mass or less with respect to 100 parts by mass of the solid content of the composition HC. When the total content of the first oligomer and the first monomer is 25 parts by mass or more with respect to 100 parts by mass of the solid content of the composition HC, the hardness HBC is easily controlled to 0.5 _GPa or less. Therefore, the uncured hard coat layer and the uncured first functional layer are easily adhered to each other. Furthermore, when the uncured hard coat layer and the uncured first functional layer are laminated, it becomes easier to prevent air from entering between the layers (air entrapment). The total content of the first oligomer and the first monomer is more preferably 28 parts by mass or more, particularly preferably 30 parts by mass or more, relative to 100 parts by mass of the solid content of the composition HC.

When the total content of the first oligomer and the first monomer is 65 parts by mass or less with respect to 100 parts by mass of the solid content of the composition HC, the hardness HBC is easily controlled to 0.05 _GPa or more. Therefore, problems such as dents and damages during slit formation and cutting, dents due to foreign matter mixed in when laminating a plurality of laminated films, squeegee marks, and suction marks are suppressed, and the yield is easily improved. The total content of the first oligomer and the first monomer is more preferably 62 parts by mass or less, particularly preferably 60 parts by mass or less, relative to 100 parts by mass of the solid content of the composition HC.

The solids content of Composition HC is all components of Composition HC, excluding solvent. The same applies to the solid content of the first functional layer forming composition.

The first reactive component preferably contains a first polymer having a weight-average molecular weight of more than 10,000 together with the first monomer and/or the first oligomer in order to suppress the tackiness of the uncured hard coat layer. The weight average molecular weight of the first polymer is greater than 10,000 and may be 20,000 or more. The weight average molecular weight of the first polymer may be 100,000 or less.

The content of the first polymer is preferably 30 parts by mass or more and 70 parts by mass or less with respect to 100 parts by mass of the solid content of the composition HC. The content of the first polymer is more preferably 32 parts by mass or more, particularly preferably 35 parts by mass or more, relative to 100 parts by mass of the solid content of the composition HC. The content of the first polymer is more preferably 68 parts by mass or less, particularly preferably 65 parts by mass or less, relative to 100 parts by mass of the solid content of the composition HC.

Preferred first reactive components include (meth)acrylate compounds similar to those exemplified for the second reactive component. From the viewpoint of adhesion to the uncured first functional layer and transparency, the first reactive component preferably contains a (meth)acrylate compound.

The acid value of the first layer-forming component is preferably 15 mgKOH/g or less, more preferably 10 mgKOH/g or less, and even more preferably 5 mgKOH/g or less. In this case, the curing reaction due to heating of the composition HC is likely to be suppressed. Therefore, as described above, the occurrence of cracks is more likely to be suppressed.

<Antiviral/antibacterial inorganic particles>
Composition HC may include antiviral/antimicrobial inorganic particles. This makes it easier for antiviral/antibacterial properties to be exhibited over a long period of time. Antiviral/antimicrobial inorganic particles similarly include those exemplified for composition F1.

The content of the antiviral/antibacterial inorganic particles in the composition HC is not particularly limited. In terms of transparency, the content of the antiviral/antibacterial inorganic particles in Composition HC with respect to 100 parts by weight of Composition HC is 100 parts by weight of the antiviral/antibacterial inorganic particles in Composition F1. It may be equal to or less than the content relative to composition F1.

<Inorganic oxide fine particles>
The composition HC may contain inorganic oxide particulates. Examples of inorganic oxide fine particles include those exemplified for composition F1. The content of the inorganic oxide fine particles is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and particularly preferably 7 parts by mass or more, relative to 100 parts by mass of the solid content of the composition HC. The content of the inorganic oxide fine particles is preferably 20 parts by mass or less, more preferably 18 parts by mass or less, and particularly preferably 15 parts by mass or less with respect to 100 parts by mass of the solid content of the composition HC.

<Photoinitiator>
The composition HC preferably contains a photoinitiator. Thereby, the polymerization of the active energy ray-curable resin component is facilitated. Photoinitiators likewise include those exemplified for composition F1.

Among others, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane- 1-one selected from the group consisting of 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 and 2,2-dimethoxy-1,2-diphenylethan-1-one At least one is preferred.

The content of the photopolymerization initiator is preferably 0.01 parts by mass or more and 10 parts by mass or less, more preferably 1 part by mass or more and 10 parts by mass or less, relative to 100 parts by mass of the solid content of the composition HC.

<solvent>
The composition HC may contain a solvent. The solvent is not particularly limited, and is appropriately selected in consideration of the components contained in the composition, the type of transparent support substrate, the coating method, and the like. Solvents likewise include those exemplified for composition F1. Among them, ester solvents, ether solvents, alcohol solvents and ketone solvents are preferred.

<others>
The composition HC can contain various additives as required. Additives include, for example, antistatic agents, plasticizers, surfactants, antioxidants, UV absorbers, surface conditioners, surface modifiers, leveling agents and light stabilizers.

The content of each additive is not particularly limited, and may be appropriately set according to the desired effect. The content of each additive may be, for example, 1 part by mass or more, 3 parts by mass or more, or 5 parts by mass or more with respect to 100 parts by mass of the solid content of the composition HC. The content of each additive may be 20 parts by mass or less, or 15 parts by mass or less, relative to 100 parts by mass of the solid content of the composition HC.

The layer-forming components contained in composition HC and composition F1 may be the same or different. Above all, it is preferable that the layer-forming components of both are the same or of the same kind. This is because the adhesion between the uncured hard coat layer and the uncured first functional layer is improved, and delamination between the layers is less likely to occur.

The composition of composition HC and composition F1 may be the same or different. In this embodiment, a layer responsible for hard coat performance and a layer responsible for antiviral/antibacterial properties are separately provided. Therefore, each layer can have different properties. For example, the composition of the first functional layer is adjusted so that other supporting substrates can be easily peeled off from the uncured first functional layer, while the uncured hard coat layer does not peel off from the transparent supporting substrate. Thus, the composition of the hard coat layer can be adjusted. Both releasability and adhesion can be achieved by changing composition HC and composition F1.

[Uncured functional layer]
The laminated film may further have at least one other uncured functional layer between the uncured hard coat layer and the uncured first functional layer. Other functional layers reinforce the optical functions of the laminated film or impart new optical functions.

Other functional layers, for example, have different optical properties than the first functional layer described above. When the first functional layer contains first low refractive particles, the other functional layer may be, for example, a high refractive index second functional layer. The second functional layer contains high refractive particles that increase the refractive index of the second functional layer. Examples of high refractive particles include zirconium oxide and titanium dioxide. The second functional layer may be a so-called high refractive index layer with a refractive index of more than 1.55 and 2.00 or less, or a so-called medium refractive index layer with a refractive index of 1.55 or more and 1.75 or less. It may be a combination.

If the first functional layer does not contain the first low refractive particles, the other functional layer may be, for example, a low refractive index third functional layer. The third functional layer contains second low refractive particles that lower the refractive index of the third functional layer. Examples of the second low refractive particles include those similar to the above first low refractive particles. The refractive index of the cured third functional layer is, for example, 1.20 or more and 1.55 or less, may be 1.25 or more and 1.50 or less, or may be 1.30 or more and 1.45 or less. .

