JP7492371B2 - Low refractive index B-stage coating film, laminated film, three-dimensional molded body, and manufacturing method thereof - Google Patents

Description

The present invention relates to a method for producing a B-stage coating film capable of forming a low refractive index layer (hereinafter, sometimes referred to as a "low refractive index B-stage coating film"). More specifically, the present invention relates to a low refractive index B-stage coating film, a laminated film, a three-dimensional molded product, and methods for producing them.

In recent years, molded articles such as the display panels of image display devices such as car navigation systems and digital signage, and automotive instrument panels, are often given curved shapes and three-dimensional shapes from the standpoint of design. Furthermore, since these molded articles are used in places exposed to direct sunlight, they are often given anti-reflection functions by forming a low refractive index layer on their surface to solve the inconvenience of eye fatigue caused by reflected light when exposed to direct sunlight, and the inconvenience of reduced contrast making it difficult to see images clearly.

As a method for forming a low refractive index layer on the surface of a molded body having a three-dimensional shape, a method in which a resin having excellent transparency such as an acrylic resin or a polycarbonate resin is used to mold a substrate having a three-dimensional shape, and then a film of a low refractive index material is formed by a method such as a sputtering method, a vacuum deposition method, or a chemical vapor deposition method; and a method in which a coating material for forming a low refractive index layer is applied and cured by a method such as a dip coating method, a spray coating method, a spin coating method, or an air knife coating method. On the other hand, these methods have the disadvantage that the productivity is insufficient because a low refractive index layer is formed for each substrate. Therefore, attempts have been made to apply a method of forming a B-stage coating film by efficiently applying a coating material onto the surface of a thermoplastic resin sheet using a roll-to-roll method such as roll coating, gravure coating, reverse coating, and die coating, and forming the resulting laminated film into a predetermined shape by a method such as hot press molding, and then completely curing the B-stage coating film; and a method of inserting the laminated film into an injection molding mold, heating and softening the laminated film to form a predetermined shape, injecting a desired thermoplastic resin into the mold, and then completely curing the B-stage coating film (for example, Patent Documents 1 and 2) to the production of a molded product having a low refractive index layer formed on the surface and an anti-reflection function.

JP 2012-521476 A JP 2016-221922 A

An object of the present invention is to provide a method for producing a low refractive index B-stage coating film. Another object of the present invention is to provide a low refractive index B-stage coating film. A further object of the present invention is to provide a low refractive index B-stage coating film excellent in three-dimensional moldability (resistance to defects such as cracking and whitening when a three-dimensional shape is imparted) and web handleability (resistance to scratches and appearance defects caused by the coating film contacting a transfer roll or the like during web handling), and a method for producing the same. Yet another object of the present invention is to provide a low refractive index coating film that is excellent in three-dimensional moldability and web handleability in the B stage and excellent in surface hardness, scratch resistance, and chemical resistance after complete curing (in the C stage), a laminated film having the coating film, a molded body containing the coating film or the laminated film, and a method for producing the same.

As a result of extensive research, the inventors have discovered that the above objectives can be achieved through a specific manufacturing method.

The aspects of the present invention to solve the above problems are as follows [1].
A method for producing a B-stage coating film capable of forming a low refractive index layer, comprising the steps of:
(1) forming a wet coating film on a surface of a film substrate using a coating material containing (A) an active energy ray curable resin, (B) low refractive index particles, and (C) a photopolymerization initiator; and
(2) a step of irradiating the wet coating film with active energy rays to bring the wet coating film into a B-stage state;
Here, the active energy rays are monochromatized using a filter so as not to include any wavelength having an absorbance equal to or greater than half the maximum absorbance of the component (C) photopolymerization initiator;
[2]
The method according to item [1], wherein the active energy rays are monochromated using a filter so as to include a wavelength having an absorbance that is 1/10 to 1/100 of the maximum absorbance of the component (C) photopolymerization initiator.
[3]
The method for producing a photopolymerization initiator according to item [1] or [2], wherein the filter is a 365 filter; the component (C) photopolymerization initiator has an absorbance peak in the wavelength range of 220 to 280 nm, the peak top value of which is the maximum absorbance; the wavelength at which the absorbance becomes half of the maximum absorbance on the longer wavelength side than the peak top of the absorbance peak is 290 nm or less; and the absorbance is half or less of the maximum absorbance at any wavelength in the wavelength range of 290 to 400 nm.
[4]
The method according to any one of items [1] to [3], wherein the filter is a 365 filter; and the component (C) photopolymerization initiator has an absorbance of 1/10 to 1/100 of the maximum absorbance at a wavelength of 300 nm.
[5]
The filter is a 365 filter; and the component (C) photopolymerization initiator is one or more selected from the group consisting of 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, and a 100:0 to 45:55 (mass ratio) mixture of 1-hydroxycyclohexyl-phenyl-ketone and benzophenone; the manufacturing method according to any one of [1] to [4].
[6]
The method according to any one of items [1] to [5], wherein the component (A) active energy ray-curable resin contains (A1) urethane (meth)acrylate.
[7]
The method according to any one of items [1] to [6], wherein the component (A1) urethane (meth)acrylate has a polystyrene-equivalent number average molecular weight (Mn) of 1,000 or more as determined from a differential molecular weight distribution curve measured by gel permeation chromatography.
[8]
The method according to any one of items [1] to [7], wherein the number of (meth)acryloyl groups in the urethane (meth)acrylate of component (A1) is 2 to 20 per 1,000 of polystyrene-equivalent number average molecular weight (Mn) determined from a differential molecular weight distribution curve measured by gel permeation chromatography.
[9]
A method for producing a laminated film, comprising the step of forming a B-stage coating film capable of forming a low refractive index layer on at least one surface of a film substrate by the production method according to any one of items [1] to [8].
[10]
A method for producing a laminated film, comprising the steps of: forming a coating film having three-dimensional formability on at least one surface of a film substrate; and forming a B-stage coating film capable of forming a low refractive index layer by the production method according to any one of items [1] to [8] on the surface of the coating film having three-dimensional formability formed in the above step.

The manufacturing method of the present invention allows the industrially stable production of a low refractive index B-stage coating film. The preferred manufacturing method of the present invention allows the industrially stable production of a low refractive index B-stage coating film having excellent three-dimensional moldability and web handling properties. The low refractive index B-stage coating film of the present invention is excellent in three-dimensional moldability and web handling properties. The preferred low refractive index B-stage coating film of the present invention is excellent in three-dimensional moldability and web handling properties in the B stage, and is excellent in surface hardness, scratch resistance, and chemical resistance after complete curing (in the C stage). Therefore, the low refractive index B-stage coating film of the present invention and the laminated film of the present invention having the low refractive index B-stage coating film of the present invention can be suitably used to impart an anti-reflection function to a molded body having a three-dimensional shape/stereoscopic shape, particularly a display panel of an image display device such as a car navigation system and digital signage, and a molded body used in a place exposed to direct sunlight, such as an instrument panel of an automobile. Therefore, the low refractive index B-stage coating film of the present invention and the molded article molded using the laminate film of the present invention having the low refractive index B-stage coating film of the present invention have good anti-reflection function, excellent surface hardness, scratch resistance, and chemical resistance, and also have good surface appearance (there are no defective phenomena such as cracks or whitening).

In this specification, the term "resin" is used to include a resin mixture containing two or more resins, and a resin composition containing components other than resin. In this specification, the term "film" is used interchangeably or interchangeably with "sheet". In this specification, the terms "film" and "sheet" are used to refer to something that can be industrially wound into a roll. The term "plate" is used to refer to something that cannot be industrially wound into a roll. In this specification, stacking a layer and another layer in order includes both stacking the layers directly and stacking the layers with one or more layers, such as an anchor coat, interposed between them.

In this specification, the term "B stage" is used for thermosetting resins in the sense specified in JIS K6800-1985, that is, "an intermediate curing state of thermosetting resins. In this state, the resin softens when heated and swells when exposed to certain solvents, but does not completely melt or dissolve." For active energy ray curable resins, it is used to mean "an intermediate curing state of active energy ray curable resins. In this state, the resin softens when heated and swells when exposed to certain solvents, but does not completely melt or dissolve."

In this specification, the term "C stage" is used for both thermosetting resins and active energy ray-curable resins to mean "the final state of the curing reaction of the curable resin. The resin in this state is insoluble and infusible. The curable resin in a completely cured coating is in this state."

In this specification, the term "more than" in relation to a numerical range is used to mean a certain number or more than a certain number. For example, 20% or more means 20% or more than 20%. The term "less than" in relation to a numerical range is used to mean a certain number or less than a certain number. For example, 20% or less means 20% or less than 20%. Furthermore, the symbol "to" in relation to a numerical range is used to mean a certain number, more than a certain number and less than another certain number, or another certain number. Here, the other certain number is a number greater than the certain number. For example, 10 to 90% means 10%, more than 10% and less than 90%, or 90%. Furthermore, the upper and lower limits of the numerical range can be arbitrarily combined, and embodiments in which any combination is adopted can be read. For example, from a statement regarding the numerical range of a certain characteristic such as "Usually 10% or more, preferably 20% or more. On the other hand, usually 40% or less, preferably 30% or less" or "Usually 10-40%, preferably 20-30%," it can be inferred that the numerical range of the certain characteristic is 10-40%, 20-30%, 10-30%, or 20-40% in one embodiment.

Other than in the examples, or where otherwise specified, all numerical values used in the specification and claims should be understood to be modified by the term "about." Without attempting to limit the application of the doctrine of equivalents to the scope of the claims, each numerical value should be construed in light of the number of significant digits and by applying ordinary rounding techniques.

1. Manufacturing method of low refractive index B-stage coating film:
The manufacturing method of the present invention is a method for manufacturing a B-stage coating film capable of forming a low refractive index layer, and includes the steps of: (1) forming a wet coating film on the surface of a film substrate using a coating material containing (A) an active energy ray-curable resin, (B) low refractive index particles, and (C) a photopolymerization initiator; and (2) irradiating the wet coating film with active energy rays to bring it into a B-stage state, wherein the active energy rays are monochromatized using a filter so as not to include wavelengths that result in an absorbance of usually ½ or more, preferably ⅓ or more, more preferably ¼ or more, even more preferably ⅕ or more, still more preferably ⅙ or more, and most preferably ⅛ or more of the maximum absorbance of the component (C) photopolymerization initiator.

In one preferred embodiment, the manufacturing method of the present invention is a method for manufacturing a B-stage coating film capable of forming a low refractive index layer, and includes: (1) a step of forming a wet coating film on the surface of a film substrate using a coating material containing (A) an active energy ray curable resin, (B) low refractive index particles, and (C) a photopolymerization initiator; and (2) a step of irradiating the wet coating film with active energy rays to bring it into a B-stage state; wherein the active energy rays are monochromatized using a filter so as not to include wavelengths that have an absorbance of usually 1/2 or more, preferably 1/3 or more, more preferably 1/4 or more, even more preferably 1/5 or more, even more preferably 1/6 or more, even more preferably 1/7 or more, and most preferably 1/8 or more of the maximum absorbance of the component (C) photopolymerization initiator; and to include wavelengths that have an absorbance of usually 1/10 to 1/100, preferably 1/15 to 1/70, and more preferably 1/20 to 1/50.

The above step (1) is a step of forming a wet coating film on the surface of the film substrate using a coating material containing the above component (A) active energy ray curable resin, the above component (B) low refractive index particles, and the above component (C) photopolymerization initiator (hereinafter sometimes referred to as "coating material for forming a low refractive index layer"). The above coating material for forming a low refractive index layer will be described in the section "2. Low refractive index B-stage coating film". The above film substrate will be described in the section "3. Laminated film".

In the above step (1), the method of forming a wet coating film on the surface of the film substrate using the coating material for forming the low refractive index layer is not particularly limited, and any known web coating method can be used. As the web coating method, from the viewpoint of applying the coating material with good productivity by a roll-to-roll method, for example, methods such as rod coating, roll coating, gravure coating, reverse coating, kiss reverse coating, and die coating are preferable.

Before irradiating with active energy rays in the above step (2), it is preferable to pre-dry the wet coating film formed using the coating material for forming the low refractive index layer. The pre-drying can be performed, for example, by passing the web through a drying oven set at a temperature of about 23 to 150°C, preferably a temperature of 50 to 120°C, at a line speed such that the time required to pass from the inlet to the outlet is about 0.5 to 10 minutes, preferably 1 to 5 minutes.

The above step (2) is a step of irradiating the wet coating film with active energy rays to bring it into a B-stage state. The amount of irradiation with the active energy rays needs to be very low in order to keep the curing of the wet coating film in a B-stage state.

Without intending to be bound by theory, if the amount of irradiation is to be very low, it is possible to consider a method of lowering the output of the light source of the active energy rays, increasing the distance between the light source and the wet coating film, or increasing the line speed of the step (2). However, from the viewpoint of stable operation of the light source, the output should be at a certain level or higher, and from the viewpoint of the handling of the manufacturing equipment, there is a limit to the method of increasing the distance between the light source and the wet coating film or increasing the line speed of the step (2). Therefore, in the manufacturing method of the present invention, a filter is used to irradiate the active energy rays in a monochromatic state so as not to include wavelengths that have an absorbance of usually 1/2 or more, preferably 1/3 or more, more preferably 1/4 or more, even more preferably 1/5 or more, even more preferably 1/6 or more, even more preferably 1/7 or more, and most preferably 1/8 or more of the maximum absorbance of the photopolymerization initiator (C), thereby achieving both a very low irradiation amount, keeping the curing of the wet coating film in a B-stage state, and industrially stable production. In one preferred embodiment of the manufacturing method of the present invention, the wavelength is selected to include a wavelength at which the absorbance is typically 1/10 to 1/100, preferably 1/15 to 1/70, and more preferably 1/20 to 1/50 of the maximum absorbance of the component (C) photopolymerization initiator, making it easy to cure the wet coating film to a B-stage state.

The maximum absorbance of the component (C) photopolymerization initiator means the maximum absorbance in the wavelength range of 220 to 400 nm on the wavelength-absorbance curve of the component (C) photopolymerization initiator.

The above-mentioned active energy rays do not include active energy rays of a certain wavelength, which means that the specific energy intensity of the active energy rays at that wavelength is usually less than 5%, preferably 2% or less, more preferably 1% or less, even more preferably 0.5% or less, and most preferably 0.1% or less.

The term "active energy rays include active energy rays of a certain wavelength" means that the specific energy intensity of the active energy rays at that wavelength is usually 5% or more, preferably 10% or more, and more preferably 15% or more.

The specific energy intensity is the energy intensity (unit: %) at a wavelength when the energy intensity of the wavelength that is most highly transmitted by the filter is taken as 100%. For example, when the active energy ray is monochromatized using a 365 filter, the specific energy intensity is the energy intensity (unit: %) at a wavelength when the energy intensity of the monochromatized active energy ray at a wavelength of 365 nm is taken as 100%. Figure 1 is a graph showing the relationship between wavelength and specific energy intensity when the ultraviolet ray generated from the high-pressure mercury lamp type ultraviolet ray irradiation device used in the examples is monochromatized using the 365 filter also used in the examples.

