JP2021177212A - Low refractive index b stage coated film, laminated film, three-dimensional compact, and method for manufacturing these - Google Patents

Abstract

To provide a low refractive index B stage coated film that is excellent in three-dimensional molding ability (unlikelihood of occurrence of a defective phenomenon including cracks and whitening when applied with a three-dimensional shape) and web handling ability (unlikelihood of occurrence of scratches and poor appearance due to contact of a coated film with a transfer roll or the like during web handling), and a method for manufacturing the same.SOLUTION: There is provided a method for manufacturing a B stage coated film that can form a low refractive index layer, and the manufacturing method includes: (1) a step of forming a wet coated film on a surface of a film substrate by using a paint including (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 coated film with an active energy ray to bring the wet coated film into a B stage state. The active energy ray is monochromatized by using a filter so as not to include a wavelength at which absorbance becomes half or more than half of the maximum absorbance of the photopolymerization initiator.SELECTED DRAWING: Figure 8

Description

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

In recent years, from the viewpoint of design, molded bodies such as display face plates of image display devices such as car navigation systems and digital signage, and instrument panels of automobiles are often given a curved surface shape and have a three-dimensional shape. It has become. In addition, since these molded bodies are used in places where they are exposed to direct sunlight, they have the inconvenience of eye fatigue due to the reflected light when they are exposed to direct sunlight, and the contrast is reduced to make the image clearer. In order to solve the inconvenience of being invisible, it is often practiced to form a low refraction layer on the surface to provide an antireflection function.

As a method of forming a low refractive index layer on the surface of a molded body having a three-dimensional shape, a substrate having a three-dimensional shape is molded using a highly transparent resin such as an acrylic resin or a polycarbonate resin, and then the substrate has a three-dimensional shape. Methods of forming a film of low refractive index material by methods such as sputtering, vacuum deposition, and chemical vapor deposition; and methods such as dip coating, spray coating, spin coating, and air knife coating, A method of applying a coating for forming a low refractive index layer and curing it; is widely adopted. On the other hand, these methods have the disadvantage that the productivity is insufficient because the low refractive index layer is formed for each substrate. Therefore, a B-stage coating film is formed by applying a paint on the surface of the thermoplastic resin sheet with high productivity by a roll-to-roll method such as roll coating, gravure coating, reverse coating, and die coating. A method of completely curing the B-stage coating film after shaping the obtained laminated film into a predetermined shape by a method such as hot press molding; the laminated film is inserted into a molding mold for injection molding, and the laminated film is formed. Is heated and softened to form a predetermined shape, a desired thermoplastic resin is injected into the molding mold, and then the B-stage coating film is completely cured; (for example, Patent Documents 1 and 2). A low refractive index layer is formed on the surface, and attempts are being made to apply it to the production of a molded product having an antireflection function.

Special Table 2012-521476 Japanese Unexamined Patent Publication No. 2016-221922

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. Further problems of the present invention are three-dimensional moldability (difficulty of defective phenomena such as cracking and whitening when a three-dimensional shape is given) and web handleability (during web handling, the coating film is transferred to a roll). It is an object of the present invention to provide a low refractive index B-stage coating film having excellent resistance to scratches and poor appearance due to contact with the like, and a method for producing the same. Another subject of the present invention is low refraction, which is excellent in three-dimensional moldability and web handling in the B stage, and excellent in surface hardness, scratch resistance, and chemical resistance after complete curing (in the C stage). It is an object of the present invention to provide a coating film having a refractive index, a laminated film having the coating film, the coating film or a molded product containing the laminated film, and a method for producing the same.

As a result of diligent research, the present inventor has found that the above problems can be achieved by a specific manufacturing method.

Various aspects of the present invention for solving the above problems are as follows [1].
A method for producing a B-stage coating film capable of forming a low refractive index layer.
A wet coating film is formed on the surface of a film substrate using a paint containing (A) an active energy ray-curable resin, (B) low refractive index particles, and (C) a photopolymerization initiator. Process; and
(2) The wet coating film is irradiated with active energy rays to bring it into a B stage state;
Here, the active energy ray is monochromatic using a filter so as not to include a wavelength having an absorbance of 1/2 or more of the maximum absorbance of the component (C) photopolymerization initiator; ..
[2].
The active energy ray is monochromatic using a filter so as to include a wavelength having an absorbance of 1/10 to 1/100 of the maximum absorbance of the component (C) photopolymerization initiator; [1]. The manufacturing method described in the section.
[3].
The filter is a 365 filter; the photopolymerization initiator of the component (C) has an absorption peak having a peak top value of maximum absorbance in the wavelength range of 220 to 280 nm; a wavelength longer than the peak top of the absorption peak. The wavelength at which the absorbance on the side is 1/2 of the maximum absorbance is 290 nm or less; the absorbance at any wavelength in the wavelength range of 290 to 400 nm is 1/2 or less of the maximum absorbance; item [1] or [2]. ] The manufacturing method described in the section.
[4].
The filter is a 365 filter; the photopolymerization initiator of the component (C) has an absorbance of 1/10 to 1/100 of the maximum absorbance at a wavelength of 300 nm; any one of items [1] to [3]. The manufacturing method described in the section.
[5].
The filter is a 365 filter; the component (C) photopolymerization initiator is 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hirodoxy-1- {4- [4- (2-hydroxy-2-methyl-). Propionyl) -benzyl] phenyl} -2-methyl-propane-1-one, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-Hydroxy-2-methyl-1-propane-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, and 1-hydroxycyclohexyl-phenylketone One or more selected from the group consisting of a mixture of 100: 0 to 45:55 (mass ratio) of benzophenone and benzophenone; the production method according to any one of [1] to [4].
[6].
The production method according to any one of [1] to [5], wherein the component (A) active energy ray-curable resin contains (A1) urethane (meta) acrylate.
[7].
The polystyrene-equivalent number average molecular weight (Mn) obtained from the differential molecular weight distribution curve measured by gel permeation chromatography of the above component (A1) urethane (meth) acrylate is 1000 or more; any of the items [1] to [6]. The manufacturing method according to item 1.
[8].
The number of (meth) acryloyl groups contained in the above component (A1) urethane (meth) acrylate is 2 to 20 per 1000 polystyrene-equivalent number average molecular weight (Mn) obtained from the differential molecular weight distribution curve measured by gel permeation chromatography. The production method according to any one of items [1] to [7].
[9].
A B-stage coating method for producing a laminated film, wherein a low refractive index layer can be formed on at least one surface of a film substrate by the production method according to any one of [1] to [8]. The above-mentioned production method, which comprises a step of forming a film;
[10].
A method for producing a laminated film, which is a step of forming a coating film having three-dimensional moldability on at least one surface of a film base material; and a step of forming a coating film having three-dimensional moldability on the surface of the coating film formed in the above step. The above-mentioned production method comprising the 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 [1] to [8] above.