Between the uncured hard coat layer and the uncured third functional layer, an uncured high refractive index second functional layer as described above may be further disposed.

The thickness of other functional layers is not particularly limited. The thickness of each other functional layer may be 10 nm or more and 300 nm or less. The thickness of each other functional layer is preferably 15 nm or more, more preferably 20 nm or more, and particularly preferably 40 nm or more. The thickness of each other functional layer is preferably 200 nm or less, more preferably 180 nm or less, and particularly preferably 150 nm or less.

The functional layer-forming composition for forming other functional layers may contain the same components as those contained in composition HC or composition F1 described above. Components contained in a plurality of other functional layers may be the same or different. The functional layer-forming composition may contain antiviral/antimicrobial inorganic particles.

Other functional layers may contain a resin component other than the active energy ray-curable resin component. Other resin components include thermoplastic resins such as alkyd resins, polyester resins, and acrylic resins; thermosetting resins such as epoxy resins, phenol resins, melamine resins, urethane resins, and silicone resins. Resin; includes polyisocyanate.

[Other supporting substrates]
The laminated film may have another supporting substrate on the surface of the uncured first functional layer opposite to the uncured hard coat layer. As a result, when the laminated film is wound into a roll or unwound from the roll, damage is easily suppressed.

Another supporting base protects the first functional layer and the laminated film, and functions as a release paper for forming the composition F1 into a film. Other supporting substrates may have an adhesive layer on the coating surface.

As other supporting substrates, films known as protective films in the art are used without particular limitation. Other supporting substrates may be colorless or colored. Other supporting substrates may be transparent.

The thickness of the other supporting substrate is not particularly limited. The thickness of the other supporting substrate may be 20 μm or more and 100 μm or less. As a result, the effect of protecting the uncured first functional layer is likely to increase. The thickness of the other supporting substrate is preferably 25 µm or more, more preferably 30 µm or more, still more preferably 33 µm or more, and particularly preferably 35 µm or more. The thickness of the other supporting substrate is preferably 85 μm or less, more preferably 80 μm or less, and particularly preferably 65 μm or less. The thickness of other supporting substrates is a value that does not include the thickness of the adhesive layer.

Other supporting substrates are made of resin, for example. Examples of resin films include polyolefin films such as polyethylene films and polypropylene films (including unstretched polypropylene films (CPP films) and biaxially stretched polypropylene films (OPP films)); modified polyolefin films obtained by modifying these films; polyethylene terephthalate, polycarbonate and polyester films such as polylactic acid; polystyrene resin films such as polystyrene films, AS resin films and ABS resin films; nylon films; polyamide films; Among them, at least one selected from polyethylene film, polystyrene film, modified polyolefin film, polymethylpentene film, OPP film and CPP film is preferable.

Additives such as an antistatic agent and an anti-ultraviolet agent may be added to the resin film, if necessary. The surface of the resin film may be subjected to corona treatment or low temperature plasma treatment.

FIG. 1 is a cross-sectional view schematically showing a laminated film according to this embodiment. The laminated film 10A includes a transparent supporting substrate 11, an uncured hard coat layer 12 disposed on one main surface thereof, and an uncured first functional layer 13 formed on the uncured hard coat layer 12. And prepare.

FIG. 2 is a cross-sectional view schematically showing another laminated film according to this embodiment. The laminated film 10B includes a transparent supporting substrate 11, an uncured hard coat layer 12 disposed on one main surface thereof, and an uncured first functional layer 13 formed on the uncured hard coat layer 12. and an uncured second functional layer 14 disposed between the hard coat layer 12 and the first functional layer 13 . The first functional layer 13 has antiviral and/or antibacterial properties as well as a low refractive index. The second functional layer 14 has a high refractive index.

FIG. 3 is a cross-sectional view schematically showing another laminated film according to this embodiment. The laminated film 10C includes a transparent supporting substrate 11, an uncured hard coat layer 12 disposed on one main surface thereof, and an uncured first functional layer 13 formed on the uncured hard coat layer 12. and an uncured second functional layer 14 and a third functional layer 15 disposed between the hard coat layer 12 and the first functional layer 13 . The second functional layer 14 has a high refractive index and the third functional layer 15 has a low refractive index.

B. Molded Article The molded article according to the present embodiment includes a cured product of the laminated film. The molded article has a transparent supporting substrate, a cured hard coat layer, and a cured first functional layer. The molded body may further have at least one other cured functional layer between the cured hard coat layer and the cured first functional layer. The molded article may or may not have the other support substrates described above. Other supporting substrates are used depending on the intended use.

For example, the molded article is obtained by irradiating an active energy ray with an integrated light amount of 200 mJ/cm ² or more to a laminated film molded into a three-dimensional shape to completely cure the uncured hard coat layer and the uncured first functional layer. It is obtained by letting

The molded product is particularly suitable as a protective material for a display and various sensors arranged around it. Examples of displays include liquid crystal displays, organic EL displays, and plasma displays. The molded article is particularly suitable as a touch panel display for vehicles and a protective material therearound. The molded body is arranged so that the first functional layer is outside the hard coat layer.

[Decoration layer]
The molding may further include a decorative layer. The decorative layer is a layer that imparts decoration such as patterns, characters, or metallic luster to the molded article. The decorative layer enhances the design of the molded product.

The molded article includes, for example, a transparent supporting substrate, a hard coat layer and a first functional layer arranged on one main surface of the transparent supporting substrate, and a decoration arranged on the other main surface of the transparent supporting substrate. a layer; The decorative layer may be provided on a portion of the other main surface of the transparent supporting base material. When the molding is a protective material for a display, the decorative layer is provided, for example, on the bezel portion surrounding the display.

The decorative layer includes, for example, at least one of a printed layer and a deposited layer. Each of the printed layer and the deposited layer is one or more layers and may comprise multiple layers. The thickness of the decorative layer is not particularly limited, and is appropriately set according to design properties and the like.

For example, a wood grain pattern, a stone grain pattern, a grain pattern, a sand grain pattern, a geometric pattern, characters, and a solid pattern are drawn on the printed layer. The print layer is formed of, for example, a colored ink containing a binder resin and a coloring agent. The binder resin is not particularly limited. Examples of binder resins include polyvinyl resins such as vinyl chloride/vinyl acetate copolymers, polyamide resins, polyester resins, polyacrylic resins, polyurethane resins, polyvinyl acetal resins, polyester urethane resins, and cellulose. Ester-based resins, alkyd resins, and chlorinated polyolefin-based resins can be used.

Colorants are not particularly limited, and include known pigments or dyes. Examples of yellow pigments include azo pigments such as polyazo, organic pigments such as isoindolinone, and inorganic pigments such as titanium nickel antimony oxide. Examples of red pigments include azo pigments such as polyazo, organic pigments such as quinacridone, and inorganic pigments such as red iron oxide. Examples of blue pigments include organic pigments such as phthalocyanine blue and inorganic pigments such as cobalt blue. Examples of black pigments include organic pigments such as aniline black. Examples of white pigments include inorganic pigments such as titanium dioxide.