The wavelength-absorbance curve of the component (C) photopolymerization initiator can be obtained by preparing a photopolymerization initiator solution of an appropriate concentration and measuring the solution using any spectrophotometer. The wavelength-absorbance curve of the component (C) photopolymerization initiator can be obtained, for example, by dissolving the photopolymerization initiator in acetonitrile for spectroscopic analysis to prepare a photopolymerization initiator acetonitrile solution of an appropriate concentration, and then using a spectrophotometer and a quartz glass cell (optical path length 10 mm) to measure the absorbance in the wavelength range of 200 to 500 nm using the photopolymerization initiator acetonitrile solution, and creating a wavelength-absorbance curve. When a mixture of two or more photopolymerization initiators is used as the component (C) photopolymerization initiator, a wavelength-absorbance curve of the mixture is created and used. As the spectrophotometer, for example, the Shimadzu Corporation spectrophotometer "SolidSpec-3700 (product name)" can be used.

The case where active energy rays are monochromatized using a 365 filter will now be described. When active energy rays are monochromatized using a 365 filter, it can be seen from Figure 1 that the specific energy intensity is nearly zero (specific energy intensity <0.1%) at wavelengths of 280 nm or less, less than 2% at wavelengths between 280 nm and 285 nm, and less than 5% at wavelengths between 285 nm and 290 nm. Therefore, when the active energy rays are monochromatized using a 365 filter, from the viewpoint of not including wavelengths at which the absorbance is usually ½ or more, preferably ⅓ or more, more preferably ¼ or more, even more preferably ⅕ or more, still more preferably ⅙ or more, still more preferably ⅙ or more, and most preferably ⅛ or more of the maximum absorbance of the photopolymerization initiator, and from the viewpoint of curability when a B-stage coating film is completely cured (to a C-stage), it is preferable to use, as the component (C), a photopolymerization initiator which has an absorbance peak whose peak top value is the maximum absorbance in the wavelength range of 220 to 280 nm, a wavelength at which the absorbance is 1/n of the peak top value (=maximum absorbance) on the longer wavelength side than the peak top of the absorbance peak is usually 290 nm or less, preferably 285 nm or less, more preferably 280 nm or less, and an absorbance of 1/n or less of the maximum absorbance at any wavelength in the wavelength range of 290 to 400 nm. Here, n is a natural number from 2 to 8, usually 2, preferably 3, more preferably 4, even more preferably 5, even more preferably 6, even more preferably 7, and most preferably 8.

As the component (C) photopolymerization initiator, it is preferable to use one that has a weak absorbance of usually 1/10 to 1/100, preferably 1/15 to 1/70, more preferably 1/20 to 1/50 of the maximum absorbance in a wavelength range in which the specific energy intensity of the active energy rays is usually 5% or more, preferably 10% or more, more preferably 15% or more, and usually 100% or less, preferably 50% or less, more preferably 30% or less. This makes it easy to both cure the wet coating film to a B-stage state and keep the curing of the wet coating film in a B-stage state.

When a 365 filter is used to produce a monochromatic image, it can be seen from FIG. 1 that the specific energy intensity is, for example, 10 to 22% at wavelengths of 295 to 320 nm. Therefore, when a 365 filter is used to produce a monochromatic image, a photopolymerization initiator that has a weak absorbance of usually 1/10 to 1/100, preferably 1/15 to 1/70, and more preferably 1/20 to 1/50 of the maximum absorbance at wavelengths of 295 to 320 nm is preferable as the above component (C).

When a 365 filter is used to produce a monochromatic image, it can be seen from Figure 1 that the specific energy intensity is 17% at a wavelength of 300 nm. Therefore, when a 365 filter is used to produce a monochromatic image, a photopolymerization initiator that has a weak absorbance of usually 1/10 to 1/100, preferably 1/15 to 1/70, and more preferably 1/20 to 1/50 of the maximum absorbance at a wavelength of 300 nm is preferable as the above component (C).

FIG. 2 is a wavelength-absorbance curve of an acetonitrile solution (concentration: 0.010% by mass (4.9×10 ⁻⁵ mol%)) of the photopolymerization initiator (C-1) used in the examples. The photopolymerization initiator (C-1) has an absorption peak at a wavelength of 242 nm, and the peak top value of the peak is the maximum absorbance. It can be seen from FIG. 2 that, on the longer wavelength side than the peak top, the absorbance becomes 1/2 of the peak top value at 254 nm, 1/3 at 258 nm, 1/4 at 260 nm, 1/5 at 262 nm, 1/6 at 264 nm, 1/7 at 266 nm, and 1/8 at 269 nm.

When the photopolymerization initiator (C-1) is used as the component (C) photopolymerization initiator, if the white active energy rays are monochromatized using a 365 filter as the filter in the step (2), active energy rays with wavelengths of 280 nm or less are almost completely blocked (specific energy intensity <0.1%), so it can be said that "the active energy rays are monochromatized using a filter so as not to include wavelengths with an absorbance of 1/8 or more of the maximum absorbance of the component (C) photopolymerization initiator." In addition, the component (C-1) has a small absorbance near a wavelength of 300 nm (1/34 of the maximum absorbance at a wavelength of 300 nm), and as described above, when monochromatized using a 365 filter, the specific energy intensity at wavelengths of 295 to 320 nm is 10 to 22%, so it is easy to both cure the wet coating film to a B-stage state and keep the curing of the wet coating film in a B-stage state.

FIG. 3 is a wavelength-absorbance curve of an acetonitrile solution (concentration: 0.005% by mass (1.5×10 ⁻⁵ mol%)) of the photopolymerization initiator (C-2) used in the examples. The photopolymerization initiator (C-2) has an absorption peak at a wavelength of 259 nm, and the peak top value of the peak is the maximum absorbance. It can be seen from FIG. 3 that, on the longer wavelength side than the peak top, the absorbance becomes 1/2 of the peak top value at 271 nm, 1/3 at 276 nm, 1/4 at 279 nm, 1/5 at 281 nm, 1/6 at 283 nm, 1/7 at 285 nm, and 1/8 at 286 nm.

When the photopolymerization initiator (C-2) is used as the component (C) photopolymerization initiator, if a 365 filter is used in step (2) to monochromatize the white active energy rays, active energy rays with wavelengths of 280 nm or less are almost completely blocked, active energy rays with wavelengths greater than 280 nm and less than 285 nm are almost blocked to a specific energy intensity of less than 2%, and active energy rays with wavelengths greater than 285 nm and less than 290 nm are almost blocked to a specific energy intensity of less than 5%, so that it can be said that "the active energy rays are monochromatized using a filter so as not to include wavelengths having an absorbance of more than 1/8 of the maximum absorbance of the component (C) photopolymerization initiator." In addition, the above component (C-2) has a small amount of absorbance near 300 nm (1/41 of the maximum absorbance at a wavelength of 300 nm), and as mentioned above, when a 365 filter is used to produce a monochromatic image, the specific energy intensity at wavelengths of 295 to 320 nm is 10 to 22%, so it is easy to both cure the wet coating film to a B-stage state and keep the cured wet coating film in a B-stage state.

FIG. 4 is a wavelength-absorbance curve of an acetonitrile solution (concentration: 0.005% by mass (1.2×10 ⁻⁵ mol%)) of the photopolymerization initiator (C-3) used in the examples. The absorbance of the photopolymerization initiator (C-3) decreases almost monotonically in the wavelength range of 220 to 400 nm, and reaches a maximum absorbance at a wavelength of 220 nm. It also has a broad absorbance peak at a wavelength of 289 nm and a shoulder absorbance peak at a wavelength of 233 nm. It can be seen from FIG. 4 that the absorbance becomes 1/2 of the maximum absorbance at 249 nm, 1/3 at 305 nm, and 1/4 at 316 nm.

When the photopolymerization initiator (C-3) is used as the component (C) photopolymerization initiator, if a 365 filter is used as the filter in the step (2) to monochromatize the white active energy rays, active energy rays with wavelengths of 280 nm or less are almost completely blocked (specific energy intensity <0.1%), so it can be said that "the active energy rays are monochromatized using a filter so as not to include wavelengths with an absorbance of 1/2 or more of the maximum absorbance of the component (B) photopolymerization initiator." On the other hand, the component (C-3) has considerable absorbance around 300 nm (1/2.8 of the maximum absorbance at a wavelength of 300 nm), so even if a 365 filter is used as the filter in the step (2) to monochromatize the white active energy rays, it can be said that "wavelengths with an absorbance of 1/3 or more of the maximum absorbance of the component (B) photopolymerization initiator are included."

Examples of light sources for the above-mentioned active energy rays include high-pressure mercury lamps and metal halide lamps.

The amount of irradiation of the active energy rays is appropriately selected and determined in consideration of the number of polymerizable functional groups of the active energy ray curable resin (A) and the type and amount of the photopolymerization initiator (C) from the viewpoint of stably performing the step (2), curing the wet coating film to a B-stage state, and maintaining the curing of the wet coating film in a B-stage state. The amount of irradiation of the active energy rays may be usually 1 to 1000 mJ/cm ² , preferably 20 to 600 mJ/cm ² , and more preferably 30 to 200 mJ/cm ² , calculated as the amount of irradiation when no filter is used (when the amount of irradiation is measured or calculated when no filter is used).

After step (2) above, an aging treatment may be performed. This can stabilize the properties of the low refractive index B-stage coating film of the present invention.

After the above step (2), it is preferable to temporarily attach a protective film over the surface of the formed low refractive index B-stage coating film. This can prevent manufacturing problems such as scratches on the low refractive index B-stage coating film before it is completely cured (to C-stage). Furthermore, after three-dimensional molding, in the process of irradiating the low refractive index B-stage coating film with active energy rays to change it from B-stage to C-stage, this can prevent manufacturing problems such as poor curing due to oxygen damage.

2. Low refractive index B-stage coating:
The low refractive index B-stage coating film of the present invention is formed by the low refractive index B-stage coating film manufacturing method of the present invention using a coating material containing (A) an active energy ray-curable resin, (B) low refractive index particles, and (C) a photopolymerization initiator.

The refractive index (RL) of the low refractive index layer (C stage (fully cured) coating film) formed using the low refractive index B stage coating film of the present invention is usually 1.5 or less, preferably 1.45 or less, and more preferably 1.4 or less, from the viewpoint of exhibiting good anti-reflection function in the molded body. On the other hand, from the viewpoint of the transparency of the molded body, it may be preferably 1.2 or more, more preferably 1.25 or more, more preferably 1.28 or more, and even more preferably 1.3 or more.

The refractive index (RL) is a value measured using an Abbe refractometer according to JIS K7142:2008 Method A, using sodium D line (wavelength 589.3 nm), 1-bromonaphthalene as the contact liquid, the surface of the sample that was the biaxially oriented polypropylene resin film side when the sample was made is the surface that is in contact with the prism, and the bar coater operation direction of the sample is the length direction of the test piece. For the sample, the coating material for forming the low refractive index layer is applied to the surface of a 20 μm thick biaxially oriented polypropylene resin film using a bar coater so that the thickness after curing is 2 μm, dried, and irradiated with active energy rays to obtain a coating film (C stage (fully cured) coating film), which is peeled off from the biaxially oriented polypropylene resin film.

The thickness of the low refractive index layer (C stage (fully cured) coating film) formed using the low refractive index B stage coating film of the present invention is appropriately determined taking into consideration the desired reflectance and the productivity when forming the low refractive index layer. From the viewpoint of reducing reflectance, the thickness of the low refractive index layer may usually be 300 nm or less, preferably 250 nm or less, more preferably 200 nm or less, and even more preferably 150 nm or less. On the other hand, from the viewpoint of productivity when forming the low refractive index layer, the thickness may usually be 10 nm or more, preferably 20 nm or more, more preferably 40 nm or more, and even more preferably 60 nm or more.

The coating material for forming the low refractive index layer and each of its components will be described below.

(A) Active energy ray curable resin:
The above-mentioned component (A), the active energy ray-curable resin, functions to form a coating film by being polymerized and cured by active energy rays such as ultraviolet rays and electron beams.

Examples of the above component (A) include (meth)acryloyl group-containing prepolymers or oligomers such as polyurethane (meth)acrylate, polyester (meth)acrylate, polyacryl (meth)acrylate, epoxy (meth)acrylate, polyalkylene glycol poly(meth)acrylate, and polyether (meth)acrylate; methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, and the like. Acrylate, isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, phenyl (meth)acrylate, phenyl cellosolve (meth)acrylate, 2-methoxyethyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 2-acryloyloxyethyl hydrogen phthalate, dimethylaminoethyl (meth)acrylate, trifluoroethyl (meth)acrylate, and trimethylsiloxyethyl. (meth)acryloyl group-containing monofunctional reactive monomers such as diethyl methacrylate; N-vinylpyrrolidone, styrene, and other monofunctional reactive monomers; diethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 2,2'-bis(4-(meth)acryloyloxypolyethyleneoxyphenyl)propane, and 2,2'-bis(4-(meth)acryloyloxypolypropyleneoxyphenyl)propane, and the like. (meth)acryloyl group-containing bifunctional reactive monomers such as trimethylolpropane tri(meth)acrylate and trimethylolethane tri(meth)acrylate; (meth)acryloyl group-containing tetrafunctional reactive monomers such as pentaerythritol tetra(meth)acrylate; and (meth)acryloyl group-containing hexafunctional reactive monomers such as dipentaerythritol hexaacrylate, or one or more of the above may be selected as constituent monomers. As the active energy ray curable resin, one or a mixture of two or more of these may be used. In this specification, (meth)acrylate means acrylate or methacrylate.

In one preferred embodiment, the above component (A) may contain (A1) urethane (meth)acrylate. This can improve the balance between web handling properties and three-dimensional moldability.

(A1) Urethane (meth)acrylate:
The urethane (meth)acrylate component (A1) is a compound having a urethane structure (-NH-CO-O-), or a derivative thereof having one or more (meth)acryloyl groups. The component (A1) is not particularly limited, but may typically be one produced using a compound having two or more isocyanate groups (-N=C=O) in one molecule, a polyol compound, and a hydroxyl group-containing (meth)acrylate, i.e., one containing structural units derived from these compounds.

Examples of the compound having two or more isocyanate groups in one molecule include compounds having two isocyanate groups in one molecule, such as diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, and methylene bis(4-cyclohexyl isocyanate). Examples of the compound having two or more isocyanate groups in one molecule include polyisocyanates such as trimethylolpropane adduct of tolylene diisocyanate, trimethylolpropane adduct of hexamethylene diisocyanate, trimethylolpropane adduct of isophorone diisocyanate, isocyanurate of tolylene diisocyanate, isocyanurate of hexamethylene diisocyanate, isocyanurate of isophorone diisocyanate, and biuret of hexamethylene diisocyanate.

As the compound having two or more isocyanate groups in one molecule, one of these or a mixture of two or more of them can be used.

Examples of the polyol compounds include polyether polyols, polyester polyols, and polycarbonate polyols.