According to the production method of the present invention, a low refractive index B stage coating film can be industrially stably produced. According to the preferred production method of the present invention, a low refractive index B-stage coating film having excellent three-dimensional moldability and web handleability can be industrially stably produced. The low refractive index B-stage coating film of the present invention is excellent in three-dimensional moldability and web handleability. The preferred low refractive index B-stage coating film of the present invention has excellent three-dimensional moldability and web handling in the B stage, and has surface hardness, scratch resistance, and chemical resistance after complete curing (in the C stage). Excellent. Therefore, the laminated film of the present invention having 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 a molded body having a three-dimensional shape / three-dimensional shape, particularly car navigation and digital. It can be suitably used for imparting an antireflection function to a display face plate of an image display device such as a signage, and a molded body used in a place exposed to direct sunlight such as an instrument panel of an automobile. Therefore, a molded product formed by using 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 has a good antireflection function and has a surface hardness. It has excellent scratch resistance and chemical resistance, and has a good surface appearance (no defective phenomena such as cracking and whitening).

In the present specification, the term "resin" is used as a term including a resin mixture containing two or more kinds of resins and a resin composition containing components other than the resin. As used herein, the term "film" is used interchangeably or interchangeably with "sheet". As used herein, the terms "film" and "sheet" are used for those that can be industrially rolled up. The term "board" is used for things that cannot be industrially rolled into rolls. Further, in the present specification, laminating a certain layer and another layer in order means directly laminating those layers and interposing one or more other layers such as an anchor coat between the layers. Includes both stacking.

In the present specification, the term "B stage" has the meaning defined in JIS K6800-1985 for a thermosetting resin, that is, "an intermediate state of curing of a thermosetting resin. The resin in this state softens when heated. , It swells when it comes in contact with some kind of solvent, but it does not completely melt or dissolve. " Regarding the active energy ray-curable resin, "The intermediate state of curing of the active energy ray-curable resin. The resin in this state softens when heated and swells when it comes into contact with a certain solvent, but it melts and dissolves completely. It is used to mean "there is no."

In the present specification, the term "C stage" refers to "the final state of the curing reaction of the curable resin. The resin in this state is insoluble and insoluble" for both the thermosetting resin and the active energy ray-curable resin. The curable resin in the completely cured coating film is in this state. ”

In the present specification, the term "greater than or equal to" relating to a numerical range is used to mean a certain numerical value or a certain numerical value or more. For example, 20% or more means 20% or more than 20%. The term "less than or equal to" related to a numerical range is used to mean a certain numerical value or less than a certain numerical value. For example, 20% or less means 20% or less than 20%. In addition, the symbol "~" related to the numerical range is used to mean a certain numerical value, more than a certain numerical value and less than another certain numerical value, or another certain numerical value. Here, it is assumed that some other numerical value is larger than a certain numerical value. For example, 10-90% means 10%, greater than 10% and less than 90%, or 90%. Further, the upper limit and the lower limit of the numerical range can be arbitrarily combined, and the embodiment in which the arbitrary combination can be read can be read. For example, "usually 10% or more, preferably 20% or more. On the other hand, usually 40% or less, preferably 30% or less." Or "usually 10 to 40%, preferably 20." From the description "~ 30%", it can be read that the numerical range of the certain property is 10 to 40%, 20 to 30%, 10 to 30%, or 20 to 40% in one embodiment. do.

Except in the examples, or unless otherwise specified, all numbers used herein and in the claims should be understood as being modified by the term "about". Without attempting to limit the application of the doctrine of equivalents to the claims, each number should be interpreted in the light of significant figures and by applying conventional rounding techniques.

1. 1. Method for manufacturing low refractive index B stage coating film:
The production method of the present invention is a method for producing a B-stage coating film capable of forming a low refractive index layer, wherein (1) an active energy ray-curable resin is placed on the surface of a film substrate. A step of forming a wet coating film using (B) low refractive index particles and (C) a coating material containing a photopolymerization initiator; and (2) the wet coating film is irradiated with active energy rays to perform a B stage. Including the step of bringing into a state; where the active energy ray is usually 1/2 or more, preferably 1/3 or more, more preferably 1/3 or more of the maximum absorbance of the component (C) photopolymerization initiator using a filter. Is a single color so as not to include a wavelength having an absorbance of 1/4 or more, more preferably 1/5 or more, still more preferably 1/6 or more, even more preferably 1/7 or more, and most preferably 1/8 or more. It is the above-mentioned manufacturing method.

The production method of the present invention is, in one of the preferred embodiments, a method for producing a B-stage coating film capable of forming a low refractive index layer, wherein (1) (A) is placed on the surface of the film substrate. ) A step of forming a wet coating using a paint containing an active energy ray-curable resin, (B) low refractive index particles, and (C) a photopolymerization initiator; and (2) activity on the wet coating. Including the step of irradiating with energy rays to bring them into a B stage state; where the active energy rays are preferably at least 1/2 of the maximum absorbance of the component (C) photopolymerization initiator using a filter. Is 1/3 or more, more preferably 1/4 or more, still more preferably 1/5 or more, still more preferably 1/6 or more, still more preferably 1/7 or more, and most preferably 1/8 or more. Monochromatic to include wavelengths that usually have an absorbance of 1/1 to 1/100, preferably 1/15 to 1/70, more preferably 1/20 to 1/50. The above manufacturing method may be used.