The deposited layer is formed of, for example, at least one metal selected from the group of aluminum, nickel, gold, platinum, chromium, iron, copper, indium, tin, silver, titanium, lead, zinc, etc., or alloys or compounds thereof. be done.

[Molding resin layer]
The molded body may further include a molded resin layer. The molded resin layer supports the hard coat layer and the first functional layer together with the transparent supporting substrate. The molded body is composed of, for example, a transparent supporting substrate, a hard coat layer and a first functional layer arranged on one main surface of the transparent supporting substrate, and a molding resin arranged on the other main surface of the transparent supporting substrate. a layer; The shape of the molded resin layer is not limited. Therefore, the degree of freedom in designing the molded body increases.

The molded article comprises a transparent supporting substrate, a hard coat layer and a first functional layer arranged on one main surface of the transparent supporting substrate, and a decorative layer arranged on the other main surface of the transparent supporting substrate. , and a molded resin layer. The decorative layer is arranged, for example, so as to be sandwiched between the cured resin layer and the molded resin layer, or arranged on the surface of the molded resin layer opposite to the cured resin layer.

The resin (molding resin) forming the molded resin layer is not particularly limited. The molded resin layer contains, for example, a thermosetting resin and/or a thermoplastic resin. Thermosetting resins include, for example, phenol resins, epoxy resins, melamine resins, urea resins, unsaturated polyesters, and thermosetting polyimides. Thermoplastic resins include so-called engineering plastics. Engineering plastics include, for example, polyamides, polyacetals, polycarbonates, ultra-high molecular weight polyethylenes, polysulfones, polyethersulfones, polyphenylene sulfides, and liquid crystal polymers.

FIG. 4 is a cross-sectional view schematically showing a molded body according to this embodiment. The molded article 20 includes a transparent supporting substrate 11, a cured hard coat layer 22 disposed on one main surface thereof, a cured first functional layer 23 formed on the hard coat layer 22, and a cured material. A decorative layer 24 and a molded resin layer 25 are provided. The decorative layer 24 is arranged so as to partially cover the other main surface of the transparent supporting base material 11 . The molded resin layer 25 is arranged so as to cover the entire other main surface of the transparent support base 11 and the entire decorative layer 24 .

In another aspect, another hardened functional layer (typically, the second functional layer and/or the third functional layer) is arranged between the hard coat layer 22 and the first functional layer 23. .

C. Method for producing laminated film The laminated film according to the present embodiment is formed by applying an active energy ray-curable hard coat layer-forming composition onto one surface of a transparent supporting substrate to form an uncured hard coat layer. a step of applying an active energy ray-curable first functional layer forming composition on one surface of another supporting substrate to form an uncured first functional layer; a lamination step of obtaining a laminated film by bonding together the surface of the hard coat layer opposite to the transparent supporting substrate and the surface of the uncured first functional layer opposite to the other supporting substrate. manufactured by the method. The first functional layer-forming composition contains the antiviral/antibacterial inorganic particles described above. The stretch ratio at 160° C. of the laminated film to be obtained is 50% or more.
FIG. 5 is a flow chart showing a method for manufacturing a laminated film according to this embodiment.

In the step of forming the uncured first functional layer, unevenness derived from the antiviral/antibacterial inorganic particles may be formed on the outer surface of the first functional layer. The material-side surface (inner surface) is smooth. Then, when the uneven outer surface and the uncured hard coat layer are adhered together and another supporting substrate is peeled off, the smooth inner surface of the first functional layer is exposed. As a result, a laminated film having a smooth first functional layer can be obtained, and haze can be easily suppressed.

In addition, according to the lamination method, the adhesion between the uncured hard coat layer and the uncured first functional layer is enhanced, but the phase mixture is easily suppressed. Therefore, the antiviral/antibacterial inorganic particles can remain on the first functional layer, which is the surface layer, and the antiviral and/or antibacterial properties are exhibited more effectively. The lamination method is a suitable method for producing an after-cured laminated film.

Furthermore, in this method, since the composition HC is applied to the transparent supporting substrate, the transparent supporting substrate and the uncured hard coat layer are adjacent to each other. Therefore, a molded article obtained from this laminated film has excellent adhesion and pencil hardness.

(1-1) Step of forming an uncured hard coat layer (S11)
An uncured hard coat layer is formed by applying the above composition HC on one side of a transparent supporting substrate. Composition HC can be prepared by techniques commonly practiced by those skilled in the art. For example, it can be prepared by mixing each of the above components using a commonly used mixing device such as a paint shaker or a mixer.

The method of applying the composition HC is not particularly limited, and is carried out by a technique commonly used by those skilled in the art. Examples of coating methods include dip coating, air knife coating, curtain coating, roller coating, bar coating (for example, wire bar coating), die coating, inkjet and gravure coating.

The coating amount of the composition HC is not particularly limited. The composition HC is applied, for example, so that the uncured hard coat layer has a thickness of 2 μm or more and 30 μm or less after drying.

After coating, a drying step may be performed. The drying conditions are not particularly limited, and are appropriately set so that at least part of the solvent contained in the composition HC is removed. Drying methods include, for example, air drying (natural drying), heat drying, and vacuum drying. Among them, drying by heating is preferable. Heating can dry and level the uncured hard coat layer. Drying is performed after the uncured hard coat layer is formed on the transparent support substrate and before the uncured hard coat layer is subjected to the lamination step. For example, the uncured hard coat layer is dried before the transparent support substrate with the uncured hard coat layer is loaded into the laminating machine.

After the uncured hard coat layer is formed, the transparent supporting substrate may be wound into a roll. This enables roll-to-roll processing up to the lamination step. Furthermore, the transparent support substrate may be wound up after a protective film is attached to the surface of the uncured hard coat layer. The protective film and the uncured hard coat layer may be attached via an adhesive layer.

(1-2) Step of forming an uncured first functional layer (S12)
The uncured first functional layer is formed by applying the above composition F1 onto one surface of another supporting substrate. The preparation and application of composition F1 are carried out by methods commonly used by those skilled in the art, similarly to composition HC.

The amount of composition F1 to be applied is not particularly limited. The composition F1 is applied, for example, so that the uncured first functional layer has a thickness of 15 nm or more and 1 mm or less after drying.

After coating, a drying step may be performed. The drying conditions are not particularly limited, and are appropriately set so that at least part of the solvent contained in composition F1 is removed. The drying method includes the same method as for drying the hard coat layer. Among them, drying by heating is preferable.

Drying is performed after the uncured first functional layer is formed on another supporting base material and before the uncured first functional layer is subjected to the lamination step. For example, the uncured first functional layer is dried before another supporting substrate with the uncured first functional layer is brought into the laminating machine.

After the uncured first functional layer is formed, another supporting substrate may be wound into a roll. This enables roll-to-roll processing up to the lamination step. Furthermore, another supporting substrate may be wound up after a protective film is attached to the surface of the uncured first functional layer. The protective film and the uncured first functional layer may be attached via an adhesive layer.

(1-3) Lamination step (S13)
The uncured first functional layer formed on another supporting substrate and the uncured hard coat layer formed on the transparent supporting substrate are bonded together. Thereby, a laminated film is obtained.