Examples of the polyether polyols include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol; polyalkylene oxides such as polyethylene oxide and polypropylene oxide; copolymers of ethylene oxide and propylene oxide; copolymers of ethylene oxide and tetrahydrofuran; copolymers of dihydric phenol compounds and polyoxyalkylene glycols; and copolymers of dihydric phenols and one or more alkylene oxides having 2 to 4 carbon atoms (e.g., ethylene oxide, propylene oxide, 1,2-butylene oxide, and 1,4-butylene oxide).

Examples of the polyester polyols include poly(ethylene adipate), poly(butylene adipate), poly(neopentyl adipate), poly(hexamethylene adipate), poly(butylene azelaate), poly(butylene sebacate), and polycaprolactone.

Examples of the polycarbonate polyols include poly(butanediol carbonate), poly(hexanediol carbonate), and poly(nonanediol carbonate).

As the polyol compound, one or a mixture of two or more of these can be used.

Examples of the hydroxyl group-containing (meth)acrylates include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and 2-hydroxy-3-(meth)acryloyloxypropyl (meth)acrylate; glycol-based (meth)acrylates such as dipropylene glycol (meth)acrylate, polyethylene glycol mono(meth)acrylate, and polypropylene glycol mono(meth)acrylate; glycerin-based (meth)acrylates such as glycerin di(meth)acrylate; modified glycidyl-based (meth)acrylates such as fatty acid-modified glycidyl (meth)acrylate; 2-hydroxyethyl Examples of such compounds include phosphorus atom-containing (meth)acrylates such as acryloyl phosphate; (meth)acrylic acid adducts of esters or ester derivatives such as 2-(meth)acryloyloxyethyl-2-hydroxypropyl phthalate; pentaerythritol-based (meth)acrylates such as pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, ethylene oxide-modified pentaerythritol tri(meth)acrylate, and ethylene oxide-modified dipentaerythritol penta(meth)acrylate; and caprolactone-modified (meth)acrylates such as caprolactone-modified 2-hydroxyethyl (meth)acrylate, caprolactone-modified pentaerythritol tri(meth)acrylate, and caprolactone-modified dipentaerythritol penta(meth)acrylate.

As the hydroxyl group-containing (meth)acrylate, one of these or a mixture of two or more of them can be used.

The number average molecular weight (Mn) of the component (A1) calculated in terms of polystyrene from the differential molecular weight distribution curve (hereinafter sometimes abbreviated as GPC curve) measured by gel permeation chromatography (hereinafter sometimes abbreviated as GPC curve) may be usually 1000 or more, preferably 1600 or more, and more preferably 2000 or more, from the viewpoint of three-dimensional moldability.

The number of (meth)acryloyl groups in the above component (A1) may be typically 2 or more, preferably 3 or more, per 1000 polystyrene-equivalent number average molecular weight (Mn) determined from a GPC curve, from the viewpoint of web handleability. From the viewpoints of surface hardness, scratch resistance, and chemical resistance after complete curing (at C stage), it may more preferably be 6 or more. On the other hand, from the viewpoint of three-dimensional moldability, it may be typically 20 or less, preferably 12 or less, more preferably 10 or less.

The GPC measurement was performed using a Tosoh Corporation high-performance liquid chromatography system "HLC-8320 (trade name)" (a system including a degasser, a liquid delivery pump, an autosampler, a column oven, and an RI (differential refractive index) detector); two Shodex GPC columns "KF-806L (trade name)" and one each of "KF-802 (trade name)" and "KF-801 (trade name)" were used as GPC columns, totaling four columns connected in the order of KF-806L, KF-806L, KF-802, and KF-801 from the upstream side; and Wako Pure Chemical Industries, Ltd.'s tetrahydrofuran for high-performance liquid chromatography (without stabilizer) was used as the mobile phase; the conditions were a flow rate of 1.0 milliliters/minute, a column temperature of 40°C, a sample concentration of 1 milligram/milliliter, and a sample injection amount of 100 microliters. The elution amount at each retention volume can be determined from the amount detected by the RI detector, assuming that the refractive index of the measurement sample does not depend on the molecular weight. A calibration curve from retention volume to polystyrene-equivalent molecular weight can be created using commercially available standard polystyrene. Note that the program should be selected appropriately so that the measured values are interpolated in the calibration curve. The analysis program "TOSOH HLC-8320GPC EcoSEC (product name)" by Tosoh Corporation can be used. For the theory of GPC and the actual measurement, reference books such as "Size Exclusion Chromatography: High-Performance Liquid Chromatography of Polymers, Author: Mori Sadao, First Edition, First Printing, December 10, 1991" by Kyoritsu Publishing Co., Ltd. and "Synthetic Polymer Chromatography, Editors: Otani Hajime, Takarazaki Tatsuya (the "崎" character is written with the upper part of the "立" character), First Edition, First Printing, July 25, 2013" by Ohmsha Co., Ltd. can be referred to.

Figure 5 shows the differential molecular weight distribution curve of the urethane (meth)acrylate (A1-1) used in the examples. Two sharp peaks are observed in the relatively low molecular weight region, and the polystyrene-equivalent molecular weights at the peak top positions are 700 and 1340, respectively, from the low molecular weight side. Multiple overlapping broad peaks are observed on the high molecular weight side of these two peaks, and the polystyrene-equivalent molecular weight of the component on the highest molecular weight side is recognized to be about 600,000. The total number average molecular weight (Mn) is 2000, the mass average molecular weight (Mw) is 26,000, and the Z-average molecular weight (Mz) is 110,000. In addition, the number of (meth)acryloyl groups per molecule is 20, so the number of (meth)acryloyl groups per 1000 polystyrene-equivalent number average molecular weight (Mn) calculated from the GPC curve is 10.

As the above component (A1), one or a mixture of two or more of these can be used.

When the component (A) contains the component (A1) urethane (meth)acrylate, the amount of the component (A1) in the component (A) may be appropriately determined taking into consideration the balance between web handleability and three-dimensional moldability, as well as the surface hardness, scratch resistance, and chemical resistance after complete curing (at C stage). The amount of the component (A1) in the component (A) may be generally 20% by mass or more, preferably 40% by mass or more, more preferably 60% by mass or more, even more preferably 80% by mass or more, and most preferably 90 to 100% by mass, based on the total amount of the component (A) being 100% by mass.

(B) Low refractive index particles:
The low refractive index particles of component (B) are particles that act to lower the refractive index of a coating film (C-stage (fully cured) coating film) formed using the coating material for forming a low refractive index layer. Examples of component (B) include particles (solid particles) of low refractive index materials such as silica, magnesium fluoride, fluorine resin, and silicone resin; and hollow particles.

The hollow particles have an outer shell layer and are porous or hollow (single-hole) inside. The hollow particles contain air (refractive index 1.0) in the pores of the porous or hollow (single-hole), which is highly effective in lowering the refractive index of the coating film.

The material constituting the hollow particles is not particularly limited as long as it forms the above-mentioned structure. Examples of materials constituting the hollow particles include low refractive index materials such as silica, magnesium fluoride, fluorine resin, and silicone resin.

The average particle size of the above component (B) is appropriately determined taking into consideration the thickness of the low refractive index layer and the productivity in manufacturing the low refractive index particles. The average particle size of the above component (B) may be usually 1 to 150 nm, preferably 5 to 100 nm, more preferably 10 to 80 nm, and even more preferably 20 to 70 nm.

In this specification, the average particle size is the particle size at which the cumulative particle size distribution curve measured by a laser diffraction/scattering method using a laser diffraction/scattering particle size analyzer is 50% by mass, starting from the smallest particles. As the laser diffraction/scattering particle size analyzer, for example, the "MT3200II (product name)" manufactured by Nikkiso Co., Ltd. can be used.

From the viewpoint of achieving a predetermined refractive index (RL) with a smaller blending amount, hollow particles are preferred as the above component (B). One or a mixture of two or more of these can be used as the above component (B).

The amount of component (B) is determined appropriately, taking into consideration the type of component (B) and from the viewpoint of setting the refractive index (RL) in the above-mentioned range. The amount of component (B) may be usually 10 to 300 parts by mass, preferably 30 to 200 parts by mass, and more preferably 50 to 160 parts by mass, per 100 parts by mass of component (A) in order to set the refractive index (RL) in the above-mentioned range.

(C) Photopolymerization initiator:
The component (C) photopolymerization initiator is a compound that generates active species such as radicals when irradiated with active energy rays. The component (C) generates active species such as radicals, thereby polymerizing and curing the component (A) active energy ray-curable resin.

The photopolymerization initiator may be, for example, benzophenone-based compounds such as benzophenone, methyl o-benzoylbenzoate, 4-methylbenzophenone, 4,4'-bis(diethylamino)benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, and 2,4,6-trimethylbenzophenone; benzoin-based compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzyl methyl ketal; acetophenone-based compounds such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, and 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one; α-hydroxyalkyl Examples of the alkylphenone compounds include phenone, acetophenone dimethyl ketal, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, and 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one; anthraquinone compounds include methylanthraquinone, 2-ethylanthraquinone, and 2-amylanthraquinone; thioxanthone compounds include thioxanthone, 2,4-diethylthioxanthone, and 2,4-diisopropylthioxanthone; acylphosphine oxide compounds include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide; biimidazole compounds; titanocene compounds; oxime ester compounds; oxime phenyl acetate compounds; hydroxyketone compounds; triazine compounds; and aminobenzoate compounds.

The component (C) photopolymerization initiator contained in the coating material for forming the low refractive index layer used in the manufacturing method of the present invention is appropriately selected according to the type of filter used in the manufacturing method of the present invention.

When a 365 filter is used as the filter, preferred examples of the component (C) include a photopolymerization initiator that has an absorbance peak in the wavelength range of 220 to 280 nm, the peak top value of which is the maximum absorbance; a wavelength at which the absorbance is 1/n of the peak top value (=maximum absorbance) on the longer wavelength side than the peak top of the absorbance peak is usually 290 nm or less, preferably 285 nm or less, and more preferably 280 nm or less; and an absorbance of 1/n or less of the maximum absorbance at any wavelength in the wavelength range of 290 to 400 nm. Here, n is a natural number from 2 to 8, and is usually 2, preferably 3, more preferably 4, even more preferably 5, even more preferably 6, even more preferably 7, and most preferably 8.

When the 365 filter is used as the filter, preferred examples of the component (C) include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, and a mixture of 1-hydroxycyclohexyl phenyl ketone and benzophenone (the mass ratio is usually 100:0 to 45:55, and in one embodiment, 90/10 to 45:55).

As the above component (C), one or a mixture of two or more of these can be used.

The amount of the component (C) may be appropriately selected by comprehensively considering the viewpoints of curing the coating film to a B-stage state, maintaining the curing of the coating film in a B-stage state, and ensuring complete curing (C-stage) after three-dimensional molding. The amount of the component (C) may be, based on 100 parts by mass of the component (A), usually 1 part by mass or more, preferably 3 parts by mass or more, more preferably 4 parts by mass or more, and even more preferably 5 parts by mass or more, from the viewpoint of curing the coating film to a B-stage state and ensuring complete curing (C-stage) after three-dimensional molding. On the other hand, from the viewpoint of maintaining the curing of the coating film in a B-stage state, it may be usually 20 parts by mass or less, preferably 15 parts by mass or less, more preferably 12 parts by mass or less, even more preferably 10 parts by mass or less, and most preferably 8 parts by mass or less.

The coating material for forming a low refractive index layer may further contain a solvent from the viewpoint of productivity when forming a wet coating film using the coating material for forming a low refractive index layer. Examples of the solvent include 1-methoxy-2-propanol, 1-ethoxy-2-propanol, ethyl acetate, n-butyl acetate, toluene, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, methyl cellosolve, ethyl cellosolve, diacetone alcohol, and acetone. The solvent may be one or a mixture of two or more of these.

The amount of the solvent is appropriately determined from the viewpoint of productivity when forming a wet coating film using the paint for forming a low refractive index layer, and from the viewpoint of productivity of the process of drying the wet coating film and recovering the solvent after forming a wet coating film using the paint for forming a low refractive index layer. From the viewpoint of productivity when forming a wet coating film using the paint for forming a low refractive index layer, the amount of the solvent may be preferably 1000 parts by mass or more, more preferably 2000 parts by mass or more, and even more preferably 3000 parts by mass or more, assuming that the amount of the component (A) is 100 parts by mass. On the other hand, from the viewpoint of productivity of the process of drying the wet coating film and recovering the solvent after forming a wet coating film using the paint (A), it may be preferably 100,000 parts by mass or less, more preferably 50,000 parts by mass or less, and even more preferably 10,000 parts by mass or less.

The coating material for forming the low refractive index layer may further contain optional components other than the above components (A) to (C) as desired, to the extent that it does not contradict the object of the present invention. Examples of the optional components include defoamers, leveling agents, surfactants, thixotropy imparting agents, antistatic agents, antifouling agents, water repellents, printability improvers, antioxidants, weather resistance stabilizers, light resistance stabilizers, ultraviolet absorbers, heat stabilizers, and dyes. The optional components may be one or a mixture of two or more of these. The amount of the optional components to be blended may be usually 10 parts by mass or less, or about 0.01 to 10 parts by mass, per 100 parts by mass of the above component (A1).

The above-mentioned coating material for forming a low refractive index layer can be obtained by mixing and stirring these components.

3. Laminated film:
The laminate film of the present invention has the low refractive index B-stage coating of the present invention. The laminate film of the present invention usually has the low refractive index B-stage coating of the present invention on at least one side of the film substrate, and the low refractive index B-stage coating forms a surface.

The laminated film of the present invention can be obtained by forming the low refractive index B-stage coating film of the present invention on at least one side of a film substrate using the coating material for forming the low refractive index layer and the manufacturing method of the present invention. The manufacturing method of the present invention was explained in the section "1. Manufacturing method of low refractive index B-stage coating film". The low refractive index B-stage coating film of the present invention and the coating material for forming the low refractive index layer were explained in the section "2. Low refractive index B-stage coating film". The above film substrate will be explained below.

Film base:
The above-mentioned film substrate is a film that serves as a substrate for forming the low refractive index B-stage coating film of the present invention on at least one surface thereof.

The case where the film substrate is one of the constituent materials of the molded body of the present invention will be described. When the film substrate is one of the constituent materials of the molded body of the present invention, the film substrate is preferably one that has high transparency and is not colored (transparent resin film) from the viewpoint of increasing the transparency of the molded body and ensuring visibility. Examples of such films include transparent resin films such as cellulose ester resins such as triacetyl cellulose; polyester resins such as polyethylene terephthalate; cyclic hydrocarbon resins such as ethylene norbornene copolymers; acrylic resins such as polymethyl methacrylate, polyethyl methacrylate, and vinylcyclohexane-methyl (meth)acrylate copolymers; aromatic polycarbonate resins; polyolefin resins such as polypropylene and poly-4-methylpentene-1; polyamide resins; polyarylate resins; polymer-type urethane acrylate resins; and polyimide resins. These films include unstretched films, uniaxially stretched films, and biaxially stretched films. These films also include laminated films in which one or more of these are laminated in two or more layers.