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

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

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

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

Although it is not intended to be bound by theory, if only the irradiation amount is made very low, the output of the light source of the active energy ray may be lowered, the distance between the light source and the wet coating film may be increased, or the above steps ( A method of increasing the line speed in 2) is also conceivable. However, from the viewpoint of stable operation of the light source, the output should be at least a certain level, and from the viewpoint of handleability of the manufacturing apparatus, the distance between the light source and the wet coating film may be increased. There is a limit to the method of increasing the line speed in the above step (2). Therefore, in the production method of the present invention, using a filter, the maximum absorbance of the above component (C) photopolymerization initiator is usually 1/2 or more, preferably 1/3 or more, more preferably 1/4 or more, and further. The active energy rays are monochromatic so as not to include a wavelength having an absorbance of preferably 1/5 or more, more preferably 1/6 or more, even more preferably 1/7 or more, and most preferably 1/8 or more. By irradiating, the irradiation amount is made very low to keep the curing of the wet coating film in the B stage state, and industrially stable production is achieved at the same time. Further, in one of the preferred embodiments of the production method of the present invention, the maximum absorbance of the component (C) photopolymerization initiator is usually 1/1 to 1/100, preferably 1/15 to 1/70, more preferably. By including a wavelength having an absorbance of 1/20 to 1/50, the wet coating film can be easily cured in the 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 of the wavelength-absorbance curve of the component (C) photopolymerization initiator.

The fact that the active energy ray does not include the active energy ray of a certain wavelength means that the specific energy intensity of the active energy ray at the wavelength is usually less than 5%, preferably 2% or less, more preferably 1% or less, still more preferably 0. It means that it is 5.5% or less, most preferably 0.1% or less.

The inclusion of the active energy ray of a certain wavelength means that the specific energy intensity of the active energy ray at the 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 when the energy intensity of the wavelength that the filter best transmits is 100%. For example, when the active energy ray is monochromatic using a 365 filter, the energy intensity (unit:%) at the wavelength when the energy intensity at the wavelength of 365 nm of the monochromatic active energy ray is 100%. be. FIG. 1 is a graph showing the relationship between the wavelength and the specific energy intensity when the ultraviolet rays generated from the high-pressure mercury lamp type ultraviolet irradiation device used in the example are monochromaticized by the 365 filter also used in the example. ..

The wavelength-absorbance curve of the component (C) photopolymerization initiator can be obtained by preparing a photopolymerization initiator solution having an appropriate concentration and measuring this using an arbitrary spectrophotometer. The wavelength-absorbance curve of the above component (C) photopolymerization initiator can be obtained by, for example, dissolving the photopolymerization initiator in acetonitrile for spectroscopic analysis to prepare a photopolymerization initiator acetonitrile solution having an appropriate concentration, and then using a spectrophotometer. It can be obtained by using a quartz glass cell (optical path length 10 mm), measuring 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 kinds of photopolymerization initiators is used as the above component (C) photopolymerization initiator, a wavelength-absorbance curve of the mixture is prepared and used. As the spectrophotometer, for example, a spectrophotometer "SolidSpec-3700 (trade name)" manufactured by Shimadzu Corporation can be used.

A case where the active energy ray is monochromatic using a 365 filter will be described. When monochromaticizing the active energy rays using a 365 filter, the specific energy intensity becomes almost zero (specific energy intensity <0.1%) at a wavelength of 280 nm or less, and less than 2% at a wavelength of more than 280 nm and 285 nm or less. It can be read from FIG. 1 that it is less than 5% at a wavelength of more than 285 nm and less than 290 nm. Therefore, when monochromaticizing the active energy rays using a 365 filter, the maximum absorbance of the photopolymerization initiator is usually 1/2 or more, preferably 1/3 or more, more preferably 1/4 or more, still more preferably 1. From the viewpoint of not including a wavelength having an absorbance of / 5, more preferably 1/6 or more, even more preferably 1/7 or more, most preferably 1/8 or more, and completely curing the B stage coating film. From the viewpoint of curability when (to the C stage), the absorbance peak having the peak top value of the maximum absorbance is in the wavelength range of 220 to 280 nm; the absorbance peaks on the longer wavelength side than the peak top of the absorption peak. The wavelength that is 1 / n of the top value (= maximum absorbance) is usually 290 nm or less, preferably 285 nm or less, more preferably 280 nm or less; the absorbance is 1 of the maximum absorbance at any wavelength in the wavelength range of 290 to 400 nm. It is preferable to use a photopolymerization initiator having an / n or less as the component (C). Here, n is a natural number of 2 to 8, and is usually 2, preferably 3, more preferably 4, still more preferably 5, even more preferably 6, even more preferably 7, and most preferably 8.

As the component (C) photopolymerization initiator, the specific energy intensity of the active energy ray is usually 5% or more, preferably 10% or more, more preferably 15% or more, and usually 100% or less, preferably 50. In the wavelength range of% or less, more preferably 30% or less, the maximum absorbance is usually 1/10 to 1/100, preferably 1/15 to 1/70, more preferably 1/20 to 1/50. It is preferable to use the one having. It is possible to easily achieve both the curing of the wet coating film in the B stage state and the curing of the wet coating film in the B stage state.

It can be seen from FIG. 1 that when monochromatic using a 365 filter, the specific energy intensity is, for example, 10 to 22% at a wavelength of 295 to 320 nm. Therefore, when monochromatic using a 365 filter, the maximum absorbance is usually 1/1 to 1/100, preferably 1/15 to 1/70, more preferably 1/20 to 1 at a wavelength of 295 to 320 nm. A photopolymerization initiator having a weak absorbance of / 50 can be said to be preferable as the above component (C).

It can be seen from FIG. 1 that the specific energy intensity is 17% at a wavelength of 300 nm when monochromatic using a 365 filter. Therefore, when monochromatic using a 365 filter, the maximum absorbance is usually 1/1 to 1/100, preferably 1/15 to 1/70, more preferably 1/20 to 1/50 at a wavelength of 300 nm. It can be said that a photopolymerization initiator having a weak absorbance of 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. On the longer wavelength side than the peak top, the absorbance is 254 nm, which is 1/2 of the peak top value, 258 nm, which is 1/3, 260 nm, which is 1/4, and 1/5. It can be read from FIG. 2 that 262 nm, 1/6 is 264 nm, 1/7 is 266 nm, and 1/8 is 269 nm.