When the other supporting substrate on which the uncured first functional layer is formed is wound up, the transparent supporting substrate including the uncured hard coat layer is carried into the laminating machine, and the other that has been wound up is The supporting base material of is carried into the laminating machine while being unwound.

When the transparent supporting substrate on which the uncured hard coat layer is formed is wound up, another supporting substrate having the uncured first functional layer is carried into the laminating machine, and the wound transparent The supporting base material is carried into the laminating machine while being unwound.

Bonding is preferably performed while applying pressure. The pressure may be, for example, 0.1 N/cm or more and 50 N/cm or less. The pressure is preferably 0.5 N/cm or higher. The pressure is preferably 30 N/cm or less.

The temperature of each layer during bonding is not particularly limited. Since each layer is uncured, it can be laminated at a low temperature. On the other hand, since the lamination method tends to suppress the occurrence of mixed phases, each layer may be heated during lamination. The temperature of each layer during bonding may be 0° C. or higher and 100° C. or lower.

After the lamination step, the laminated film may be wound into a roll. In this case, it is preferable that the other supporting substrate is not peeled off.

The resulting laminated film may be heated for leveling. Heating is performed, for example, in an atmosphere of 150° C. or higher and 190° C. or lower for 30 seconds or longer and 60 seconds or shorter. Other supporting substrates may be peeled off prior to heating. Leveling may be performed using heat applied during the preforming process.

A laminated film having another uncured functional layer between an uncured hard coat layer and an uncured first functional layer is produced, for example, by the following steps.
First, another uncured functional layer is formed on a new supporting substrate. Next, the surface of the uncured hard coat layer opposite to the transparent supporting substrate and the surface of the other uncured functional layer opposite to the new supporting substrate are bonded together. After peeling off the new supporting substrate, the uncured first functional layer supported by another supporting substrate is attached to the exposed other uncured functional layer. If necessary, the step of bonding another uncured functional layer to an uncured hard coat layer or another uncured functional layer laminated thereon is repeated before bonding the first functional layer.

As a result, a laminated film containing, in this order, a transparent supporting substrate, an uncured hard coat layer, at least one uncured functional layer, an uncured first functional layer, and another supporting substrate is obtained. can get. Other supporting substrates may or may not be stripped.

FIG. 6 is a schematic diagram illustrating the lamination step in the method for manufacturing a laminated film according to this embodiment. An uncured hard coat layer 12 is formed on one surface of the transparent supporting substrate 11 . This laminate is obtained in the step of forming an uncured hard coat layer. This laminate is conveyed in a flat state from left to right in FIG.

On the other hand, an uncured first functional layer 13 is laminated on one surface of another supporting base material 16 . This laminate is obtained in the step of forming an uncured first functional layer. This laminate is conveyed in a flat state from left to right in FIG.

While transporting these laminates, the surface of the uncured hard coat layer 12 opposite to the transparent supporting substrate 11 and the surface of the uncured first functional layer 13 opposite to the other supporting substrate 16 were coated. while applying pressure by a pair of rollers 30. to paste together. As a result, a laminated film including the transparent supporting substrate 11, the uncured hard coat layer 12, the uncured first functional layer 13, and the other supporting substrate 16 in this order is obtained.

Various dimensions in the illustrated example are merely one aspect. The thickness and size of each layer and each base material, the position and size of the roller, and the like may be appropriately set.

D. Method for Producing Molded Article The molded article according to the present embodiment is produced by a method including a curing step of irradiating the laminated film with an active energy ray having an accumulated light amount of 200 mJ/cm ² or more.

The curing step is optionally preceded by an injection molding step, or a preform step and an injection molding step. In the preforming step, the laminated film is formed into a desired three-dimensional shape by thermoforming.

If a preforming step is performed, the curing step may be performed multiple times. For example, after the preforming step, a semi-curing step may be performed in which active energy rays are applied so as to partially cure the laminated film. In this case, after the injection molding process, a main curing process is performed in which active energy rays are applied so as to cure the remaining part of the laminated film. In the main curing step, active energy rays with an accumulated light amount of 200 mJ/cm ² or more are irradiated.

A decorative layer may be arranged on the other main surface of the laminated film. The step of forming the decorative layer (decorating step) is performed, for example, before the curing step (preferably the preforming step).

If the laminated film comprises another supporting substrate, the other supporting substrate may be peeled off prior to the curing step. This increases the degree of freedom in selecting other supporting substrates. In the laminated film according to this embodiment, both the hard coat layer and the first functional layer are laminated in an uncured state, so that the adhesion between the layers is high. Therefore, when peeling off another supporting substrate, partial peeling of the uncured first functional layer and air entrainment between the uncured first functional layer and the uncured hard coat layer are suppressed. easy. In particular, other supporting substrates may be stripped off prior to the preform step. As a result, the surface of the first functional layer is easily flattened by heat during the preforming process. Other supporting substrates may be peeled off after the preform process. This makes it easier to prevent foreign matter from entering the laminated film.

In one aspect, the molded article is manufactured by a method comprising a decorating step (S21), a preforming step (S22), a curing step (S23) and an injection molding step (S24) in this order. FIG. 7 is a flow chart showing a method for manufacturing a molded body according to this embodiment.

In one embodiment, the molded body undergoes the decorating step (S21), the preforming step (S22), the semi-curing step (S23-1), the injection molding step (S24) and the main curing step (S23-2) in this order. Manufactured by a method comprising: FIG. 8 is a flow chart showing another method for manufacturing a molded body according to this embodiment.

When the laminated film is wound into a roll, the laminated film is unwound from the roll, slitted, or cut into a desired shape and size prior to the decorating step. good too.
Each step will be described below.

(2-1) Decorating step (S21)
A decorative layer (typically, a printed layer and a vapor deposition layer) is formed on the other main surface of the transparent support substrate of the laminated film.

A method for forming the printed layer is not particularly limited. Examples of methods for forming the printed layer include offset printing, gravure printing, screen printing, roll coating and spray coating. The formation method of the vapor deposition layer is also not particularly limited. Methods for forming the deposited layer include, for example, a vacuum deposition method, a sputtering method, an ion plating method and a plating method.

(2-2) Preform step (S22)
The laminate film is preformed into a shape along the desired three-dimensional shape. Injection molding (typically, insert mold lamination (IML) molding) becomes possible by shaping the laminated film into a nearly three-dimensional shape in advance. In IML molding, a laminated film is inserted into a mold, and molding resin is injected toward the laminated film. After the preforming step, a trimming step for removing unnecessary portions of the laminated film may be performed.

The preforming method is not particularly limited. Preforms are produced, for example, by vacuum forming, air pressure forming, vacuum pressure forming. In preforms, the mold and the laminated film are installed in the same processing chamber. The laminated film is installed so that the transparent supporting substrate faces the mold. The laminated film is heated and the processing chamber is evacuated and/or pressurized. Thereby, the laminated film is deformed along the mold. The laminated film is then cooled and removed from the mold. During preforming, the laminated film may be heated at 90° C. or higher and 190° C. or lower for 20 seconds or more and 5 minutes or less.