The total light transmittance of the transparent resin film may be generally 85% or more, preferably 88% or more, and more preferably 90% or more. The higher the total light transmittance, the better. By using a transparent resin film with a total light transmittance of 85% or more, it is possible to obtain a molded article requiring high transparency, such as a low refractive index B-stage coating film laminate film suitable as a component for a display panel of an image display device such as a car navigation system or digital signage, and an instrument panel of an automobile, and a molded article using the same. Here, the total light transmittance is a value measured using a turbidity meter according to JIS K7361-1:1997. As the turbidity meter, for example, the turbidity meter "NDH2000 (product name)" manufactured by Nippon Denshoku Kogyo Co., Ltd. can be used.

The yellowness index of the transparent resin film may be usually 3 or less, preferably 2 or less, and more preferably 1 to -1. By using a transparent resin film with a yellowness index of 3 or less, it is possible to obtain a molded article that requires high colorlessness, such as a low refractive index B-stage coating film laminate film suitable as a component for a display faceplate of an image display device such as a car navigation system or digital signage, and an instrument panel of an automobile, and a molded article using the same. Here, the yellowness index is a value measured using a colorimeter according to JIS K7105:1981. As the colorimeter, for example, a colorimeter "SolidSpec-3700 (product name)" manufactured by Shimadzu Corporation can be used.

The retardation of the transparent resin film may be usually 75 nm or less, preferably 50 nm, more preferably 40 nm or less, even more preferably 30 nm or less, even more preferably 20 nm or less, and most preferably 15 nm or less. The lower the retardation, the better. By using a transparent resin film with a retardation of 75 nm or less, it is possible to obtain a molded article that requires clear transparency, such as a low refractive index B-stage coating film laminate film suitable as a component for a display panel of an image display device such as a car navigation system or digital signage, and an instrument panel of an automobile, and a molded article using the same. Here, the retardation is a value measured by the parallel Nicol rotation method. As a measuring device, for example, a phase difference measuring device "KOBRA-WR (product name)" by Oji Scientific Instruments Co., Ltd. using the parallel Nicol rotation method can be used.

When the film substrate is one of the constituent materials of the molded body of the present invention, the thickness of the film substrate is appropriately determined taking into consideration the use of the molded body. When the film substrate is one of the constituent materials of the molded body of the present invention, the thickness of the film substrate may be usually 20 μm or more, preferably 50 μm or more, from the viewpoint of handleability. The thickness of the film substrate may be usually 100 μm or more, preferably 150 μm or more, from the viewpoint of strength of the molded body. On the other hand, the thickness of the film substrate may be usually 2000 μm or less, preferably 800 μm or less, more preferably 600 μm or less, from the viewpoint of weight reduction of the molded body.

When the above-mentioned film substrate is one of the constituent materials of the molded body of the present invention, from the viewpoint of increasing the adhesion between the above-mentioned film substrate and the low refractive index B-stage coating film of the present invention, or the low refractive index layer (C-stage (fully cured) coating film) formed using the low refractive index B-stage coating film of the present invention, the coating film forming surface of the above-mentioned film substrate may be subjected to an easy-adhesion treatment such as a corona discharge treatment or anchor coat formation.

The following describes the case where the low refractive index B-stage coating film of the present invention is transferred to another substrate (e.g., a film, a sheet, a plate, or a substrate of any shape) (i.e., the film substrate does not constitute the molded article of the present invention).

When the low refractive index B-stage coating film of the present invention is used by transferring it to another substrate, the film substrate is not particularly limited, and any film substrate can be used. In this case, from the viewpoints of web handling and economy, the film substrate is preferably a non-stretched film or a biaxially stretched film of a polyester resin such as polyethylene terephthalate, and a non-stretched film or a biaxially stretched film of a polypropylene resin.

When the low refractive index B-stage coating film of the present invention is used by transferring it to another substrate, the thickness of the film substrate may be typically 20 μm or more, preferably 30 μm or more, from the viewpoint of web handling. On the other hand, the thickness of the film substrate may be typically 100 μm or less, preferably 75 μm or less, from the viewpoint of economy.

When the low refractive index B-stage coating film of the present invention is transferred to another substrate, the coating surface of the film substrate may be treated to facilitate peeling.

Coating film with three-dimensional formability:
In one embodiment, the laminated film of the present invention may have a coating film having three-dimensional formability on at least one side of the film substrate, and the low refractive index B-stage coating film of the present invention on the surface of the coating film having three-dimensional formability. By forming the coating film having three-dimensional formability, it is possible to impart desired functions and characteristics, for example, to increase the surface hardness or improve the anti-reflection function.

The thickness of the coating film having the above-mentioned three-dimensional formability is appropriately determined taking into consideration the functions and characteristics to be imparted to the laminated film of the present invention by forming the coating film layer. From the viewpoint of reliably obtaining the functions and characteristics to be obtained by forming the coating film layer, the thickness of the coating film having the above-mentioned three-dimensional formability may be usually 0.1 μm or more, preferably 1 μm or more, more preferably 5 μm or more, and even more preferably 8 μm or more. On the other hand, from the viewpoint of handling properties when forming the coating film layer, the thickness may be usually 100 μm or less, preferably 60 μm or less, and more preferably 30 μm or less.

Examples of coating films having the above-mentioned three-dimensional formability include B-stage coating films and urethane-based curable resin coating films.

B-stage coating film as a coating film having three-dimensional formability:
The B-stage coating film is a coating film in an intermediate curing state of a curable resin, and is a coating film that is completely cured (C-stage) at the same time when the low refractive index B-stage coating film of the present invention is completely cured (C-stage) by irradiating active energy rays. In one typical embodiment, the B-stage coating film is formed using a coating material containing an active energy ray curable resin and a photopolymerization initiator. Examples of the active energy ray curable resin include those exemplified in the description of the coating material for forming the low refractive index layer. The active energy ray curable resin can be one of these or a mixture of two or more of them.

This section describes an embodiment in which the B-stage coating film is formed on at least one side of the film substrate, and then a wet coating film is formed on the surface of the B-stage coating film using the low refractive index layer forming paint, thereby forming the low refractive index B-stage coating film of the present invention.

The photopolymerization initiator to be included in the coating material for forming the B-stage coating film is appropriately selected according to the type of filter used in forming the low refractive index B-stage coating film of the present invention. When using a 365 filter as the filter, preferred photopolymerization initiators include, for example, a photopolymerization initiator having an absorbance peak in the wavelength range of 220 to 280 nm, the peak top value of which is the maximum absorbance; a wavelength at which the absorbance is 1/n of the peak top value (=maximum absorbance) on the longer wavelength side than the peak top of the absorbance peak is usually 290 nm or less, preferably 285 nm or less, more preferably 280 nm or less; and a wavelength at which the absorbance is 1/n or less of the maximum absorbance at any wavelength in the range of 290 to 400 nm. Here, n is a natural number from 2 to 8, usually 2, preferably 3, more preferably 4, even more preferably 5, even more preferably 6, even more preferably 7, and most preferably 8. When the 365 filter is used as the filter, preferred examples of the photopolymerization initiator include 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, and a mixture of 1-hydroxycyclohexyl-phenyl-ketone and benzophenone (mass ratio is usually 100:0 to 45:55, in one embodiment 90/10 to 45:55). As the photopolymerization initiator, one or a mixture of two or more of these can be used.

The amount of the photopolymerization initiator to be included in the coating material for forming the B-stage coating film is appropriately selected by comprehensively considering the viewpoints of curing the coating film to a B-stage state, maintaining the curing of the coating film in a B-stage state even after irradiation with active energy rays when forming the low refractive index B-stage coating film of the present invention, and ensuring complete curing (C-stage) after three-dimensional molding. The amount of the photopolymerization initiator to be included may be usually 0.01 to 1 times, preferably 0.05 to 0.6 times, and more preferably 0.1 to 0.4 times the amount of the component (C) photopolymerization initiator included in the coating material for forming the low refractive index layer, from the viewpoint of maintaining the curing of the coating film in a B-stage state even after irradiation with active energy rays when forming the low refractive index B-stage coating film of the present invention. The amount of the photopolymerization initiator may be, relative to 100 parts by mass of the active energy ray-curable resin, usually 0.01 parts by mass or more, preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, even more preferably 0.5 parts by mass or more, and most preferably 1 part by mass or more, from the viewpoint of curing the coating film to a B-stage state and from the viewpoint of ensuring complete curing (C-stage) after three-dimensional molding. On the other hand, from the viewpoint of keeping the curing of the coating film in a B-stage state, it may be usually 20 parts by mass or less, preferably 12 parts by mass or less, more preferably 8 parts by mass or less, even more preferably 5 parts by mass or less, and most preferably 3 parts by mass or less.

We will now explain an embodiment in which the B-stage coating film is formed on at least one side of the film substrate, and then the low refractive index B-stage coating film of the present invention is formed by transfer onto the surface of the B-stage coating film.

The photopolymerization initiator to be contained in the coating material for forming the B-stage coating film is appropriately determined taking into consideration the method for forming the B-stage coating film. Examples of the photopolymerization initiator include those exemplified in the description of the coating material for forming the low refractive index layer. The photopolymerization initiator may be one of these or a mixture of two or more of them.

The amount of the photopolymerization initiator to be included in the coating material for forming the B-stage coating film is appropriately selected by comprehensively considering the viewpoints of curing the coating film in a B-stage state, maintaining the curing of the coating film in a B-stage state, and ensuring complete curing (C-stage) after three-dimensional molding. The amount of the photopolymerization initiator to be included may be usually 1 part by mass or more, preferably 2 parts by mass or more, more preferably 3 parts by mass or more, and even more preferably 4 parts by mass or more, based on 100 parts by mass of the active energy ray curable resin, from the viewpoint of curing the coating film in a B-stage state and ensuring complete curing (C-stage) after three-dimensional molding. On the other hand, from the viewpoint of maintaining the curing of the coating film in a B-stage state, it may be usually 20 parts by mass or less, preferably 15 parts by mass or less, more preferably 12 parts by mass or less, and even more preferably 10 parts by mass or less.

A method for producing a B-stage coating film that has three-dimensional formability. 1:
In one preferred embodiment, the method for producing a B-stage coating film as a coating film having three-dimensional formability includes: (1) a step of forming a wet coating film on the surface of a film substrate using a coating material containing (a) an active energy ray-curable resin and (b) a photopolymerization initiator; and (2) a step of irradiating the wet coating film with active energy rays to bring it into a B-stage state; wherein the active energy rays are monochromatized using a filter so as not to include wavelengths that result in an absorbance of usually ½ or more, preferably ⅓ or more, more preferably ¼ or more, even more preferably ⅕ or more, still more preferably ⅙ or more, and most preferably ⅛ or more of the maximum absorbance of the component (b) photopolymerization initiator.

In one preferred embodiment, the manufacturing method may include (1) a step of forming a wet coating film on the surface of a film substrate using a coating material containing (a) an active energy ray curable resin and (b) a photopolymerization initiator; and (2) a step of irradiating the wet coating film with active energy rays to bring it into a B-stage state; wherein the active energy rays are monochromatized using a filter so as not to include wavelengths that result in an absorbance of usually 1/2 or more, preferably 1/3 or more, more preferably 1/4 or more, even more preferably 1/5 or more, even more preferably 1/6 or more, even more preferably 1/7 or more, and most preferably 1/8 or more of the maximum absorbance of the component (b) photopolymerization initiator; and to include wavelengths that result in an absorbance of usually 1/10 to 1/100, preferably 1/15 to 1/70, and more preferably 1/20 to 1/50.

The maximum absorbance of the component (b) photopolymerization initiator means the maximum absorbance in the wavelength range of 220 to 400 nm on the wavelength-absorbance curve of the component (b) photopolymerization initiator.

The above-mentioned active energy rays do not include active energy rays of a certain wavelength, which means that the specific energy intensity of the active energy rays at that wavelength is usually less than 5%, preferably 2% or less, more preferably 1% or less, even more preferably 0.5% or less, and most preferably 0.1% or less.

The term "active energy rays include active energy rays of a certain wavelength" means that the specific energy intensity of the active energy rays at that wavelength is usually 5% or more, preferably 10% or more, and more preferably 15% or more.

Here, the specific energy intensity is the energy intensity (unit: %) at the wavelength that is most transparent through the filter, when the energy intensity at that wavelength is taken as 100%.

The above-mentioned step (1) is a step of forming a wet coating film on the surface of a film substrate using a coating material containing the above-mentioned component (a) active energy ray curable resin and the above-mentioned component (b) photopolymerization initiator.

The film substrate used in the above step (1) can be the same as the film substrate used in producing the laminated film of the present invention.

The active energy ray curable resin component (a) used in the coating material (a coating material containing the active energy ray curable resin component (a) and the photopolymerization initiator component (b)) used in the step (1) can be, for example, those exemplified in the description of the coating material for forming the low refractive index layer. The coating material preferably contains (a1) urethane (meth)acrylate as the active energy ray curable resin component (a).

When the component (a) contains the component (a1) urethane (meth)acrylate, the amount of the component (a1) in the component (a) may be generally 20% by mass or more, preferably 40% by mass or more, and more preferably 60 to 100% by mass, based on the amount of all the components (a) being 100% by mass, from the viewpoint of improving the balance between web handleability and three-dimensional moldability.

As the component (a1), for example, the same as the component (A1) urethane (meth)acrylate that can be contained as a preferred component in the coating material for forming the low refractive index layer can be used. In addition, since a coating film having three-dimensional formability is produced by a method similar to the method for producing the low refractive index B-stage coating film of the present invention, and the low refractive index B-stage coating film of the present invention is further formed on the surface of the coating film having three-dimensional formability, the preferred component (A1) urethane (meth)acrylate is also preferably used as the component (a1). As the component (a1), one or a mixture of two or more of these can be used.

As the component (a) active energy ray-curable resin, one or a mixture of two or more of these can be used.

As for the component (b) photopolymerization initiator to be included in the coating material used in the above step (1) (a coating material containing the component (a) active energy ray curable resin and the component (b) photopolymerization initiator), since a coating film having three-dimensional formability is produced by a method similar to the method for producing the low refractive index B-stage coating film of the present invention, and the low refractive index B-stage coating film of the present invention is further formed on the surface of the coating film having three-dimensional formability, the one that is preferable as the component (B) photopolymerization initiator to be included in the coating material for forming the low refractive index layer is also preferably used as the component (b). As the component (b), one or a mixture of two or more of these can be used.

The amount of component (b) may be, relative to 100 parts by mass of component (a), usually 0.01 parts by mass or more, preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, even more preferably 0.5 parts by mass or more, and most preferably 1 part by mass or more, from the viewpoint of curing the coating film to a B-stage state and from the viewpoint of ensuring complete curing (C-stage) after three-dimensional molding. On the other hand, from the viewpoint of keeping the curing of the coating film in a B-stage state, it may be usually 20 parts by mass or less, preferably 12 parts by mass or less, more preferably 8 parts by mass or less, even more preferably 5 parts by mass or less, and most preferably 3 parts by mass or less.