When the photopolymerization initiator (C-1) is used as the component (C) photopolymerization initiator, in the step (2), if a 365 filter is used as the filter to monochromatic the white active energy ray, Since the active energy rays having a wavelength of 280 nm or less are almost completely shielded (specific energy intensity <0.1%), "the above active energy rays are the maximum of the above component (C) photopolymerization initiator using a filter. It is monochromatic so as not to include a wavelength having an absorbance of 1/8 or more of the absorbance. " Further, the above component (C-1) has a slight absorbance (1/34 of the maximum absorbance at a wavelength of 300 nm) even in the vicinity of a wavelength of 300 nm, and as described above, when monochromatic using a 365 filter, the wavelength is 295 to 320 nm. Since the specific energy intensity of the wet coating film is 10 to 22%, it is possible to easily achieve both the curing of the wet coating film in the B stage state and the curing of the wet coating film in the 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. On the longer wavelength side than the peak top, the absorbance is 271 nm, which is 1/2 of the peak top value, 276 nm, which is 1/3, 279 nm, which is 1/4, and 1/5. It can be read from FIG. 3 that 281 nm and 1/6 are 283 nm, 1/7 is 285 nm, and 1/8 is 286 nm.

When the photopolymerization initiator (C-2) is used as the component (C) photopolymerization initiator, if the white active energy ray is monochromatic using a 365 filter in the step (2), the wavelength is 280 nm or less. Active energy rays with a wavelength of more than 280 nm and 285 nm or less are almost completely shielded with a specific energy intensity of less than 2%, and active energy rays with a wavelength of more than 285 nm and 290 nm or less are almost completely shielded with a specific energy intensity of less than 5%. Therefore, "the active energy ray is monochromatic using a filter so as not to include a wavelength having an absorbance of 1/8 or more of the maximum absorbance of the component (C) photopolymerization initiator". Can be done. Further, the above component (C-2) has a slight absorbance (1/41 of the maximum absorbance at a wavelength of 300 nm) even in the vicinity of 300 nm, and as described above, when monochromatic using a 365 filter, the wavelength is 295 to 320 nm. Since the specific energy strength is 10 to 22%, it is possible to easily achieve both the curing of the wet coating film in the B stage state and the curing of the wet coating film in the 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 substantially monotonously in the wavelength range of 220 to 400 nm, and reaches the maximum absorbance at a wavelength of 220 nm. It also has a broad absorption peak at a wavelength of 289 nm and a shoulder absorption peak at a wavelength of 233 nm. It can be read from FIG. 4 that the absorbance is 249 nm when it becomes 1/2 of the maximum absorbance, 305 nm when it becomes 1/3, and 316 nm when it becomes 1/4.

When the photopolymerization initiator (C-3) is used as the component (C) photopolymerization initiator, in the step (2), if a 365 filter is used as the filter to monochromatic the white active energy ray, Since the active energy rays having a wavelength of 280 nm or less are almost completely shielded (specific energy intensity <0.1%), "the above active energy rays are the maximum of the above component (B) photopolymerization initiator using a filter. It is monochromatic so as not to include a wavelength having an absorbance of 1/2 or more of the absorbance. " On the other hand, the above-mentioned component (C-3) has a considerable absorbance (12.8 of the maximum absorbance at a wavelength of 300 nm) even in the vicinity of 300 nm, and a 365 filter is used as the above-mentioned filter in the above-mentioned step (2). Even if the white active energy rays are monochromatic, it can be said that "the wavelength having an absorbance of 1/3 or more of the maximum absorbance of the photopolymerization initiator of the above component (B) is included".

Examples of the light source of the active energy ray include a high-pressure mercury lamp and a metal halide lamp.

The irradiation amount of the active energy rays is determined from the viewpoint of stably performing the step (2), curing the wet coating film in the B stage state, and keeping the curing of the wet coating film in the B stage state. It is appropriately selected and determined in consideration of the number of polymerizable functional groups of the component (A) active energy ray-curable resin, the type and blending amount of the component (C) photopolymerization initiator, and the like. ^{The irradiation amount of the above active energy rays is usually 1 to 1000 mJ / cm 2} when converted to the irradiation amount when the filter is not used (when the irradiation amount is measured or calculated without using the filter). , It may be preferably 20 to 600 mJ / cm ^{2 and} more preferably 30 to 200 mJ / cm ² .

After the above step (2), an aging process may be performed. The characteristics of the low refractive index B stage coating film of the present invention can be stabilized.

After the above step (2), it is preferable to superimpose a protective film on the surface of the formed low refractive index B stage coating film and temporarily attach the protective film. It is possible to suppress manufacturing troubles such as scratches on the low refractive index B stage coating film before it is completely cured (to the C stage). Further, in the step of irradiating the low refractive index B stage coating film with active energy rays after three-dimensional molding to change from the B stage to the C stage, it is possible to suppress manufacturing troubles such as curing failure due to oxygen damage.

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

The refractive index (RL) of the low refractive index layer (C stage (completely cured) coating film) formed by using the low refractive index B stage coating film of the present invention is a viewpoint of exhibiting a good antireflection function in the molded product. Therefore, it is usually 1.5 or less, preferably 1.45 or less, and more preferably 1.4 or less. On the other hand, from the viewpoint of transparency of the molded product, it may be preferably 1.2 or more, more preferably 1.25 or more, more preferably 1.28 or more, still more preferably 1.3 or more.

The refractive index (RL) is determined by the Abbe refractive index meter according to the method A of JIS K7142: 2008, sodium D line (wavelength 589.3 nm), contact solution 1-bromonaphthalene, and biaxial at the time of sample preparation. It is a value measured under the condition that the surface on the stretched polypropylene resin film side is in contact with the prism and the bar coater operating direction of the sample is the length direction of the test piece. The coating material for forming a low refractive index layer is applied to a sample on the surface of a biaxially stretched polypropylene resin film having a thickness of 20 μm using a bar coater so that the thickness after curing is 2 μm, and dried. Then, the coating film (C stage (completely cured) coating film) obtained by irradiating with active energy rays is peeled off from the biaxially stretched polypropylene-based resin film and used.