(2-3) Semi-curing step (S23-1)
An active energy ray is applied so that a part of the laminated film is cured. Thereby, a laminated film in a semi-cured state is obtained. The semi-curing process prevents the laminated film from sticking to the mold during the injection molding process, and adjusts the stretch ratio of the laminated film to the level required for the injection molding process, thereby suppressing the occurrence of cracks during the injection molding process. can do. The integrated light quantity of the active energy rays is, for example, 1 mJ/cm ² or more and less than 200 mJ/cm ² . After the semi-curing step, a trimming step for removing unnecessary portions of the laminated film may be performed.

The type of active energy ray is not particularly limited. The active energy ray is appropriately selected according to the type of resin component contained in the layer-forming composition. The active energy ray is not particularly limited, and may be ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. Among them, ultraviolet light having a wavelength of 380 nm or less is preferable. Ultraviolet rays are applied using, for example, a high-pressure mercury lamp or an extra-high pressure mercury lamp.

(2-4) Injection molding step (S24)
In injection molding, for example, the first functional layer is opposed to a mold, and a molding resin is injected toward the transparent supporting substrate. As a result, the laminated film is shaped into the shape of the mold, and a molded resin layer is formed on the other main surface of the transparent supporting substrate.

(2-5) Curing step (S23), main curing step (S23-2)
The laminate film is irradiated with active energy rays to completely cure the laminate film. A compact is thus obtained. The cumulative amount of active energy rays used in the step of completely curing the laminated film is 200 mJ/cm ² or more. The cumulative amount of active energy rays may be 5000 mJ/cm ² or less, and may be 3000 mJ/cm ² or less. The active energy ray may be of the same type as that used in the semi-curing step, or may be different.

As described above, the above-described embodiment is an example, and known treatments, processing steps, and the like may be introduced as desired.

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these. In the examples, "parts" and "%" are based on mass unless otherwise specified. Hereinafter, the first polymer and the second polymer may be collectively referred to as reactive polymers. Similarly, the first and second monomers may be collectively referred to as reactive monomers, and the first and second oligomers may be collectively referred to as reactive oligomers.

Components used in Examples and Comparative Examples are as follows.
(reactive acrylic polymer)
Acrylic polymer A: Mw70,000
Acrylic polymer B: Mw20,000

Acrylic polymers A and B were prepared as follows.
[Preparation of acrylic polymer A]
A mixture of 30.0 parts of 2,3-epoxypropyl methacrylate, 70 parts of methyl methacrylate and 1.5 parts of t-butylperoxy-2-ethylhexanoate was prepared. Separately, 40.0 parts of toluene was put into a 500 ml reaction vessel equipped with a stirring blade, a nitrogen inlet tube, a cooling tube and a dropping funnel, and heated to 110°C. While stirring the inside of the reaction vessel, the above mixture was added dropwise at a constant rate over 2 hours under a nitrogen atmosphere. After completion of dropping, the reaction was carried out for 1 hour at a temperature of 110°C. Thereafter, a mixed solution of 1.0 part of t-butylperoxy-2-ethylhexanoate and 25.0 parts of toluene was added dropwise to the reaction vessel over 1 hour. Then, the inside of the reaction vessel was heated to 145° C., and the reaction was further performed for 2 hours. Subsequently, the inside of the reaction vessel was cooled to 110° C. or lower, and 59.0 parts of toluene was added to obtain precursor A1.

226.5 parts of precursor A1, 15.66 parts of acrylic acid, 0.43 parts of hydroquinone monomethyl ether, and 56 parts of toluene were charged into another reaction vessel of the same shape as the above, and air was blown in to stir. while heating to 90°C. A mixed solution of 3.0 parts of toluene and 0.81 parts of tetrabutylammonium bromide was further added to the reaction vessel at a temperature of 90° C. and reacted for 1 hour. Subsequently, the mixture was heated to 105° C., and the reaction was carried out at a temperature of 105° C. until the acid value of the solid content in the reaction liquid became 8 or less. Thereafter, a mixed solution of 0.43 parts of hydroquinone monomethyl ether and 3.0 parts of toluene was added to the above reaction solution, and the temperature was adjusted to 75°C. Subsequently, a mixed solution of 10.1 parts of Karenz MOI (manufactured by Showa Denko), 5.0 parts of toluene and 0.043 parts of dibutyltin dilaurate was added and reacted at 70° C. for 2 hours. After that, the mixture was cooled to 60° C. or lower, and a mixed solution of 2.0 parts of methanol and 10.0 parts of toluene was added. As a result, an acrylic polymer A having a weight average molecular weight of 70,000 was obtained.

The acid value is measured according to JIS K5601-2-1, by titrating the above reaction solution with a 0.1N potassium hydroxide (KOH) solution, and using the following formula: acid value = {(dropped amount of KOH solution [ml ])×(molar concentration of KOH solution [mol/L]}/(mass of solid content [g]). The same applies hereinafter.

[Preparation of acrylic polymer B]
A mixture of 30.0 parts of 2,3-epoxypropyl methacrylate, 70 parts of methyl methacrylate and 10.0 parts of t-butylperoxy-2-ethylhexanoate was prepared. Separately, 40.0 parts of toluene was put into a 500 ml reaction vessel equipped with a stirring blade, a nitrogen inlet tube, a cooling tube and a dropping funnel, and heated to 110°C. While stirring the inside of the reaction vessel, the above mixture was added dropwise at a constant rate over 2 hours under a nitrogen atmosphere. After completion of dropping, the reaction was carried out for 1 hour at a temperature of 110°C. Thereafter, a mixed solution of 1.0 part of t-butylperoxy-2-ethylhexanoate and 25.0 parts of toluene was added dropwise to the reaction vessel over 1 hour. Then, the inside of the reaction vessel was heated to 145° C., and the reaction was further performed for 2 hours. Subsequently, the inside of the reaction vessel was cooled to 110° C. or lower, and 59.0 parts of toluene was added to obtain precursor B1.

306.5 parts of precursor B1, 15.66 parts of acrylic acid, 0.43 parts of hydroquinone monomethyl ether, and 56 parts of toluene were charged into another reaction vessel of the same shape as above, and air was blown into the reaction vessel and stirred. while heating to 90°C. A mixed solution of 3.0 parts of toluene and 0.81 parts of tetrabutylammonium bromide was further added to the reaction vessel at a temperature of 90° C. and reacted for 1 hour. Subsequently, the mixture was heated to 105° C., and the reaction was carried out at a temperature of 105° C. until the acid value of the solid content in the reaction liquid became 8 or less. Thereafter, a mixed solution of 0.43 parts of hydroquinone monomethyl ether and 3.0 parts of toluene was added to the above reaction solution, and the temperature was adjusted to 75°C. Subsequently, a mixed solution of 10.1 parts of Karenz MOI (manufactured by Showa Denko), 5.0 parts of toluene and 0.043 parts of dibutyltin dilaurate was added and reacted at 70° C. for 2 hours. After that, the mixture was cooled to 60° C. or lower, and a mixed solution of 2.0 parts of methanol and 10.0 parts of toluene was added. As a result, an acrylic polymer B having a weight average molecular weight of 20,000 was obtained.