In the above step (1), the method of forming a wet coating film on the surface of the film substrate using a coating material containing the above component (a) active energy ray curable resin and the above component (b) photopolymerization initiator is not particularly limited, and a known web coating method can be used. As the above method, from the viewpoint of applying the coating material with good productivity by a roll-to-roll method, for example, methods such as rod coating, roll coating, gravure coating, reverse coating, kiss reverse coating, and die coating are preferable.

Before irradiating with active energy rays in the above step (2), it is preferable to pre-dry the wet coating film formed using a coating material containing the above component (a) active energy ray-curable resin and the above component (b) photopolymerization initiator. The pre-drying can be performed, for example, by passing the web through a drying oven set at a temperature of about 23 to 150°C, preferably a temperature of 50 to 120°C, at a line speed such that the time required to pass from the inlet to the outlet is about 0.5 to 10 minutes, preferably 1 to 5 minutes.

The above-mentioned step (2) is a step of irradiating the above-mentioned wet coating film with active energy rays to bring it into a B-stage state. The amount of irradiation of the above-mentioned active energy rays is kept very low by using a filter in order to keep the hardening of the above-mentioned wet coating film in a B-stage state.

Examples of light sources for the above-mentioned active energy rays include high-pressure mercury lamps and metal halide lamps.

The amount of irradiation of the active energy rays is appropriately selected and determined from the viewpoints of stably performing the step (2), curing the wet coating film to a B-stage state, and maintaining the curing of the wet coating film in a B-stage state, taking into consideration the number of polymerizable functional groups of the component (a) active energy ray-curable resin, the type and blending amount of the component (b) photopolymerization initiator, etc. The amount of irradiation of the active energy rays, converted into the amount of irradiation when no filter is used, may be usually 1 to 1000 mJ/cm ² , preferably 30 to 700 mJ/cm ^2, and more preferably 50 to 500 mJ/cm ² .

After step (2) above, an aging treatment may be performed. This can stabilize the properties of the B-stage coating film.

A method for producing a B-stage coating film as a coating film having three-dimensional formability. 2:
In another preferred embodiment, the method for producing a B-stage coating film as a coating film having three-dimensional formability includes: (1) forming a wet coating film on a surface of a film substrate, usually on one surface of the film substrate, using a coating material for forming a B-stage coating film; (2) treating the wet coating film formed in the above step (1) at a temperature of 80 to 160° C., preferably 90 to 150° C., more preferably 100 to 140° C. for 1 to 20 minutes, preferably 3 to 15 minutes, more preferably 4 to 10 minutes, thereby drying and curing the wet coating film to a B-stage state; and (3) cooling the temperature of the coating film treated in the above step (2) to usually 60° C. or less, preferably 50° C. or less, more preferably 40° C. or less; wherein the coating material for forming the B-stage coating film includes (a) an active energy ray curable resin, (b) a photopolymerization initiator, and (c) a thermal polymerization initiator. This may be a method for producing a B-stage coating film.

The paint for forming the B-stage coating film will now be described. Examples of the component (a) active energy ray curable resin include those exemplified in the description of the paint for forming the low refractive index layer. The component (a) active energy ray curable resin preferably contains (a1) urethane (meth)acrylate. The component (a) active energy ray curable resin preferably contains (a2) mercaptoalkyl glycol urils.

The above-mentioned component (a1) can be, for example, the one described above as the component (A1) urethane (meth)acrylate that can be included as a preferred component in the coating material for forming the low refractive index layer.

The number average molecular weight (Mn) of the component (a1) calculated as polystyrene equivalent, obtained from the GPC curve measured by GPC, may be usually 1000 or more, preferably 1600 or more, more preferably 2000 or more, from the viewpoint of three-dimensional moldability. On the other hand, from the viewpoint of coatability, it may be usually 50,000 or less, preferably 30,000 or less.

The polystyrene-equivalent mass average molecular weight (Mw) of the component (a1) determined from the GPC curve measured by GPC may be typically 2,000 or more, preferably 4,000 or more, from the viewpoint of three-dimensional moldability. On the other hand, from the viewpoint of coatability, it may be typically 100,000 or less, preferably 50,000 or less.

The GPC measurement method is described above.

The number of (meth)acryloyl groups in the above component (a1) may be typically 2 or more, preferably 3 or more, per 1000 polystyrene-equivalent number average molecular weight (Mn) determined from a GPC curve, from the viewpoint of web handling (the resistance to scratches and poor appearance caused by the coating film coming into contact with a transfer roll, etc. during web handling). From the viewpoints of surface hardness, scratch resistance, and chemical resistance after complete curing (at C stage), it may more preferably be 6 or more. On the other hand, from the viewpoint of three-dimensional moldability, it may be typically 20 or less, preferably 12 or less, more preferably 10 or less.

As the above component (a1), one or a mixture of two or more of these can be used.

When the component (a) contains the component (a1), the amount of the component (a1) is usually 10% by mass or more, preferably 40% by mass or more, more preferably 70% by mass or more, and even more preferably 80 to 100% by mass, based on 100% by mass of the total of the components (a), from the viewpoint of reliably obtaining the effect of using the component (a1).

It is preferable to use (a2) a mercaptoalkyl glycol uril as the active energy ray curable resin (a) above. This can improve in a well-balanced manner three-dimensional moldability in the B stage; web handling properties (resistance to scratches and poor appearance caused by the coating film coming into contact with a transfer roll, etc. during web handling); and surface hardness, scratch resistance, and chemical resistance after complete curing (in the C stage).

The number of mercaptoalkyl groups in the above component (a2) is preferably 2 to 4, and more preferably 4, from the viewpoint of reliably obtaining the effect of using the above component (a2).

Examples of the above component (a2) include mercaptoalkyl glycolurils having two mercaptoalkyl groups in one molecule, such as 1,3-bis(3-mercaptopropyl) glycoluril; mercaptoalkyl glycolurils having four mercaptoalkyl groups in one molecule, such as 1,3,4,6-tetrakis(2-mercaptoethyl) glycoluril and 1,3,4,6-tetrakis(3-mercaptopropyl) glycoluril; and the like.

As the above component (a2), one or a mixture of two or more of these can be used.

When the component (a) contains the component (a2), the blending ratio of the component (a2) may be, with the sum of the components (a) being 100% by mass, usually 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more, and even more preferably 4% by mass or more, from the viewpoint of reliably obtaining the effect of using the component (a2). On the other hand, from the viewpoint of three-dimensional moldability in the B stage, it may be usually 20% by mass or less, preferably 15% by mass or less, more preferably 12% by mass or less, and even more preferably 10% by mass or less.

It is more preferable to use the component (a) active energy ray curable resin containing the component (a1) urethane (meth)acrylate and the component (a2) mercaptoalkyl glycol uril. This can further improve in a well-balanced manner both the three-dimensional moldability in the B stage and the surface hardness, scratch resistance, and chemical resistance after complete curing (in the C stage).

When the component (a) contains the components (a1) and (a2), the amount of the component (a1) is usually 99 to 80% by mass (the amount of the component (a2) is 1 to 20% by mass), preferably 98 to 85% by mass (the amount of the component (a2) is 2 to 15% by mass), more preferably 97 to 88% by mass (the amount of the component (a2) is 3 to 12% by mass), and even more preferably 96 to 90% by mass (the amount of the component (a2) is 4 to 10% by mass), where the sum of the amount of the component (a1) and the amount of the component (a2) is 100% by mass.

When the component (a) contains the components (a1) and (a2), the sum of the amount of the components (a1) and (a2) is usually 80% by mass or more, preferably 90% by mass or more, more preferably 95% by mass or more, and even more preferably 98 to 100% by mass, based on the total amount of the components (a) being 100% by mass, from the viewpoint of the balance between the three-dimensional formability in the B stage and the surface hardness, scratch resistance, and chemical resistance after complete curing (in the C stage).

As the component (a) active energy ray-curable resin, one or a mixture of two or more of these can be used.

As for the component (b) photopolymerization initiator to be included in the coating material for forming the B-stage coating film, since the low refractive index B-stage coating film of the present invention is further formed on the surface of the coating film having three-dimensional formability, the photopolymerization initiator that is preferable as the component (B) photopolymerization initiator to be included in the coating material for forming the low refractive index layer is also preferably used as the component (b).

When the low refractive index B-stage coating film is formed by applying the coating material for forming the low refractive index layer on the surface of a coating film having three-dimensional moldability, the amount of component (b) may be, from the viewpoint of curing the coating film to a B-stage state and from the viewpoint of ensuring complete curing (C-stage) after three-dimensional molding, usually 0.01 parts by mass or more, preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, even more preferably 0.5 parts by mass or more, and most preferably 1 part by mass or more, relative to 100 parts by mass of component (a). On the other hand, from the viewpoint of keeping the curing of the coating film in a B-stage state, it may be usually 20 parts by mass or less, preferably 12 parts by mass or less, more preferably 8 parts by mass or less, even more preferably 5 parts by mass or less, and most preferably 3 parts by mass or less.

When the low refractive index B-stage coating film is formed by transfer onto the surface of a coating film having three-dimensional moldability, the amount of component (b) may be, relative to 100 parts by mass of component (a), usually 1 part by mass or more, preferably 2 parts by mass or more, more preferably 3 parts by mass or more, and even more preferably 4 parts by mass or more, from the viewpoint of curing the coating film to a B-stage state and from the viewpoint of ensuring complete curing (C-stage) after three-dimensional molding. On the other hand, from the viewpoint of keeping the curing of the coating film in a B-stage state, it may be usually 20 parts by mass or less, preferably 15 parts by mass or less, more preferably 12 parts by mass or less, and even more preferably 10 parts by mass or less.

The above-mentioned component (c) thermal polymerization initiator is a compound that generates active species such as radicals when heated. The above-mentioned component (c) acts to harden the coating film to a B-stage state.

The above-mentioned component (c) thermal polymerization initiator may, for example, be 2,2'-azobisisobutyronitrile (2,2'-azobis(2-methylpropionitrile)), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2-methylpropionate)dimethyl, 1,1'-azobis(methyl cyclohexanecarboxylate), 2,2'-azobis(n-butyl-2-methylpropionamide), 2,2'-azobis(2-methylpropionamidine) dihydrochloride, dimethyl 1,1-azobis(1-cyano cyclohexanecarboxylate), and 2,2'-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride; organic peroxides such as benzoyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, di-tert-butyl peroxide, and dicumyl peroxide; benzenesulfonic acid esters such as cyclohexyl p-toluenesulfonate; sulfonium salts such as benzyl(4-hydroxyphenyl)methylsulfonium hexafluoroantimonate, (4-hydroxyphenyl)methyl(2-methylbenzyl)sulfonium hexafluoroantimonate, and diphenyl(methyl)sulfonium tetrafluoroborate; and dicyandiamide.

The above-mentioned component (c) is preferably a compound that generates radicals. As the above-mentioned component (c), from the viewpoint of being inactive near room temperature and suppressing unintended curing reactions, and from the viewpoint of being completely consumed in the process of curing the coating film to a B-stage state and being able to stably maintain the coating film in a B-stage state until three-dimensional molding is performed, an azo compound is preferable, and an azo compound having a molecular weight (molecular weight calculated from the chemical formula) of 250 or more, preferably 300 to 1000, is more preferable.

As the above component (c), one or a mixture of two or more of these can be used.

The amount of the component (c) may be appropriately selected by comprehensively considering the viewpoints of curing the coating film in a B-stage state, maintaining the cured coating film in a B-stage state, and stably maintaining the coating film in a B-stage state until three-dimensional molding is performed. The amount of the component (c) may be, from the viewpoint of curing the coating film in a B-stage state, usually 0.001 parts by mass or more, preferably 0.005 parts by mass or more, more preferably 0.01 parts by mass or more, and even more preferably 0.02 parts by mass or more, relative to 100 parts by mass of the component (a). On the other hand, from the viewpoint of maintaining the cured coating film in a B-stage state and stably maintaining the coating film in a B-stage state until three-dimensional molding is performed, it may be usually 1 part by mass or less, preferably 0.5 parts by mass or less, more preferably 0.3 parts by mass or less, even more preferably 0.2 parts by mass or less, and most preferably 0.1 parts by mass or less.

The above-mentioned step (1) is a step of forming a wet coating film on one side of the film substrate using the above-mentioned B-stage coating film forming paint. The above-mentioned step (1) is usually a step of forming a wet coating film on one side of the film substrate using the above-mentioned B-stage coating film forming paint.

The film substrate used in the above step (1) can be the same as the film substrate used in producing the laminated film of the present invention.

In the above step (1), the method of forming a wet coating film on the surface of the film substrate using the B-stage coating film forming paint is not particularly limited, and any known web coating method can be used. As the web coating method, from the viewpoint of applying the paint with good productivity by a roll-to-roll method, for example, methods such as rod coating, roll coating, gravure coating, reverse coating, kiss reverse coating, and die coating are preferable.

The above-mentioned step (2) is a step in which the wet coating film formed in the above-mentioned step (1) is dried and cured to a B-stage state by treating it at a temperature of 80 to 160°C, preferably 90 to 150°C, more preferably 100 to 140°C for a time of 1 to 20 minutes, preferably 3 to 15 minutes, more preferably 4 to 10 minutes.

Without intending to be bound by theory, the processing time of the above step (2) is considerably shorter than the time required to completely cure (C stage) the coating film using a thermal polymerization initiator, and the progress of the heat-induced curing reaction is stopped by the above step (3). Furthermore, the above paint for forming a B stage coating film contains a fairly small amount of thermal polymerization initiator, and the progress of the curing reaction should be quite slow. For this reason, it is believed that the coating film remains in a B stage state.

The treatment in step (2) above can be carried out by any method. For example, the treatment in step (2) above can be carried out by passing the web through a drying oven set at a temperature of 80 to 160°C, preferably 90 to 150°C, and more preferably 100 to 140°C, at a line speed such that the time required for passing from the inlet to the outlet is 1 to 20 minutes, preferably 3 to 15 minutes, and more preferably 4 to 10 minutes.

The above step (3) is a step of cooling the temperature of the coating film treated in the above step (2) to usually 60°C or less, preferably 50°C or less, and more preferably 40°C or less, thereby stopping the progress of the thermal curing reaction. The above step (3) is preferably performed immediately after the above step (2) in order to stop the progress of the thermal curing reaction.

The treatment in step (3) can be carried out by any method. The treatment in step (3) can be carried out, for example, by handling the web. The heat quantity of the coating film treated in step (2) is usually not so large. Therefore, it is expected that the web can be cooled sufficiently quickly to a temperature of 60°C or less by handling the web while being held by a transfer roll that is not temperature controlled. The treatment in step (3) can be carried out preferably by handling the web while being held by a chill roll. The temperature of the chill roll is usually set to 60°C or less, preferably 50°C or less, and more preferably room temperature (23°C) to 40°C. The chill roll is not limited to one roll, and may be two or more rolls.