The thickness of the low refractive index layer (C stage (completely cured) coating film) formed by using the low refractive index B stage coating film of the present invention is the desired reflectance and the production when forming the low refractive index layer. Determine as appropriate in consideration of gender. From the viewpoint of reducing the reflectance, the thickness of the low refractive index layer may be usually 300 nm or less, preferably 250 nm or less, more preferably 200 nm or less, and further preferably 150 nm or less. On the other hand, from the viewpoint of productivity when forming the low refractive index layer, it may be usually 10 nm or more, preferably 20 nm or more, more preferably 40 nm or more, still more preferably 60 nm or more.

Hereinafter, the above-mentioned coating material for forming a low refractive index layer and each component thereof will be described.

(A) Active energy ray-curable resin:
The active energy ray-curable resin of the component (A) has a function of forming a coating film by polymerizing and curing with active energy rays such as ultraviolet rays and electron beams.

Examples of the component (A) include polyurethane (meth) acrylate, polyester (meth) acrylate, polyacrylic (meth) acrylate, epoxy (meth) acrylate, polyalkylene glycol poly (meth) acrylate, and polyether (meth). ) (Meta) acryloyl group-containing prepolymer or oligomer such as acrylate; methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (Meta) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, phenyl (meth) acrylate, phenylcellosolve (meth) acrylate, 2-methoxyethyl (meth) (Meta) such as acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2-acryloyloxyethyl hydrogen phthalate, dimethylaminoethyl (meth) acrylate, trifluoroethyl (meth) acrylate, and trimethylsiloxyethyl methacrylate. ) Acryloyl group-containing monofunctional reactive monomer; monofunctional reactive monomer such as N-vinylpyrrolidone and styrene; 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) acryloyloxypolypropylene oxyphenyl) (Meta) acryloyl group-containing bifunctional reactive monomer such as propane; (meth) acryloyl group-containing trifunctional reactive monomer such as trimethylolpropanetri (meth) acrylate and trimethylol ethanetri (meth) acrylate; pentaerythritol tetra One or more selected from (meth) acryloyl group-containing tetrafunctional reactive monomers such as (meth) acrylate; and (meth) acryloyl group-containing hexafunctional reactive monomers such as dipentaerythritol hexaacrylate, or the above. Examples thereof include resins containing one or more kinds of constituent monomers. As the active energy ray-curable resin, one kind or a mixture of two or more kinds of these can be used. In addition, in this specification, (meth) acrylate means acrylate or methacrylate.

The component (A) may contain (A1) urethane (meth) acrylate in one of the preferred embodiments. The balance between web handling and three-dimensional moldability can be improved.

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

Examples of the compound having two or more isocyanate groups in one molecule include diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, and methylenebis (4-cyclohexyl isocyanate). Examples thereof include compounds having an isocyanate group. Examples of the compound having two or more isocyanate groups in one molecule include trimethylolpropane adduct of tolylene diisocyanate, trimethylol propane adduct of hexamethylene diisocyanate, trimethylol propane adduct of isophorone diisocyanate, and tolylene diisocyanate. Examples thereof include polyisocyanates such as isocyanurates of isocyanates, isocyanurates of hexamethylene diisocyanates, isocyanurates of isophorone diisocyanates, and biurets of hexamethylene diisocyanates.

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

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

Examples of the polyether polyol 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; ethylene. Copolymers of oxides and tetrahydrofuran; Copolymers of divalent phenol compounds and polyoxyalkylene glycols; and alkylene oxides of divalent phenols and 2-4 carbon atoms (eg, ethylene oxide, propylene oxide, 1, 2). -Copolymers with one or more of (butylene oxide, 1,4-butylene oxide, etc.); and the like.

Examples of the polyester polyol include poly (ethylene adipate), poly (butylene adipate), poly (neopentyl adipate), poly (hexamethylene adipate), poly (butylene azelaate), poly (butylene sebacate), and the like. Polycaprolactone and the like can be given.

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

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

Examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 6-. Hydroxyalkyl (meth) acrylates such as hydroxyhexyl (meth) acrylates and 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylates; dipropylene glycol (meth) acrylates, polyethylene glycol mono (meth) acrylates, And glycol-based (meth) acrylates such as polypropylene glycol mono (meth) acrylates; glycerin-based (meth) acrylates such as glycerinji (meth) acrylates; fatty acid-modified-modified glycidyl-based (meth) acrylates such as glycidyl (meth) acrylates; Phosphor atom-containing (meth) acrylates such as 2-hydroxyethylacryloyl phosphate; (meth) acrylic acid adducts of esters or ester derivatives such as 2- (meth) acryloyloxyethyl-2-hydroxypropylphthalate; pentaerythritol tris ( Pentaerythritol-based (meth) acrylates such as meta) acrylates, dipentaerythritol penta (meth) acrylates, ethylene oxide-modified pentaerythritol tri (meth) acrylates, and ethylene oxide-modified dipentaerythritol penta (meth) acrylates; and caprolactone-modified Examples thereof include 2-hydroxyethyl (meth) acrylate, caprolactone-modified pentaerythritol tri (meth) acrylate, and caprolactone-modified (meth) acrylate such as caprolactone-modified dipentaerythritol penta (meth) acrylate.

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

A polystyrene-equivalent number average molecular weight (hereinafter, may be abbreviated as GPC) obtained from a differential molecular weight distribution curve (hereinafter, may be abbreviated as GPC curve) measured by gel permeation chromatography (hereinafter, may be abbreviated as GPC) of the above component (A1). Mn) 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 contained in the above component (A1) is usually 2 or more, preferably 3 or more, per 1000 polystyrene-equivalent number average molecular weight (Mn) obtained from the GPC curve, from the viewpoint of web handleability. May be. From the viewpoint of surface hardness, scratch resistance, and chemical resistance after complete curing (in the C stage), the number may be more preferably 6 or more. On the other hand, from the viewpoint of three-dimensional moldability, the number may be usually 20 or less, preferably 12 or less, and more preferably 10 or less.