(reactive oligomer)
KRM-8452: Daicel Allnex Co., Ltd., polyfunctional urethane acrylate oligomer, Mw 3,884, acrylic equivalent 120 g / eq

(reactive monomer)
Aronix M-402: manufactured by Toagosei Co., Ltd., DPHA

(antiviral/antimicrobial particles)
Ionpure ZAF HS: manufactured by Ishizuka Glass Co., Ltd., metal (Ag, Cu, Zn) ion-supported glass, inorganic particles, average particle size 100 nm
Cufitec: manufactured by NBC Meshtec Co., Ltd., monovalent copper compound, inorganic particles, average particle size 500 nm
ELCOM1023: manufactured by Nikki Shokubai Kasei Co., Ltd., Ag ion-supported silica/aluminum oxide, inorganic particles, average particle size 15 nm
Zeomic HD10N: manufactured by Sinanen Zeomic Co., Ltd., metal (Ag, Zn) ion-supported zeolite, inorganic particles, average particle size 1.5 μm
Sulamoni D100: manufactured by Osaka Gas Chemicals Co., Ltd., quaternary ammonium salt, organic matter

(Inorganic oxide fine particles)
OSCAL-1842: manufactured by Nikki Shokubai Kasei Co., Ltd., reactive silica organosol, particle size 10 nm

(low refractive particles)
Sururia 4320: manufactured by Nikki Shokubai Kasei Co., Ltd., average particle size 55 nm
(High refractive particles)
NANON5 ZR-010: manufactured by Solar Co., Ltd., zirconium oxide, average particle size 20 nm

(Photoinitiator)
Omnirad 127: manufactured by IGM RESINS, α-hydroxyacetophenone Omnirad 184: manufactured by IGM RESINS, α-hydroxyalkylphenone

(Surface conditioner)
OPTOOL DAC-HP: manufactured by Daikin Industries, Ltd. (surface modifier)
Megafac RS-57: manufactured by DIC Corporation (light stabilizer)
TINUVIN292: manufactured by BASF Japan

[Preparation of composition F1-A]
Acrylic polymer B (reactive polymer) 7.2 parts, KRM-8452 (reactive oligomer) 17.9 parts, Aronix M-402 (reactive monomer) 10.8 parts, Ionpure ZAF HS (antiviral inorganic particles ) 32.4 parts, OPTOOL DAC-HP (surface conditioner) 17.1 parts, MEGAFACE RS-57 (surface modifier) 11.9 parts, and Omnirad 127 (photoinitiator) 2.7 parts. Mixed. This mixture was diluted with propylene glycol monomethyl ether to prepare a milky white composition F1-A having a solid concentration of 3%.

[Preparation of Compositions F1-B to F1-F and F1-a to F1-b]
Milky white compositions F1-B, F1-D, F1-E, F1-F and transparent compositions F1-B, F1-D, F1-E, F1-F and transparent Compositions F1-C, F1-a, F1-b were prepared. Compositions F1-D also incorporate low refractive particles. The refractive index of the first functional layer formed from composition F1-D is 1.20 or more and 1.55 or less.

[Adjustment of Second Functional Layer Forming Composition F2]
A milky white composition F2 having a solid concentration of 3% was prepared in the same manner as composition F1-A, except that the formulation shown in Table 1B was used. The refractive index of the second functional layer formed of composition F2 is more than 1.55 and 2.00 or less.

[Preparation of composition HC-A]
Acrylic polymer A (reactive polymer) 31.0 parts, KRM-8452 (reactive oligomer) 35.2 parts, Aronix M-402 (reactive monomer) 20.7 parts, TINUVIN292 (light stabilizer) 3.0 parts , 4.0 parts of OSCAL 1842 (inorganic oxide fine particles), and 6.1 parts of Omnirad 184 (photoinitiation) were mixed. This mixture was diluted with methyl isobutyl ketone to prepare a transparent composition HC-A with a solid content concentration of 35%.

[Preparation of compositions HC-B and HC-C]
Transparent compositions HC-B and HC-C having a solid concentration of 35% were prepared in the same manner as composition HC-A, except that the formulations shown in Table 1C were used.

[Example 1]
(1) Production of laminated film (1-1) Formation of uncured first functional layer Torefan #40-2500 (another supporting substrate, manufactured by Toray Industries, Inc., biaxially oriented polypropylene film (OPP), thickness 40 μm ), the composition F1-A was applied by a gravure coater so that the thickness after drying was 100 nm. After that, it was dried at 80° C. for 1 minute to volatilize the solvent and form an uncured first functional layer. A transfer material L1 including an uncured first functional layer and another supporting base material was wound into a roll.
Hereinafter, the first functional layer formed of compositions F1-A to F1-F and F1-a to F1-b may be referred to as "F1 layer".

(1-2) Formation of uncured hard coat layer AW-10U (transparent support substrate, manufactured by Wavelock Advanced Technology, two-layer (PMMA/PC) film made of PMMA and PC, thickness 300 μm) Composition HC-A was applied to the surface of PMMA by a gravure coater so that the thickness after drying was 8 μm. After that, it was dried at 80° C. for 1 minute to volatilize the solvent and form an uncured hard coat layer.
Hereinafter, the hard coat layer formed by the compositions HC-A to HC-C may be referred to as "HC layer".

(1-3) Lamination While unwinding the transfer material L1 wound into a roll, the uncured HC layer surface supported by the transparent supporting substrate TB1 and the uncured HC layer surface supported by the other supporting substrate are laminated. The F1 layer surface was bonded together. As a result, a laminated film having a transparent supporting substrate, an uncured HC layer, an uncured F1 layer, and another supporting substrate in this order was produced. Finally, the laminated film was wound into a roll so that the other supporting substrate was on the inside.

(2) Production of Molded Body (2-1) Formation of Decorative Layer First, the laminated film was unwound from a roll and cut into a desired shape and size. A decorative (printed) layer was formed by screen printing on the side opposite to the uncured HC layer of the transparent support substrate of the cut laminated film, and dried at a drying temperature of 80° C. for 10 minutes. This decorating process was repeated 5 times and then dried at 90° C. for 1 hour. A black paint (RIM ink Gokukoku, manufactured by Jujo Chemical Co., Ltd.) was used to form the printed layer.

(2-2) Peeling of Another Supporting Substrate Next, another supporting substrate was peeled off from the uncured F1 layer at a speed of 50 mm/sec. After that, the obtained laminated film was subjected to heat treatment at 160° C. for 30 seconds.

(2-3) Preform A laminated film having a printed layer was heated at 190° C. for 30 seconds, and preformed by vacuum pressure molding using a three-dimensional mold with a maximum depth of 6 mm.

(2-4) Curing The preformed laminate film was irradiated with an active energy ray with an integrated light intensity of 2000 mJ/cm ² . Trimming was then performed.

(2-5) Injection Molding Finally, injection molding was performed to obtain a molded body having a molded resin layer (polycarbonate) on the printed layer side of the transparent support substrate. In the examples, ultraviolet rays are used as active energy rays unless otherwise specified.