When the treatment in step (2) is carried out by passing the web through a drying oven set at a predetermined temperature at a predetermined line speed, the treatment in step (3) can be carried out by handling the web emerging from the drying oven while holding it on a transfer roll that is not temperature controlled, preferably a chill roll set at a predetermined temperature.

After step (3) above, an aging treatment may be performed. This can stabilize the properties of the B-stage coating film.

Urethane-based curable resin coating film as a coating film having three-dimensional formability:
The urethane-based curable resin coating film is a coating film formed by using a curable resin composition containing a polyol compound, a curable resin having a hydroxyl group such as an acrylic-based curable resin having a hydroxyl group, and a compound having two or more isocyanate groups in one molecule. The urethane-based curable resin coating film maintains a certain degree of flexibility even after being completely cured (C stage), and has three-dimensional moldability.

A coating film with three-dimensional formability that functions as a high refractive index layer:
In one embodiment, the coating film having three-dimensional moldability may contain high refractive index particles. The coating film having three-dimensional moldability contains high refractive index particles and functions as a high refractive index layer, thereby enhancing the anti-reflection function. In an embodiment in which the coating film having three-dimensional moldability contains high refractive index particles, the refractive index (RH) of the coating film having three-dimensional moldability may be preferably 1.55 or more, more preferably 1.6 or more, from the viewpoint of increasing the refractive index difference with the refractive index (RL) of the low refractive index layer formed using the low refractive index B stage coating film of the present invention and exhibiting a good anti-reflection function. On the other hand, from the viewpoint of the color of reflected light, it may be usually 2.0 or less, preferably 1.9 or less, more preferably 1.8 or less, even more preferably 1.7 or less, and most preferably 1.65 or less.

The refractive index (RH) is a value measured using an Abbe refractometer according to JIS K7142:2008 Method A, using sodium D line (wavelength 589.3 nm), 1-bromonaphthalene as the contact liquid, the surface of the sample that was the biaxially oriented polypropylene resin film side when the sample was made is the surface that is in contact with the prism, and the direction of operation of the bar coater of the sample is the length direction of the test piece. For the sample, the paint for forming the coating film having the above-mentioned three-dimensional formability is applied to the surface of a 20 μm thick biaxially oriented polypropylene resin film using a bar coater so that the thickness after curing is 2 μm, and the coating film obtained by drying and curing is peeled off from the biaxially oriented polypropylene resin film for use.

Examples of the high refractive index particles include metal oxides such as titanium oxide, zinc oxide, indium oxide, tin oxide, zirconium oxide, and aluminum oxide; and composite oxides in which these metal oxides are doped with different elements such as antimony and tin.

The high refractive index particles may be surface-treated with a silane coupling agent such as vinyl silane and amino silane; a titanate coupling agent; an aluminate coupling agent; an organic compound having an ethylenically unsaturated bond group such as a (meth)acryloyl group, a vinyl group, or an allyl group, or a reactive functional group such as an epoxy group; or a surface treatment agent such as a fatty acid or a fatty acid metal salt.

The average particle size of the high refractive index particles is appropriately determined taking into consideration the need to maintain the transparency of the coating film and the productivity of producing the high refractive index particles. The average particle size of the high refractive index particles may usually be 1 to 300 nm, preferably 5 to 200 nm, more preferably 10 to 150 nm, and even more preferably 15 to 100 nm. The method for measuring and the definition of the average particle size are described above in the explanation of the component (B) low refractive index particles.

The high refractive index particles may be one of these or a mixture of two or more of them.

The amount of the high refractive index particles is determined appropriately, taking into consideration the type of the high refractive index particles, from the viewpoint of setting the refractive index (RH) in the above-mentioned range. The amount of the high refractive index particles may be usually 10 to 300 parts by mass, preferably 30 to 200 parts by mass, more preferably 45 to 150 parts by mass, and even more preferably 60 to 120 parts by mass, per 100 parts by mass of the base resin of the coating material for forming the coating film having the above-mentioned three-dimensional formability, from the viewpoint of setting the refractive index (RH) in the above-mentioned range.

4. Molded body:
The molded article of the present invention has a low refractive index layer (C stage (fully cured) coating film) formed using the low refractive index B stage coating film of the present invention. The low refractive index layer usually constitutes a part or all of the surface of the molded article of the present invention. In one typical embodiment, a low refractive index layer (C stage (fully cured) coating film) formed using the low refractive index B stage coating film of the present invention is formed on the surface of the molded article of the present invention in a location that is exposed to direct sunlight.

The molded article of the present invention can be produced by imparting a desired shape to the low refractive index B-stage coating film of the present invention, and then completely curing (C-stage) the low refractive index B-stage coating film. Examples of such molded articles include films, sheets, and plates having a low refractive index layer (C-stage (completely cured) coating film) formed using the low refractive index B-stage coating film of the present invention; molded articles obtained by imparting a desired shape to the laminated film of the present invention by three-dimensional molding such as vacuum molding, pressure molding, and press molding, and then completely curing (C-stage) the low refractive index B-stage coating film of the laminated film; and composite molded articles obtained by inserting the laminated film of the present invention into a mold as a skin material, injecting any thermoplastic resin as a core material, and then completely curing (C-stage) the low refractive index B-stage coating film of the laminated film.

This section describes an example of a method for producing a molded article of the present invention by using the laminated film of the present invention (coating film is in B stage) and applying a three-dimensional molding method to impart a three-dimensional shape, and then completely curing (to C stage) the low refractive index B-stage coating film of the laminated film, in the case of vacuum molding.

Figure 6 is a conceptual diagram showing an example of a vacuum molding device. First, as shown in Figure 6(a), the laminated film (coating film is in B stage) 1 is heated and softened using a heating device 2 such as an infrared heater. Next, the laminated film 1 is removed from the heating device 2 and quickly covered with a mold 3 (Figure 6(b)). At this time, the mold 3 may be preheated. Next, the space 4 between the laminated film 1 and the mold 3 is depressurized, the laminated film 1 is adhered to the mold 3, the shape of the mold 3 is transferred to the laminated film 1, and a molded body 5 (coating film is in B stage) is obtained (Figure 2(c)). Before releasing the molded body 5 from the mold 3, the mold 3 may be cooled. Next, the low refractive index B stage coating film of the molded body 5 is completely cured (to C stage) using any active energy ray irradiation device, thereby producing the molded body of the present invention.

The pressure in the space 4 may be preferably 10 KPa or less, more preferably 1 KPa or less, from the viewpoint of sufficient adhesion without leaving any air between the B-stage coating laminate film 1 and the molding die 3. The adhesion force increases as the pressure in the space 4 decreases, but considering that reducing the pressure increases costs exponentially and the mechanical strength of the laminate film 1, the lower limit of the pressure in the space 4 may be practically about 10 ^-5 KPa.

The amount of irradiation of the active energy rays is appropriately selected and determined from the viewpoint of a necessary and sufficient amount of irradiation for completely curing (C-stage) the low refractive index B-stage coating film. The amount of irradiation of the active energy rays may be usually 10 to 10,000 mJ/cm ² , preferably 200 to 2,000 mJ/cm ² , and more preferably 300 to 700 mJ/cm ² .

In one embodiment, the molded article of the present invention may have a low refractive index layer (C-stage (fully cured) coating film) formed using the low refractive index B-stage coating film of the present invention, and an optional substrate. The molded article of this embodiment can be produced by using the substrate instead of the mold 3, adhering and integrating the laminated film 1 to the substrate, and then completely curing (to C-stage) the low refractive index B-stage coating film.

Since the molded article of the present invention has the above-mentioned preferable properties, it can be suitably used as an article used in places exposed to direct sunlight, for example, as a display panel for image display devices such as car navigation systems and digital signage, and as an instrument panel for automobiles.

Since the molded article of the present invention has the preferred properties as described above, it can be suitably used as an article (including a member of an article). Examples of the article include image display devices such as liquid crystal displays, plasma displays, and electroluminescence displays, and their display panels, transparent conductive substrates, and housings; televisions, personal computers, tablet-type information devices, smartphones, and their housings and display panels; refrigerators, washing machines, cupboards, wardrobes, and panels that constitute these devices; windows and doors of buildings; vehicles, vehicle windows, windshields, roof windows, and instrument panels; head-up displays, electronic signs, and their protective plates; show windows; solar cells, and their housings and front panels; and the like.

The present invention will be described below with reference to examples, but the present invention is not limited to these.

Measurement method (a) Three-dimensional formability:
The laminated film (coating film is in B stage) was preheated using an infrared heater, and then the laminated film was spread over a mold preheated to 130°C (see Fig. 7; Fig. 7(a) front view, height (h) 10 mm, radius of curvature (R) of the curved portion around the mold 16.25 mm; Fig. 7(b) plan view, outer diameter (φ) 90 mm) so that the surface of the laminated film opposite to the coating film surface of the laminated film faces the mold. After waiting for 30 seconds, the pressure in the space between the laminated film and the mold was reduced to 1.0 x 10 ^-3 KPa, and the shape of the mold was transferred to the laminated film, to obtain a molded body (coating film is in B stage). The B-stage coating film of the molded body was irradiated with a high-pressure mercury lamp type ultraviolet irradiation device under the condition of an accumulated light amount of 600 mJ/cm ² to completely cure (to C stage), to obtain a molded body (coating film is in C stage). The appearance of the molded product (the coating film was in C stage) was visually observed and evaluated according to the following criteria.
A: No cracks, breaks, or defects in appearance were observed.
B: No cracks or breaks were found. However, when viewed up close through the light, there were some areas that were slightly cloudy.
C: Slight cracks or breaks were observed in the curved portion around the periphery.
D: Cracks and cracks were observed throughout the entire surface.

(b) Tack-free test (index of web handling properties):
The laminated film (coating film is in B stage) was preheated at 80°C for 6 minutes, and then a latex glove ("Latex Dispo NEO GT1351M (trade name)" by Okamoto Corporation) was placed on the low refractive index B stage coating film surface of the laminated film, and a 500g weight was placed on top of the latex glove, and the latex glove and the weight were immediately removed from the low refractive index B stage coating film surface of the laminated film. The low refractive index B stage coating film surface of the laminated film was visually observed while shining light from a fluorescent lamp at various angles of incidence, and was evaluated according to the following criteria.
A: No traces of contact with latex gloves were found.
B: When the area where the latex glove had come into contact was held up to a light and looked at closely, it was slightly cloudy and just about distinguishable.
C: The area where the latex glove came into contact had a clear decrease in transparency and was easily identifiable.
D: Roughness was observed on the surface of the coating film due to contact with a latex glove.

Technically, the above-mentioned test (ii) tack-free test is considered to be an indicator of web handling properties (the resistance of the coating film to scratches or poor appearance caused by contact with a transfer roll, etc. during web handling). If the above-mentioned test (ii) tack-free test is at a low level, it goes without saying that after forming the low refractive index B-stage coating film, the coating film should be protected with a protective film before it comes into contact with a transfer roll, etc.

In the following tests (c) to (n), a laminate film (coating film in B stage) was irradiated with ultraviolet light at an integrated light quantity of 600 mJ/ ^cm2 to turn the coating film into a C stage coating film (completely cured), and the film was used as a sample.

(C) Total light transmittance:
According to JIS K7361-1:1997, the total light transmittance (unit: %) of the laminated film (coating film is C stage) was measured using a turbidity meter "NDH2000 (product name)" manufactured by Nippon Denshoku Industries Co., Ltd.

(2) Hays:
The haze (unit: %) of the laminated film (coating film is in C stage) was measured using a turbidity meter "NDH2000 (product name)" manufactured by Nippon Denshoku Industries Co., Ltd. in accordance with JIS K7136:2000.

(e) Minimum reflectance:
A spectrophotometer "SolidSpec-3700 (product name)" and a reflection unit "Absolute reflectance measurement device, incident angle 5° (product name)" manufactured by Shimadzu Corporation were used, and a black adhesive sheet was attached to the surface opposite the low refractive index layer side of the laminated film (coating film is C stage) under the condition of 5 degree regular reflection (the reflection unit was installed in front of the integrating sphere) in accordance with the instructions for the spectrophotometer. The lowest reflectance was read as the minimum reflectance (unit: %) from the spectrum obtained by smoothing the spectrum by polynomial approximation. The black adhesive sheet was obtained by mixing 20 parts by mass of black acrylic adhesive master batch "Black-OT-1338 (trade name)" of Resino Color Kogyo Co., Ltd. and 100 parts by mass of adhesive "LKU-01 (trade name)" of Fujikura Kasei Co., Ltd. on one side of a 25 μm thick biaxially stretched polyethylene terephthalate resin film "E5431 (trade name)" of Toyobo Co., Ltd., and applying the mixture using an applicator so that the thickness after drying would be 35 μm. The L* value obtained by measuring the color of the adhesive layer of the black adhesive sheet was 3.13. The L* value was obtained by measuring the XYZ coordinates under standard light D65 illumination, geometric condition c, and conditions including components that become specular reflection, using a spectrophotometer "CM600d" of Konita Minolta Japan Co., Ltd., in accordance with JIS Z 8722:2009, and converting this to L*a*b* coordinates.

(f) Cross-cut test (coating adhesion):
According to JIS K5600-5-6:1999, 100 squares (1 square = 1 mm x 1 mm) were cut into the low refractive index layer side of the laminated film (coating film is C stage), and then adhesion test tape was attached to the squares, squeezed with fingers, and then peeled off. The evaluation criteria were in accordance with Table 1 of the above JIS standard.
Category 0: The edges of the cut are completely smooth and there are no peeling marks on any of the grids.
Category 1: Small separations of the coating at the intersections of cuts. No more than 5% of the cross-cut area is significantly affected.
Category 2: The coating has flaked along the edges of the cuts and/or at the intersections. Clearly more than 5% but not more than 15% of the cross-cut areas are affected.
Category 3: The coating has suffered partial or complete major flaking along the edges of the cuts and/or partial or complete flaking of various areas of the mesh. Cross-cut areas are affected by significantly more than 15% but not more than 35%.
Category 4: The coating has partially or completely peeled off along the edges of the cuts and/or has partially or completely peeled off in several areas. The cross-cut area is clearly more than 35% affected but not more than 65%.
Class 5: The degree of peeling exceeds Class 4.

(g) Water contact angle (initial water contact angle):
The water contact angle (unit: degree) of the surface of the low refractive index layer of the laminate film (coating film was C stage) was measured using an automatic contact angle meter "DSA20 (product name)" manufactured by KRUSS Co., Ltd. by a method of calculation from the width and height of a water droplet (see JIS R 3257:1999).

(H) Pencil hardness:
According to JIS K5600-5-4:1999, the surface of the low refractive index layer of the laminated film (coating film is C stage) was measured using a pencil "Uni (product name)" manufactured by Mitsubishi Pencil Co., Ltd. under the conditions of a test length of 25 mm and a load of 750 g. The judgment of whether scratches were generated or not was made by visually observing the sample surface under a fluorescent lamp at a position 50 cm away from the fluorescent lamp.