GPC measurement is a system that includes Tosoh Corporation's high performance liquid chromatography system "HLC-8320 (trade name)" (degasser, liquid feed pump, autosampler, column oven and RI (differential refractometer) detector. ) As a GPC column, two GPC columns "KF-806L (trade name)" from Shodex, and one each of "KF-802 (trade name)" and "KF-801 (trade name)". A total of 4 bottles were used by connecting them in the order of KF-806L, KF-806L, KF-802, and KF-801 from the upstream side; tetrahydrofuran for high performance liquid chromatography of Wako Pure Chemical Industries, Ltd. (without stabilizer). ) As the mobile phase; the flow rate is 1.0 ml / min, the column temperature is 40 ° C., the sample concentration is 1 mg / ml, and the sample injection amount is 100 microliters. The elution amount at each holding capacity can be obtained from the amount detected by the RI detector, assuming that the refractive index of the measurement sample does not depend on the molecular weight. Moreover, the calibration curve from the holding capacity to the polystyrene-equivalent molecular weight can be prepared using a commercially available standard polystyrene. At that time, it should be noted that the measured value should be appropriately selected so as to be interpolated in the calibration curve. As the analysis program, "TOSOH HLC-8320GPC EcoSEC (trade name)" manufactured by Tosoh Corporation can be used. Regarding the theory of GPC and the actual measurement, Kyoritsu Publishing Co., Ltd.'s "Size Exclusion Chromatography, High Performance Liquid Chromatography of Polymers, Author: Sadao Mori, First Edition, First Print, December 10, 1991", Ohm Co., Ltd. You can refer to reference books such as "Synthetic Polymer Chromatography, Editor: Hajime Otani, Tatsuya Torasaki (" Saki "is" Standing "at the top of the structure), First Edition, 1st Print, July 25, 2013". can.

FIG. 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 region of relatively low molecular weight, and the polystyrene-equivalent molecular weights at the peak top positions are 700 and 1340 in order from the low molecular weight side. A plurality of overlapping and 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 26000, and the Z average molecular weight (Mz) is 110,000. Further, since the number of (meth) acryloyl groups per molecule is 20, the number of (meth) acryloyl groups per 1000 of polystyrene-equivalent number average molecular weight (Mn) obtained from the GPC curve is 10.

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

When a component (A1) containing urethane (meth) acrylate is used as the component (A), the amount of the component (A1) in the component (A) is a balance between web handleability and three-dimensional moldability. In addition, the surface hardness, scratch resistance, and chemical resistance after complete curing (in the C stage) may be taken into consideration and appropriately determined. The amount of the component (A1) in the component (A) is usually 20% by mass or more, preferably 40% by mass or more, more preferably 60% by mass or more, assuming that the total amount of the above component (A) is 100% by mass. It may be more preferably 80% by mass or more, and most preferably 90 to 100% by mass.

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

The hollow particles are particles having an outer shell layer and having a porous or hollow (single pore) inside. Since the hollow particles contain air (refractive index 1.0) in the pores of the porous or hollow (single pore), the effect of lowering the refractive index of the coating film is great.

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

The average particle size of the component (B) is appropriately determined in consideration of the thickness of the low refractive index layer and the productivity when producing low refractive index particles. The average particle size of the 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 the present specification, the average particle size is 50% by mass in the particle size distribution curve measured by the laser diffraction / scattering method using a laser diffraction / scattering particle size analyzer. Is the particle size. As the laser diffraction / scattering type particle size analyzer, for example, "MT3200II (trade name)" manufactured by Nikkiso Co., Ltd. can be used.

As the component (B), hollow particles are preferable from the viewpoint of obtaining a predetermined refractive index (RL) with a smaller blending amount. As the component (B), one kind or a mixture of two or more kinds of these can be used.

The blending amount of the component (B) is appropriately determined from the viewpoint of setting the refractive index (RL) within the above range in consideration of the type of the component (B). The blending amount of the component (B) is usually 10 to 300 parts by mass, preferably 30 to 200 parts by mass, from the viewpoint of setting the refractive index (RL) in the above range with respect to 100 parts by mass of the component (A). , More preferably 50 to 160 parts by mass.

(C) Photopolymerization initiator:
The component (C) photopolymerization initiator is a compound that generates active species such as radicals by irradiation with active energy rays. The component (C) functions to polymerize and cure the active energy ray-curable resin of the component (A) by generating active species such as radicals.

Examples of the photopolymerization initiator include benzophenone, methyl-o-benzoylbenzoate, 4-methylbenzophenone, 4,4'-bis (diethylamino) benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-. Benzophenone compounds such as 4'-methyldiphenylsulfide, 3,3', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, and 2,4,6-trimethylbenzophenone; benzoin, benzoin methyl ether, benzoin Benzophenones such as ethyl ether, benzoin isopropyl ether, and benzylmethyl ketal; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenylketone, and 2-hirodoxy-1- {4- [4- [4- Acetphenone compounds such as (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propane-1-one; α-hydroxyalkylphenone, acetophenone dimethylketal, 2-hydroxy-2-methyl- Alkylphenone compounds such as 1-phenyl-propane-1-one and 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one; methylanthraquinone Anthraquinone compounds such as 2-ethylanthraquinone and 2-amyl anthraquinone; thioxanthone compounds such as thioxanthone, 2,4-diisopropylthioxanthone, and 2,4-diisopropylthioxanthone; bis (2,4,6-trimethylbenzoyl) Phenylphosphine oxide and acylphosphine oxide compounds such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide; biimidazole compounds; titanocene compounds; oxime ester compounds; oxymphenyl acetate ester compounds; hydroxyketone Phenyl compounds; triazine compounds; and aminobenzoate compounds can be mentioned.