[evaluation]
The following evaluations were performed on the laminated film and molded article. Table 2 shows the results.
(a) Thickness An evaluation sample of 10 mm×10 mm was cut out from the laminated film. A cross section of the evaluation sample was deposited with a microtome (LEICA RM2265). The deposited cross section was observed with a laser microscope (VK8700, manufactured by KEYENCE) or a transmission electron microscope (JEM2100, manufactured by JEOL Ltd.), and the thicknesses of the HC layer and the F1 layer were measured at 10 points each. The average values were used as the thicknesses of the HC layer and the F1 layer, respectively.

(b) Appearance The laminate film was cut into a size of 50 mm×50 mm, irradiated with an active energy ray of 2000 mJ/cm ² to be cured, and then visually evaluated for appearance according to the following criteria.
Good: No surface roughness observed under fluorescent light Poor: Surface roughness observed under fluorescent light

(c) Luminous reflectance A black paint (product name: CZ-805 BLACK (manufactured by Nikko Vicks Co., Ltd.)) was applied to the surface of the transparent support substrate of the laminated film opposite to the uncured HC layer, and a bar coater was applied. Then, the laminated film coated with the black paint was left at room temperature for 5 hours and dried to prepare an uncured evaluation sample. bottom.

The luminous reflectance was measured by the SCI method from the first functional layer side of the evaluation sample, and evaluated according to the following criteria. SD7000 manufactured by Nippon Denshoku Industries Co., Ltd. was used for the measurement, and the measurement wavelength range was 380 nm or more and 780 nm or less.
Best: Luminous reflectance of 1.0% or less Good: Luminous reflectance of more than 1.0% and 4.0% or less Acceptable: Luminous reflectance of more than 4.0%

(d) Stretch Ratio A test piece of 200 mm length×10 mm width was cut out from the laminated film. This test piece is set in a tensile tester with a chuck-to-chuck distance of 150 mm, and under the conditions of a tensile force of 5.0 kgf and a tensile speed of 300 mm / min in an atmosphere of 160 ° C., the evaluation sample is 10% in the long side direction. Stretched. The presence or absence of cracks in the evaluation sample after stretching was visually confirmed.

If no cracks occurred, a new evaluation sample was cut out and then stretched by 20% in the long side direction. Similarly, the presence or absence of cracks was visually confirmed. This procedure was repeated with 10% increments of draw ratio. The stretch ratio at which cracks were first observed was taken as the stretch ratio of the laminated film. An evaluation sample cut out from the same laminated film was subjected to the above evaluation three times, and the average value of the stretch ratios obtained in each time was taken as the stretch ratio _E160 of the laminated film.

(e) Followability to a three-dimensional shape Using a mold with a maximum depth of 6 mm, each laminated film was preformed, and the followability to a three-dimensional shape was evaluated.
Evaluation criteria are as follows.
Good: Cracks and whitening are not visible even when molded into a three-dimensional shape Poor: Cracks and whitening are visible when molded into a three-dimensional shape

(f) Indentation Hardness Hardness _HBC and hardness _HAC were measured from the uncured F1 layer side of the laminated film and the F1 layer side of the molding, respectively.
Hardness is determined by NANOMECHANICS, INC. It was measured by a continuous stiffness measurement method (method used: Advanced Dynamic E and H. NMT) using an iMicro Nanoindenter manufactured by the company.

Specifically, a minute AC load was superimposed on a quasi-static test load and applied to the surface of the evaluation sample. A load was applied until a maximum load of 50 mN was reached. As an indenter, a Berkovich-type diamond indenter (tip curvature radius: 20 nm) was used. From the vibration component of the generated displacement and the phase difference between the displacement and the load, the continuous stiffness with respect to depth was calculated, and the hardness profile with respect to depth was obtained. The hardness of this profile at a depth of 1000 nm was calculated.

iMicro dedicated software was used to calculate load and stiffness. In calculating the stiffness, the Poisson's ratio of the coating layer was set to 0.35. The load was controlled so that the strain rate (∂P/∂t)/P was 0.2.

(g) Haze value Using a haze meter (Nippon Denshoku NDH4000), the haze value of the laminated film was measured according to JIS K7136.

(h) Bondability In the laminated film immediately after the lamination step, the degree of adhesion between layers was evaluated.
Evaluation criteria are as follows.
Good: Layers stick together Fair: Layers stick together, but adhesion is weak Poor: Layers do not stick together at all

(i) Peelability A laminate film having another supporting substrate was cut into a size of 100 mm x 150 mm. At 25° C. and at a speed of 50 mm/sec, the other supporting substrate was peeled off from the first functional layer with the peeling direction set at 170°. The laminated film after peeling was evaluated according to the following criteria.
Good: No appearance defects such as whitening or zipping marks are observed on the laminated film after peeling. Poor: Appearance defects such as whitening or zipping marks are observed on the laminated film after peeling.

(j) Pencil hardness The pencil hardness was measured from the first functional layer side of the molded body and evaluated. The measurement was performed according to JIS K5600-5-4 (1999), scratch hardness (pencil method).

(k) Abrasion Resistance The surface of the F1 layer of the molded body was rubbed 2,000 times with a friction element to which a cotton cloth was fixed while applying a vertical load of 4 N per 1 cm ² of the laminated film surface. After that, the surface of the F1 layer of the compact was visually observed.
Evaluation criteria are as follows.
Good: No scratches or peeling visible after 2,000 rubbings Poor: Scratches or peeling visible after 2,000 rubbings

(l) Antiviral activity Measurement was carried out according to ISO 21702 "Determination of antiviral activity of plastics and other non-porous surfaces" using molded bodies as samples. Bacteriophage Q-beta was used as a test virus.

[Comparative Example 1]
In the same manner as in Example 1, an uncured HC layer was formed on the transparent support substrate TB1. Then, the HC layer was semi-cured by irradiating the HC layer with an active energy ray with an accumulated light amount of 50 mJ/cm ² .
Composition F1-E was applied to the semi-cured HC layer. Composition F1-E was subsequently dried to form an F1 layer with a dry thickness of 100 nm. Finally, the film was irradiated with an active energy ray with an accumulated light amount of 2000 mJ/cm ² to obtain a pre-cured laminated film. Using this laminated film, a molded body was produced in the same manner as in Example 1 and evaluated. Table 2 shows the results.

[Examples 2-8, 10-11, Comparative Examples 2-3]
In the same manner as in Example 1, the compositions prepared according to the formulations shown in Tables 1A to 1C were used to prepare laminated films and moldings having the configurations shown in Table 2. The resulting laminated film and molded article were evaluated in the same manner as in Example 1. Table 2 shows the results.

[Example 9]
An uncured hard coat layer and an uncured F1 layer (F1-D layer) were formed in the same manner as in (1-1) and (1-2) of Example 1, respectively.
Separately, in the same manner as the uncured F1 layer forming step (1-1), an uncured second functional layer (F2 layer, thickness 70 nm) having the composition shown in Table 1B is formed on the transfer material L2. got The transfer material L2 was wound into a roll. While unwinding the transfer material L2, the uncured F2 layer surface supported by another supporting base material and the uncured HC layer surface supported by the transparent supporting base material were bonded together.