(i) Scratch resistance:
A test piece measuring 150 mm long and 50 mm wide was taken so that the machine direction of the laminated film (coating film is C stage) was the longitudinal direction of the test piece. The test piece was placed in a crockmeter type tester (friction tester type 1) of JIS L0849:2013 so that the low refractive index layer of the laminated film (coating film is C stage) was on the surface. The friction terminal of the tester was covered with four layers of gauze (medical type 1 gauze from Kawamoto Sangyo Co., Ltd.) and set so as to be in contact with the test piece. A load of 500 g was placed on the test piece, and the coating surface of the test piece was rubbed back and forth 250 times under the conditions of a friction terminal movement distance of 60 mm and a speed of 1 round trip/second. The presence or absence of scratches was then judged by visually observing the rubbed area of the test piece under a fluorescent lamp at a position 50 cm away from the fluorescent lamp. If no scratches were found, the same part of the test piece was rubbed back and forth 250 times and then visually observed. Evaluation was based on the following criteria.
A: No scratches were observed even after 1000 reciprocal strokes.
B: No scratches were observed after 750 reciprocating movements, but scratches were observed after 1000 reciprocating movements.
C: No scratches were observed after 500 reciprocating movements, but scratches were observed after 750 reciprocating movements.
D: No scratches were observed after 250 reciprocating movements, but scratches were observed after 500 reciprocating movements.
E: Scratches were visible after 250 reciprocations.

(J) Chemical resistance:
A test liquid was prepared by mixing 20 ml of Johnson &Johnson's sunscreen Neutrogena Ultra Sheer Dry Touch Sunblock (trade name) with 10 drops of Pilot Ink Red (trade name) red ink from Pilot Co., Ltd. A test piece measuring 100 mm x 100 mm was taken from a laminated film (coating film is C stage), and a paper wiper (Kimwipe (trade name) from Nippon Paper Crecia Co., Ltd.) cut to a size of 30 mm x 40 mm was spread and placed on the surface of the low refractive index layer of the test piece, and 10 drops of the test liquid were evenly dropped onto the paper wiper using a dropper. After dropping, air bubbles between the paper wiper and the test piece were removed using tweezers, the paper wiper and the test piece were brought into close contact with each other, and then the test piece was stored for 4 hours in an environment at a temperature of 80° C. (humidity was not controlled), after which the paper wiper containing the test liquid on the test piece was removed, the test piece was wiped with a paper wiper soaked in water, and then wiped dry with a dry paper wiper to remove the test liquid adhering to the surface of the test piece.Then, the test piece was visually observed by a person with corrected vision of 1.0 with the naked eye or using a loupe (10x), and evaluated according to the following criteria.
A: No cracks were observed even with a magnifying glass. No difference in color tone was observed between the area of the low refractive index layer surface of the laminated film that had been in contact with the test liquid and the area that had not been in contact with the test liquid.
B: No cracks were observed even with a magnifying glass, but there was a difference in color between the area of the low refractive index layer surface of the laminated film that had been in contact with the test liquid and the area that had not been in contact with the test liquid (the area that had been in contact was reddish compared to the area that had not been in contact).
C: No cracks were observed with the naked eye, but were observed using a magnifying glass.
D: Cracks were visible to the naked eye.

Raw materials used (A) Active energy ray curable resin:
(A1) Urethane (meth)acrylate:
(A1-1) "Art Resin UN-953 (product name)" multifunctional urethane (meth)acrylate from Negami Chemical Industrial Co., Ltd. Solid content 40% by mass, number of functional groups (number of (meth)acryloyl groups per molecule; the same applies below) 20, number average molecular weight 2000, mass average molecular weight 26000, Z average molecular weight 110000.
(A1-2) Negami Chemical Industrial Co., Ltd.'s multifunctional urethane (meth)acrylate "Art Resin UN-952 (product name)", solid content 60 mass%, number of functional groups 10, number average molecular weight 2500, mass average molecular weight 9100, Z average molecular weight 23000.
(A1-3) Negami Chemical Industrial Co., Ltd.’s multifunctional urethane (meth)acrylate “Art Resin UN-954 (product name)”, solid content 60% by mass, number of functional groups 6, number average molecular weight 2000, mass average molecular weight 4800, Z average molecular weight 9600.
(A1-4) Negami Chemical Industrial Co., Ltd.'s multifunctional urethane (meth)acrylate "Art Resin UN-909 (product name)", solid content 70 mass%, number of functional groups 9, number average molecular weight 1500, mass average molecular weight 13000, Z average molecular weight 60000.
(A1-5) "KRM8452 (product name)" multifunctional urethane (meth)acrylate from Daicel Allnex Corporation. Solid content 100% by mass, number of functional groups 10, number average molecular weight 900, mass average molecular weight 2400, Z average molecular weight 4700.
(A1-6) Kyoeisha Chemical Co., Ltd.'s multifunctional urethane (meth)acrylate "UF-C051 (product name)". Solid content 100% by mass, number of functional groups 2, number average molecular weight 1600, mass average molecular weight 34000, Z average molecular weight 57000.

(A2) Active energy ray-curable resin other than urethane (meth)acrylate:
(A2-1) "SIRIUS501 (product name)" by Osaka Organic Chemical Industry Co., Ltd. A copolymer having a dendrimer structure of dipentaerythritol hexaacrylate and tetrafunctional thiol. Solid content 50% by mass, mass average molecular weight 12,000, number average molecular weight 940, Z-average molecular weight 73,000, sulfur content 2.2% by mass.
(A2-2) 1,3,4,6-tetrakis(2-mercaptoethyl)glycoluril “TS-G (product name)” from Shikoku Chemical Industry Co., Ltd.

(B) Low refractive index particles:
(B-1) Hollow silica dispersion "THRULYA4320 (product name)" from JGC Catalysts and Chemicals. The amount of hollow silica in the dispersion is 20% by mass. The average particle size of the hollow silica is 60 nm.

(C) Photopolymerization initiator:
(C-1) α-hydroxyalkylphenone photopolymerization initiator (1-hydroxycyclohexyl-phenyl ketone) "Omnirad 184 (trade name)" from IGM Resins.
(C-2) Acetophenone-based photopolymerization initiator (2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one) "Omnirad 127 (trade name)" from IGM Resins.
(C-3) Acylphosphine oxide photopolymerization initiator (bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide) "Omnirad 819 (trade name)" manufactured by IGM Resins.

(D) Other ingredients:
(D-1) Acryloyl group-containing fluoropolyether water repellent "KY-1203 (product name)" manufactured by Shin-Etsu Chemical Co., Ltd. Solid content: 20% by mass.
(D-2) Acrylic silicone leveling agent "NSH8430HF (product name)" from Kusumoto Chemicals Co., Ltd. Solid content: 10% by mass.
(D-3) Fujifilm Wako Pure Chemical Industries, Ltd.'s azo compound-based thermal polymerization initiator "VE-073 (trade name)", dimethyl 1,1-azobis(1-cyclohexanecarboxylate).
(D-4) Propylene glycol monomethyl ether dispersion of silica fine particles "PGM-AC-2140Y (product name)" manufactured by Nissan Chemical Co., Ltd. Solid content 42% by mass, average particle size 15 nm.
(D-5)) Zirconium oxide methyl isobutyl ketone dispersion "ZRMIBK15WT%-P01 (product name)" by CIK Nanotech Co., Ltd. The amount of zirconium oxide in the dispersion is 15% by mass. The average particle size of zirconium oxide is 30 nm.

(E) Solvent:
(E-1) 1-Methoxy-2-propanol (referred to as "PGM" in the table)
(E-2) Methyl isobutyl ketone (referred to as "MIBK" in the table)

(L) Coating material for forming low refractive index layer:
(L-1) 250 parts by mass of the above (A1-1) (100 parts by mass in terms of solid content), 500 parts by mass of the above (B-1) (100 parts by mass in terms of solid content (hollow silica)), 7 parts by mass of the above (C-2), 36 parts by mass of the above (D-1) (7.2 parts by mass in terms of solid content), and 7600 parts by mass of the above (E-1) were mixed and stirred to obtain a coating material (L-1) for forming a low refractive index layer.In addition, in the table, all values are shown in terms of solid content, except for the solvent (above (E-1) 1-methoxy-2-propanol).

(L-2 to 8) Paints for forming low refractive index layers were obtained in the same manner as (L-1) above, except that the formulation of the paint for forming low refractive index layers was changed as shown in Table 1. Note that all values shown in the table are calculated as solids, except for the solvent (1-methoxy-2-propanol (E-1) above).

(L-9) A coating material for forming a low refractive index layer was obtained in the same manner as (L-1) above, except that the amount of (C-2) was changed to 5 parts by mass. Note that all values shown in the table are calculated as solids, except for the solvent (1-methoxy-2-propanol (E-1) above).

(P) Transparent resin film:
(P-1) A device equipped with a two-kind, three-layer multi-manifold type coextrusion T-die and a take-up machine equipped with a mechanism for pressing the molten film between a first mirror roll (a roll that holds the molten film and sends it to the next transfer roll) and a second mirror roll was used, and poly(meth)acrylamide "PLEXIMID TT50 (trade name)" from Evonik was continuously coextruded as both outer layers (α1 layer and α2 layer) of the two-kind, three-layer multilayer resin film, and aromatic polycarbonate "Calibur 301-4 (trade name)" from Sumika Styron Polycarbonate Co., Ltd. was continuously coextruded from the coextrusion T-die, and the α1 layer was supplied and fed between the rotating first mirror roll and second mirror roll so that the α1 layer was on the first mirror roll side, and pressed to obtain a transparent resin film having a total thickness of 170 μm, a layer thickness of 50 μm for the α1 layer, a layer thickness of 70 μm for the β layer, and a layer thickness of 50 μm for the α2 layer. The conditions were as follows: T-die temperature 300° C., first mirror roll temperature 130° C., second mirror roll temperature 120° C., and take-off speed 9.5 m/min.

Example 1
(1) Both sides of the above (P-1) were subjected to a corona discharge treatment. The wettability index of both sides was 64 mN/m.
(2) Next, using a film Mayer bar type coating device, the above (L-1) was applied onto the surface of the α1 layer side of the above (P-1) so that the thickness after curing would be 100 nm, forming a wet coating film. After that, the wet coating film was pre-dried by passing it through a drying oven set at an oven temperature of 60°C at a line speed such that the time required for passing from the entrance to the exit was 1 minute.
(3) Next, a high-pressure mercury lamp type ultraviolet ray irradiation device 6 and a mirror-finished metal roll 7 having a diameter of 25.4 cm are placed opposite each other, and a curing device (FIG. 8) equipped with a 365 filter (Eye Graphics Co., Ltd.'s "365 Filter (product name)") 8 is used, and the mirror-finished metal roll 7 is heated to 60°C, the lamp output is 80 W/cm, and the cumulative light amount calculated assuming that the 365 filter 8 is not used is 60 mJ/cm ^2. The laminate (web 9) having the above-mentioned wet coating film pre-dried on the surface of the α1 layer side of the above-mentioned (P-1) is treated so that the surface of the above-mentioned wet coating film side of the laminate (web 9) faces the ultraviolet ray irradiation device 6, to obtain a laminate film (coating film is B stage). The "cumulative light amount" in the table is the value calculated assuming that the 365 filter 8 is not used, assuming that the cumulative light amount of ultraviolet light in the low refractive index B stage coating film formation process is not used.
(4) The above tests (a) to (g) were carried out. The results are shown in Table 1.

Example 2
The same procedure as in Example 1 was carried out except that the 365 filter was not used in the ultraviolet irradiation step for forming the low refractive index B-stage coating film. The results are shown in Table 1.

Examples 3 to 9
The same procedure as in Example 1 was repeated, except that the coating material for forming the low refractive index layer was changed from the coating material (L-1) to the coating material shown in Table 1. The results are shown in Table 1.

The manufacturing method of the present invention made it possible to industrially stably produce a low refractive index B-stage coating film. The preferred manufacturing method of the present invention made it possible to industrially stably produce a low refractive index B-stage coating film with excellent three-dimensional moldability and web handling properties. After the low refractive index B-stage coating film was completely cured (to C-stage), the laminated film of the present invention had good anti-reflection function, transparency, and adhesion to the film substrate. Furthermore, it was considered that the anti-fouling properties were also good based on the water contact angle value.

2. Example of forming a coating film having three-dimensional formability:
Next, an example of an embodiment is disclosed in which a coating film having three-dimensional formability is provided on one side of a film substrate, and a low refractive index B-stage coating film of the present invention is provided on the surface of the coating film having three-dimensional formability.

(H) Coating material for forming a coating film having three-dimensional formability (referred to as "Coating material H" in the table):
(H-1) 117 parts by mass of the above (A1-3) (70 parts by mass in terms of solid content), 60 parts by mass of the above (A2-1) (30 parts by mass in terms of solid content), 1.5 parts by mass of the above (C-2), 2 parts by mass of the above (D-2) (0.2 parts by mass in terms of solid content), and 80 parts by mass of the above (E-2) were mixed and stirred to obtain a coating material (H-1) for forming a coating film having three-dimensional moldability. In addition, all values in the table are shown in terms of solid content, except for the solvent (the above (E-2) methyl isobutyl ketone).

(H-2) 155 parts by mass of the above (A1-2) (93 parts by mass in terms of solid content), 7 parts by mass of the above (A2-2), 7 parts by mass of the above (C-2), 2 parts by mass of the above (D-2) (0.2 parts by mass in terms of solid content), 0.02 parts by mass of the above (D-3), 333 parts by mass of the above (D-4) (140 parts by mass in terms of solid content), and 135 parts by mass of the above (E-2) were mixed and stirred to obtain a coating material for forming a coating film (H-2) having three-dimensional moldability. Note that all values shown in the table are in terms of solid content, except for the solvent (methyl isobutyl ketone (E-2) above).

(H-3) 155 parts by mass of the above (A1-2) (93 parts by mass in terms of solid content), 7 parts by mass of the above (A2-2), 7 parts by mass of the above (C-2), 2 parts by mass of the above (D-2) (0.2 parts by mass in terms of solid content), 0.02 parts by mass of the above (D-3), and 333 parts by mass of the above (D-5) (50 parts by mass in terms of solid content) were mixed and stirred to obtain a coating material for forming a coating film having three-dimensional moldability (H-3). Note that all values shown in the table are in terms of solid content.