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

When a 365 filter is used as the filter, the preferred component (C) is, for example, having an absorption peak having a peak top value of maximum absorbance in the wavelength range of 220 to 280 nm; more than the peak top of the absorption peak. The wavelength at which the absorbance is 1 / n of the peak top value (= maximum absorbance) on the long wavelength side is usually 290 nm or less, preferably 285 nm or less, more preferably 280 nm or less; at any wavelength in the wavelength range of 290 to 400 nm. Also has an absorbance of 1 / n or less of the maximum absorbance; photopolymerization initiators can be mentioned. Here, n is a natural number of 2 to 8, and is usually 2, preferably 3, more preferably 4, still more preferably 5, even more preferably 6, even more preferably 7, and most preferably 8.

When a 365 filter is used as the filter, the preferred component (C) is, for example, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hirodoxy-1- {4- [4- (2-hydroxy-2-). Methyl-propionyl) -benzyl] phenyl} -2-methyl-propane-1-one, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, 1- [4- (2-hydroxyethoxy)- Phenyl] -2-hydroxy-2-methyl-1-propane-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, and 1-hydroxycyclohexyl- Examples thereof include a mixture of phenylketone and benzophenone (mass ratio is usually 100: 0 to 45:55, 90/10 to 45:55 in one embodiment).

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

The blending amount of the above component (C) is from the viewpoint of curing the coating film in the B stage state, from the viewpoint of keeping the coating film cured in the B stage state, and from the viewpoint of ensuring complete curing (to the C stage) after three-dimensional molding. It may be selected as appropriate in consideration of comprehensively. The blending amount of the component (C) is from the viewpoint of curing the coating film in the B stage state with respect to 100 parts by mass of the component (A), and from the viewpoint of surely completely curing (to the C stage) after three-dimensional molding. Therefore, it may be usually 1 part by mass or more, preferably 3 parts by mass or more, more preferably 4 parts by mass or more, and further preferably 5 parts by mass or more. On the other hand, from the viewpoint of keeping the curing of the coating film in the B stage state, it is usually 20 parts by mass or less, preferably 15 parts by mass or less, more preferably 12 parts by mass or less, still more preferably 10 parts by mass or less, and most preferably 8 parts by mass. It may be:

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 cellsolve, and ethyl cell solution. , Diacetone alcohol, acetone and the like. As the solvent, one kind or a mixture of two or more kinds of these can be used.

The blending amount of the solvent is determined from the viewpoint of productivity when forming a wet coating film using the coating material for forming a low refractive index layer, and after forming a wet coating film using the coating material for forming a low refractive index layer. , The wet coating film is appropriately determined from the viewpoint of productivity in the process of drying and recovering the solvent. The blending amount of the solvent is preferably 1000 parts by mass, with the blending amount of the component (A) being 100 parts by mass from the viewpoint of productivity when forming a wet coating film using the coating material for forming a low refractive index layer. It may be 2 parts or more, more preferably 2000 parts by mass or more, and further preferably 3000 parts by mass or more. On the other hand, from the viewpoint of productivity in the process of forming a wet coating film using the coating material (A) and then drying the wet coating film and recovering the solvent, it is preferably 100,000 parts by mass or less, more preferably 50,000. It may be parts by mass or less, more preferably 10,000 parts by mass or less.

The coating material for forming a low refractive index layer may further contain any component other than the above components (A) to (C), if desired, as long as it does not contradict the object of the present invention. Examples of the optional components include antifoaming agents, leveling agents, surfactants, thixophilic imparting agents, antistatic agents, anticontamination agents, water repellents, printability improving agents, antioxidants, weather resistance stabilizers, and the like. Examples thereof include light resistance stabilizers, ultraviolet absorbers, heat stabilizers, and dyes. As the optional component, one kind or a mixture of two or more kinds of these can be used. The blending amount of the optional component may be usually 10 parts by mass or less, or about 0.01 to 10 parts by mass with respect to 100 parts by mass of the component (A1).

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

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

The laminated film of the present invention is obtained by forming the low refractive index B stage coating film of the present invention on at least one surface of a film substrate by the production method of the present invention using the above-mentioned coating material for forming a low refractive index layer. be able to. The production method of the present invention has been described in the section "1. Production method of low refractive index B stage coating film". The low refractive index B stage coating film of the present invention and the above-mentioned coating material for forming a low refractive index layer have been described in the section “2. Low refractive index B stage coating film”. Hereinafter, the film base material will be described.

Film substrate:
The film base material is a film that serves as a base material 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 base material is one of the constituent materials of the molded product of the present invention will be described. When the film base material is one of the constituent materials of the molded product of the present invention, the film base material has high transparency from the viewpoint of enhancing the transparency of the molded product and ensuring visibility. A non-colored film (transparent resin film) is preferable. Examples of such a film include a cellulose ester resin such as triacetyl cellulose; a polyester resin such as polyethylene terephthalate; a cyclic hydrocarbon resin such as an ethylene norbornene copolymer; polymethyl methacrylate, poly ethyl methacrylate, and the like. And acrylic resins such as vinylcyclohexane and methyl (meth) acrylate copolymers; aromatic polycarbonate resins; polyolefin resins such as polypropylene and poly-4-methylpentene-1; polyamide resins; polyallylate resins; Examples thereof include transparent resin films such as polymer-type urethane acrylate-based resins; and polyimide-based resins; These films include non-stretched films, uniaxially stretched films, and biaxially stretched films. Further, these films include a laminated film 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 usually 85% or more, preferably 88% or more, and more preferably 90% or more. The higher the total light transmittance, the more preferable. By using a transparent resin film having a total light transmittance of 85% or more, a molded body that requires high transparency, for example, a display face plate of an image display device such as a car navigation system and a digital signage, and an automobile instrument. It is possible to obtain a low refractive index B-stage coating film laminated film suitable as a member such as a panel, and a molded product 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, a turbidity meter "NDH2000 (trade name)" manufactured by Nippon Denshoku Industries 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 having a yellowness index of 3 or less, molded bodies that require high colorlessness, such as display face plates of image display devices such as car navigation systems and digital signage, and instrument panels of automobiles, etc. A low-refractive-index B-stage coating film laminated film suitable as a member of the above and a molded product using the same can be obtained. Here, the yellowness index is a value measured using a chromaticity meter according to JIS K7105: 1981. As the chromaticity meter, for example, a chromaticity meter "SolidSpec-3700 (trade 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 or less, more preferably 40 nm or less, still more preferably 30 nm or less, still 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, molded bodies that require clear transparency, such as display face plates for image display devices such as car navigation systems and digital signage, and instrument panels for automobiles, etc. A low refractive index B-stage coating film laminated film suitable as a member and a molded product using the same can be obtained. Here, the retardation is a value measured by the parallel Nicol rotation method. As the measuring device, for example, a phase difference measuring device "KOBRA-WR (trade name)" by the parallel Nicol rotation method of Oji Measuring Instruments Co., Ltd. can be used.