The other supporting substrate was then peeled off to expose the uncured F2 layer. The uncured F1 layer was attached to the F2 layer while unwinding the transfer material L1. As a result, a laminated film and a molded body were produced, which were provided with an uncured HC layer, an F2 layer and an F1 layer in this order. The resulting laminated film and molded article were evaluated in the same manner as in Example 1. Table 2 shows the results.

As can be seen from Table 2, the laminated films and molded articles of Examples 1 to 11 have high antiviral properties, hardness, and moldability. Furthermore, excellent wear resistance was demonstrated. It is considered that this is because the surface of the first functional layer is smooth.

On the other hand, since the laminate film of Comparative Example 1 is cured, it has a low stretch ratio and is inferior in moldability (ability to conform to a three-dimensional shape). In addition, the laminated film of Comparative Example 1 also has low abrasion resistance. It is considered that this is because the antiviral/antibacterial inorganic particles are present in the vicinity of the surface of the outermost layer, thereby forming irregularities. The laminated film and molded article of Comparative Example 2 contain an organic substance as an antiviral/antibacterial component, and are inferior in pencil hardness. In addition, the laminate film of Comparative Example 2 has a poor appearance (surface roughness). This is probably due to the poor compatibility between the resin component contained in the first functional layer and the antiviral/antibacterial component. The laminated film and molded article of Comparative Example 3 do not exhibit antiviral properties because the functional layer 1 does not contain an antiviral/antibacterial component.

According to the present invention, it is possible to provide a laminated film that has antiviral and/or antibacterial properties, is excellent in moldability, and provides a molded article having high hardness. Therefore, this laminated film is particularly preferably used for producing protective materials for displays.

10A, 10B, 10C laminated film 11 transparent support substrate 12 uncured hard coat layer 13 uncured first functional layer 14 uncured second functional layer 15 uncured third functional layer 16 other supporting substrate 20 Molded body 22 Cured hard coat layer 23 Cured first functional layer 24 Decorative layer 25 Molded resin layer 30 Roller

Claims (23)

a transparent support substrate;
an uncured hard coat layer formed on at least one surface of the transparent supporting substrate;
an uncured first functional layer formed on the uncured hard coat layer;
The transparent supporting substrate and the uncured hard coat layer are adjacent to each other,
The uncured hard coat layer contains an active energy ray-curable hard coat layer-forming composition,
The uncured first functional layer contains an active energy ray-curable first functional layer-forming composition,
The first functional layer-forming composition contains inorganic particles having at least one of antiviral and antibacterial properties,
A laminated film having a stretch ratio of 50% or more at 160°C. The laminated film according to claim 1, wherein the hardness measured by a nanoindentation method from the uncured first functional layer side is 0.05 GPa or more and 0.5 GPa or less. The laminated film according to claim 1 or 2, wherein the laminated film irradiated with an active energy ray having an integrated light quantity of 2000 mJ/cm ² has a pencil hardness of 2H or more measured from the first functional layer side. The laminated film according to any one of claims 1 to 3, which has a haze value of 2% or less. The laminated film according to any one of claims 1 to 4, wherein the uncured first functional layer has a thickness of 15 nm or more and 1 µm or less. The inorganic particles have at least antiviral properties,
The laminated film according to any one of claims 1 to 5, wherein the laminated film irradiated with an active energy ray with an integrated light amount of 2000 mJ/cm ² has an antiviral activity value of 2.0 or more. The hard coat layer-forming composition comprises a first layer-forming component,
The first layer-forming component includes a first reactive component having two or more polymerizable functional groups in one molecule,
The first reactive component according to any one of claims 1 to 6, wherein the first oligomer has a weight average molecular weight of 10,000 or less and the first monomer has a weight average molecular weight of 10,000 or less. laminated film. 8. The laminated film of Claim 7, wherein the first reactive component further comprises a first polymer having a weight average molecular weight of greater than 10,000. 9. The method according to claim 7 or 8, wherein the total content of the first oligomer and the first monomer is 25 parts by mass or more and 65 parts by mass or less with respect to 100 parts by mass of the solid content of the hard coat layer-forming composition. Laminated film as described. The laminated film according to any one of claims 1 to 9, wherein the luminous reflectance including specular light measured from the uncured first functional layer side is 4% or less. The laminated film according to any one of claims 1 to 10, wherein the composition for forming the first functional layer further contains first low refractive particles that reduce the refractive index of the uncured first functional layer. An uncured second functional layer is further provided between the uncured hard coat layer and the uncured first functional layer,
12. The laminated film according to claim 11, wherein the uncured second functional layer contains high refractive particles that increase the refractive index of the uncured second functional layer. An uncured third functional layer is further provided between the uncured hard coat layer and the uncured first functional layer,
The laminated film according to any one of claims 1 to 12, wherein the uncured third functional layer contains second low refractive particles that reduce the refractive index of the uncured third functional layer. An uncured second functional layer is further provided between the uncured hard coat layer and the uncured third functional layer,
14. The laminated film according to claim 13, wherein the uncured second functional layer contains high refractive particles that increase the refractive index of the uncured second functional layer. 15. The method according to any one of claims 1 to 14, further comprising another support substrate disposed on the surface of the uncured first functional layer opposite to the uncured hard coat layer. laminated film. A shaped body comprising a laminated film according to any one of claims 1 to 15 which has been cured. The hard coat layer is arranged on one main surface of the transparent supporting substrate,
17. The molded article according to claim 16, further comprising a decorative layer arranged on the other main surface of said transparent support base material. The hard coat layer is arranged on one main surface of the transparent supporting substrate,
18. The molded article according to claim 16 or 17, further comprising a molded resin layer arranged on the other main surface of said transparent supporting substrate. a step of applying an active energy ray-curable hard coat layer-forming composition onto one surface of a transparent supporting substrate to form an uncured hard coat layer;
a step of applying an active energy ray-curable composition for forming a first functional layer onto one surface of another supporting substrate to form an uncured first functional layer;
The surface of the uncured hard coat layer opposite to the transparent supporting substrate and the surface of the uncured first functional layer opposite to the other supporting substrate are laminated to form a laminated film. and a lamination step to obtain,
The first functional layer-forming composition contains inorganic particles having at least one of antiviral and antibacterial properties,
A method for producing a laminated film, wherein the laminated film has a stretch ratio of 50% or more at 160°C. A method for producing a molded article, comprising a curing step of irradiating the laminated film according to any one of claims 1 to 15 with active energy rays having an integrated light amount of 200 mJ/cm ² or more. In the laminated film, the uncured hard coat layer is arranged on one main surface of the transparent supporting substrate,
21. The method for producing a molded article according to claim 20, wherein a decorative layer is arranged on the other main surface of the transparent supporting substrate. In the laminated film, the uncured hard coat layer is arranged on one main surface of the transparent supporting substrate,
22. The method for producing a molded article according to claim 20, further comprising an injection molding step of placing the laminated film in a mold and injecting a molding resin toward the transparent support substrate. The mold imparts a three-dimensional shape to the laminated film,
23. The method of manufacturing a molded article according to claim 22, further comprising a preforming step of forming the laminated film into a shape along the three-dimensional shape before the injection molding step.

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