Example 10
(1) Both sides of the above (P-1) were subjected to a corona discharge treatment. The wettability index of both sides was 64 mN/m.
(2) Next, the above (H-1) was applied onto the α1 layer side surface of the above (P-1) using a die-type coating device so as to have a thickness of 18 μm after curing to form a wet coating film. After that, the wet coating film was pre-dried by passing it through a drying oven whose oven temperature was set to 90° C. at a line speed such that the time required for passing from the entrance to the exit was 2 minutes.
(3) Next, using a curing device ( FIG. 8 ) in which a high-pressure mercury lamp type ultraviolet irradiation device 6 and a mirror-finished metal roll 7 having a diameter of 25.4 cm were placed opposite each other and equipped with a 365 filter (I-Graphics Co., Ltd.'s "365 Filter (product name)") 8, the laminate (web 9) having the above pre-dried wet coating film on the surface of the α1 layer side of (P-1) was treated under conditions of a mirror-finished metal roll 7 temperature of 60° C., a lamp output of 160 W/cm, and an accumulated light amount of 400 mJ/cm ² calculated assuming that the 365 filter 8 was not used, with the surface of the laminate (web 9) with the wet coating film facing the ultraviolet irradiation device 6, and cured to a B-stage state.
(4) Next, the above-mentioned (L-1) was applied to the surface of the coating film (B-stage coating film) having three-dimensional formability formed on the surface of the α1 layer side of the above-mentioned (P-1) using a film Mayer bar type coating device so as to have a thickness of 100 nm after curing to form a wet coating film, and then the wet coating film was pre-dried by passing it through a drying oven set at an oven temperature of 60°C at a line speed such that the time required for passing from the entrance to the exit was 1 minute.
(5) Next, a curing device (FIG. 8) was used in which a high-pressure mercury lamp type ultraviolet ray irradiation device 6 and a mirror-finished metal roll 7 having a diameter of 25.4 cm were placed opposite each other, and equipped with a 365 filter (Eye Graphics Co., Ltd.'s "365 Filter (product name)") 8. The above pre-dried wet coating film was treated under the conditions of a mirror-finished metal roll 7 temperature of 60° C., a lamp output of 80 W/cm, and an accumulated light amount of 150 mJ/cm ² calculated assuming that the 365 filter 8 was not used, so that the surface of the laminate (web 9) on which the wet coating film was placed was the ultraviolet ray irradiation device 6 side, to obtain a laminate film (coating film was in B stage). The "accumulated light amount" in the table is the value calculated by assuming that the 365 filter 8 was not used, based on the accumulated light amount of ultraviolet light in the low refractive index B stage coating film formation process.
(6) The above tests (a) to (n) were carried out. The results are shown in Table 2.

Example 11
The same procedure as in Example 10 was repeated, except that the coating material for forming the low refractive index layer (L-9) was used instead of the coating material (L-1). The results are shown in Table 2.

Example 12
(1) Both sides of the above (P-1) were subjected to a corona discharge treatment. The wettability index of both sides was 64 mN/m.
(2) Next, the above (H-2) was applied onto the α1 layer side of the above (P-1) using a die-type coating device so that the thickness after complete curing (C stage) would be 18 μm, forming a wet coating film.
(3) Next, the wet coating film was dried and cured to a B-stage state by passing it through a drying furnace set at an internal temperature of 130° C. at a line speed such that the time required for passing from the entrance to the exit was 6 minutes.
(4) The web emerging from the drying oven was handled while being held by a chill roll set at a temperature of 25° C., and then wound up.
(5) Next, the above (L-1) was applied to the easily peelable surface of a 50 μm-thick biaxially oriented polyethylene terephthalate resin film that had been treated to be easily peelable on one side using a film Mayer bar type coating device to give a thickness of 100 nm after curing to form a wet coating film. After that, the wet coating film was pre-dried by passing it through a drying oven set at an oven temperature of 60° C. at a line speed such that the time required for passing from the entrance to the exit was 1 minute.
(6) Next, a curing device (FIG. 8) was used in which a high-pressure mercury lamp type ultraviolet ray irradiation device 6 and a mirror-finished metal roll 7 having a diameter of 25.4 cm were placed opposite each other, and equipped with a 365 filter ("365 Filter (product name)" by Eye Graphics Co., Ltd.) 8, and the above pre-dried wet coating film was treated under the conditions of a mirror-finished metal roll 7 temperature of 60° C., a lamp output of 80 W/cm, and an accumulated light amount of 150 mJ/cm ² calculated assuming that the 365 filter 8 was not used, so that the surface of the laminate (web 9) on which the wet coating film was placed was on the ultraviolet ray irradiation device 6 side, to form a low refractive index B stage coating film. The "accumulated light amount" in the table is the value calculated for the accumulated light amount of ultraviolet light in the low refractive index B stage coating film formation process assuming that the 365 filter 8 was not used.
(7) Next, the low refractive index B-stage coating film formed in the above step (6) was transferred onto the surface of the coating film (B-stage coating film) having three-dimensional formability formed on the surface of the α1 layer side of the above (P-1) by a thermal lamination method to obtain a laminated film (the coating film is B-stage).
(8) The above tests (a) to (n) were carried out. The results are shown in Table 2.

Example 13
The same procedure as in Example 12 was repeated, except that the coating material for forming a coating film having three-dimensional formability was used instead of the coating material (H-2) (H-3). The results are shown in Table 2.

The manufacturing method of the present invention allows for the industrially stable production of low refractive index B-stage coating films. The preferred manufacturing method of the present invention allows for the industrially stable production of low refractive index B-stage coating films with excellent three-dimensional formability and web handling properties. After the low refractive index B-stage coating film was completely cured (to C-stage), the laminate film of the present invention had good anti-reflection function, transparency, adhesion to the film substrate, and anti-soiling properties. The preferred laminate film of the present invention also had good scratch resistance.

Examples of low refractive index B-stage coating embodiments of the present invention are summarized as follows.
[1]
A B-stage coating film for forming a low refractive index layer,
(A) an active energy ray-curable resin,
(B) low refractive index particles; and (C) a coating material containing a photopolymerization initiator;
wherein the component (C) photopolymerization initiator has an absorption peak in the wavelength range of 220 to 280 nm, the peak top value of which is the maximum absorbance; the wavelength at which the absorbance is half the maximum absorbance on the longer wavelength side than the peak top of the absorption peak is 290 nm or less; and the absorbance is half or less of the maximum absorbance at any wavelength in the wavelength range of 290 to 400 nm;
The above B-stage coating film for forming a low refractive index layer.
[2]
The B-stage coating film for forming a low refractive index layer according to item [1], wherein the component (C) photopolymerization initiator has an absorbance of 1/10 to 1/100 of the maximum absorbance at a wavelength of 300 nm.
[3]
The component (C) photopolymerization initiator is one or more selected from the group consisting of 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, and a 100:0 to 45:55 (mass ratio) mixture of 1-hydroxycyclohexyl-phenyl-ketone and benzophenone; the B-stage coating film for forming a low refractive index layer according to item [1] or [2].
[4]
The B-stage coating film for forming a low refractive index layer according to any one of items [1] to [3], wherein the component (A) active energy ray curable resin contains (A1) urethane (meth)acrylate.
[5]
The B-stage coating film for forming a low refractive index layer according to any one of items [1] to [4], wherein the component (A1) urethane (meth)acrylate has a polystyrene-equivalent number average molecular weight (Mn) of 1,000 or more, as determined from a differential molecular weight distribution curve measured by gel permeation chromatography.
[6]
The B-stage coating film for forming a low refractive index layer according to any one of items [1] to [5], wherein the number of (meth)acryloyl groups in the urethane (meth)acrylate of component (A1) is 2 to 20 per 1,000 of polystyrene-equivalent number average molecular weight (Mn) calculated from a differential molecular weight distribution curve measured by gel permeation chromatography.
[7]
A laminate film, comprising a film substrate and a B-stage coating film for forming a low refractive index layer according to any one of items [1] to [6] on at least one surface of the film substrate, the B-stage coating film forming a surface of the laminate film.
[8]
A laminate film comprising a layer of a coating film having three-dimensional formability on at least one surface of a film substrate, and a B-stage coating film for forming a low refractive index layer according to any one of items [1] to [6], in that order, and the B-stage coating film forms a surface.
[9]
A molded article having a low refractive index layer formed using the B-stage coating film for forming a low refractive index layer according to any one of items [1] to [6].
[10]
A molded article molded using the laminate film according to item [7] or [8].
[11]
An article comprising the molded article according to item [9] or [10].

1 is a graph showing the relationship between wavelength and specific energy intensity when monochromatized using a 365 filter. 1 is a wavelength-absorbance curve of an acetonitrile solution of a photopolymerization initiator (C-1) used in an example. 1 is a wavelength-absorbance curve of an acetonitrile solution of a photopolymerization initiator (C-2) used in an example. 1 is a wavelength-absorbance curve of an acetonitrile solution of a photopolymerization initiator (C-3) used in an example. 1 is a GPC curve of the urethane (meth)acrylate (A1-1) used in the examples. FIG. 1 is a conceptual diagram illustrating vacuum forming. FIG. 2A is a front view and FIG. 2B is a plan view of a mold used in the examples. FIG. 2 is a conceptual diagram of an ultraviolet irradiation device used in the examples.

Reference Signs List 1: Laminated film 2: Heating device 3: Mold 4: Space between laminated film and mold 5: Molded body 6: Ultraviolet ray irradiation device 7: Mirror-finished metal roll 8: 365 filter 9: Web

Claims (15)

A method for producing a B-stage coating film capable of forming a low refractive index layer, comprising the steps of:
(1) On the surface of the film substrate,
(A) an active energy ray-curable resin,
(B) forming a wet coating film using a coating material containing low refractive index particles and (C) a photopolymerization initiator (excluding coating materials containing two or more types of photopolymerization initiators that absorb ultraviolet light having different wavelengths and generate radicals); and
(2) a step of irradiating the wet coating film with active energy rays to bring the wet coating film into a B-stage state;
Here, the active energy rays are monochromatized using a filter so as not to include any wavelength having an absorbance equal to or greater than half the maximum absorbance of the component (C) photopolymerization initiator;
The filter is a 365 filter;
The component (C) photopolymerization initiator has an absorbance of 1/10 to 1/100 of the maximum absorbance at a wavelength of 300 nm;
The above manufacturing method:
Here, the maximum absorbance of the component (C) photopolymerization initiator means the maximum absorbance in the wavelength range of 220 to 400 nm on the wavelength-absorbance curve of the component (C) photopolymerization initiator.
A method for producing a B-stage coating film capable of forming a low refractive index layer, comprising the steps of:
(1) On the surface of the film substrate,
(A) an active energy ray-curable resin,
(B) forming a wet coating film using a coating material containing low refractive index particles and (C) a photopolymerization initiator; and
(2) a step of irradiating the wet coating film with active energy rays to bring the wet coating film into a B-stage state;
Here, the active energy rays are monochromatized using a filter so as not to include any wavelength having an absorbance equal to or greater than half the maximum absorbance of the component (C) photopolymerization initiator;
The filter is a 365 filter;
The component (C) photopolymerization initiator is
having an absorption peak with a peak top value of maximum absorbance in the wavelength range of 220 to 280 nm;
the wavelength at which the absorbance reaches half the maximum absorbance on the longer wavelength side than the peak top of the absorption peak is 290 nm or less;
The absorbance at any wavelength in the range of 290 to 400 nm is half or less of the maximum absorbance;
The above manufacturing method:
Here, the maximum absorbance of the component (C) photopolymerization initiator means the maximum absorbance in the wavelength range of 220 to 400 nm on the wavelength-absorbance curve of the component (C) photopolymerization initiator.
the filter is a 365 filter;
The component (C) photopolymerization initiator has an absorbance of 1/10 to 1/100 of the maximum absorbance at a wavelength of 300 nm;
The method according to claim 2 .
the filter is a 365 filter;
The component (C) photopolymerization initiator is at least one selected from the group consisting of 1-hydroxy-cyclohexyl-phenyl-ketone and 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one;
The manufacturing method according to any one of claims 1 to 3 .
The coating material comprises the component (A) 100 parts by mass of an active energy ray-curable resin,
The method according to any one of claims 1 to 4 , comprising: 10 to 300 parts by mass of the component (B) low refractive index particles; and 1 to 20 parts by mass of the component (C) photopolymerization initiator.
The method according to any one of claims 1 to 5 , wherein the component (A) active energy ray curable resin contains (A1) urethane (meth)acrylate.
The method according to claim 6 , wherein the component (A1), urethane (meth)acrylate, has a polystyrene-equivalent number average molecular weight (Mn) of 1,000 or more as determined from a differential molecular weight distribution curve measured by gel permeation chromatography.
The method according to claim 6 or 7, wherein the number of (meth)acryloyl groups in the urethane (meth)acrylate of the component (A1) is 2 to 20 per 1,000 of polystyrene-equivalent number average molecular weight (Mn) determined from a differential molecular weight distribution curve measured by gel permeation chromatography.
The method according to any one of claims 6 to 8 , wherein the component (A1) urethane (meth)acrylate comprises a polyfunctional urethane (meth)acrylate.
A method for producing a laminated film, comprising the steps of:
A step of forming a B-stage coating film capable of forming a low refractive index layer on at least one surface of a film substrate by the production method according to any one of claims 1 to 9 ;
The above manufacturing method.
A method for producing a laminated film, comprising the steps of:
A step of forming a coating film having three-dimensional formability on at least one surface of a film substrate; and
A step of forming a B-stage coating film capable of forming a low refractive index layer by the production method according to any one of claims 1 to 9 on the surface of the coating film having three-dimensional formability formed in the above step;
The above manufacturing method comprising:
Here, the coating film having three-dimensional formability is a B-stage coating film or a urethane-based curable resin coating film,
The urethane-based curable resin coating film is a coating film formed using a curable resin composition containing a polyol compound, a curable resin having a hydroxyl group, and a compound having two or more isocyanate groups in one molecule.
A method for producing the laminated film according to claim 11 ,
The step of forming a coating film having three-dimensional formability includes:
(11) a sub-step of forming a wet coating film on the surface of the film substrate using a coating material containing (a1) an active energy ray curable resin and (b1) a photopolymerization initiator; and
(12) a sub-step of irradiating the wet coating film with active energy rays to bring the wet coating film into a B-stage state;
Here, the active energy rays are monochromatized using a filter so as not to include a wavelength that is equal to or greater than half of the maximum absorbance of the component (b1) photopolymerization initiator;
A process for producing a B-stage coating film as the coating film having the three-dimensional formability,
A method for producing the laminated film.
The method for producing a laminated film according to claim 12 , wherein the active energy rays are monochromatized using a filter so as to include a wavelength having an absorbance that is 1/10 to 1/100 of the maximum absorbance of the component (b1) photopolymerization initiator.
A method for producing the laminated film according to claim 11 ,
The step of forming a coating film having three-dimensional formability includes:
(21) a sub-step of forming a wet coating film on the surface of the film substrate using a B-stage coating film-forming paint;
(22) a sub-step of drying and curing the wet coating film formed in the above step (21) at a temperature of 80 to 160° C. for 1 to 20 minutes to thereby produce a B-stage coating; and
(23) a sub-step of cooling the temperature of the coating film treated in the above step (22) to 60° C. or less;
The coating material for forming a B-stage coating film contains (a2) an active energy ray curable resin, (b2) a photopolymerization initiator, and (c2) a thermal polymerization initiator.
A process for producing a B-stage coating film as the coating film having the three-dimensional formability,
A method for producing the laminated film.
The B-stage coating material for forming a coating film is
100 parts by mass of the component (a2) active energy ray curable resin,
0.01 to 20 parts by mass of the component (b2) photopolymerization initiator; and
The component (c2) is 0.001 to 1 part by mass of a thermal polymerization initiator;
The method for producing the laminated film according to claim 14 .