When the film base material is one of the constituent materials of the molded product of the present invention, the thickness of the film base material is appropriately determined in consideration of the use of the molded product. When the film base material is one of the constituent materials of the molded product of the present invention, the thickness of the film base material may be usually 20 μm or more, preferably 50 μm or more from the viewpoint of handleability. From the viewpoint of the strength of the molded product, the thickness of the film base material may be usually 100 μm or more, preferably 150 μm or more. On the other hand, the thickness of the film base material may be usually 2000 μm or less, preferably 800 μm or less, and more preferably 600 μm or less from the viewpoint of weight reduction of the molded product.

When the film base material is one of the constituent materials of the molded product of the present invention, the film base material and the low refractive index B stage coating film of the present invention or the low refractive index B stage coating film of the present invention are used. From the viewpoint of improving the adhesion to the low refractive index layer (C stage (completely cured) coating film) formed by using the film, the coating film-forming surface of the film substrate is easily adhered by corona discharge treatment or anchor coat formation. It may be processed.

When the low refractive index B-stage coating film of the present invention is transferred to another substrate (for example, a film, a sheet, a plate, and a substrate of an arbitrary shape) and used (that is, the film substrate is the molding of the present invention). When the body is not constructed.) Will be explained.

When the low refractive index B-stage coating film of the present invention is transferred to another substrate and used, the film substrate is not particularly limited, and any film substrate can be used. In this case, the film base material includes a non-stretched film of a polyester resin such as polyethylene terephthalate, a biaxially stretched film, a non-stretched film of a polypropylene resin, and two from the viewpoint of web handleability and economy. Axial stretch film is preferable.

When the low refractive index B-stage coating film of the present invention is transferred to another substrate and used, the thickness of the film substrate may be usually 20 μm or more, preferably 30 μm or more from the viewpoint of web handleability. On the other hand, the thickness of the film base material may be usually 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 and used, the coating film-forming surface of the film substrate may be easily peeled off.

Coating film with three-dimensional moldability:
In one of the embodiments, the laminated film of the present invention has a coating film having three-dimensional moldability on at least one surface of the film base material, and is on the surface of the coating film having three-dimensional moldability. In addition, it may have the low refractive index B stage coating film of the present invention. By forming the coating film having the above three-dimensional moldability, it is possible to impart desired functions and characteristics, for example, to increase the surface hardness and the antireflection function.

The thickness of the coating film having three-dimensional moldability is appropriately determined in consideration of the function and characteristics to be imparted to the laminated film of the present invention by forming the layer of the coating film. The thickness of the coating film having three-dimensional moldability is usually 0.1 μm or more, preferably 1 μm or more, more preferably from the viewpoint of surely obtaining the function and characteristics to be obtained by forming the layer of the coating film. May be 5 μm or more, more preferably 8 μm or more. On the other hand, from the viewpoint of handleability when forming the layer of the coating film, it may be usually 100 μm or less, preferably 60 μm or less, and more preferably 30 μm or less.

Examples of the coating film having three-dimensional moldability include a B-stage coating film and a urethane-based curable resin coating film.

B-stage coating film as a coating film with three-dimensional moldability:
The B-stage coating film is a coating film in an intermediate state of curing of a curable resin, and when the low refractive index B-stage coating film of the present invention is completely cured (to the C stage) by irradiating it with active energy rays. It is a coating film that is completely cured (to the C stage) at the same time. The B-stage coating film is formed in one of the typical embodiments by 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 a low refractive index layer. As the active energy ray-curable resin, one kind or a mixture of two or more kinds of these can be used.

After forming the B-stage coating film on at least one surface of the film substrate, a wet coating film is further formed on the surface of the B-stage coating film using the coating film for forming a low refractive index layer. , The embodiment of forming the low refractive index B stage coating film of the present invention will be described.

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

The blending amount of the photopolymerization initiator contained in the coating film for forming the B-stage coating film is the active energy for forming the low refractive index B-stage coating film of the present invention from the viewpoint of curing the coating film to the B-stage state. The selection is made appropriately from the viewpoint of keeping the curing of the coating film in the B stage state even after being irradiated with the line and the viewpoint of surely completely curing (to the C stage) after the three-dimensional molding. The blending amount of the photopolymerization initiator is the low refractive index from the viewpoint of keeping the coating film in the B stage state even after being irradiated with the active energy rays for forming the low refractive index B stage coating film of the present invention. Usually 0.01 to 1 times, preferably 0.05 to 0.6 times, more preferably 0.1 to 0.4 times the amount of the above-mentioned component (C) photopolymerization initiator contained in the coating material for forming a rate layer. It may be there. The blending amount of the photopolymerization initiator is from the viewpoint of curing the coating film to the B stage state with respect to 100 parts by mass of the active energy ray-curable resin, and after three-dimensional molding, it is surely completely cured (to the C stage). From the viewpoint of the above, it is usually 0.01 part by mass or more, preferably 0.05 part by mass or more, more preferably 0.1 part by mass or more, further preferably 0.5 part by mass or more, and most preferably 1 part by mass or more. It's okay. On the other hand, from the viewpoint of keeping the curing of the coating film in the B stage state, it is usually 20 parts by mass or less, preferably 12 parts by mass or less, more preferably 8 parts by mass or less, still more preferably 5 parts by mass or less, and most preferably 3 parts by mass. It may be:

An embodiment in which the B-stage coating film is formed on at least one surface of the film substrate, and then the low refractive index B-stage coating film of the present invention is further formed on the surface of the B-stage coating film by transfer. Will be described.

The photopolymerization initiator contained in the coating material for forming the B-stage coating film is appropriately determined in consideration of 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 a low refractive index layer. As the photopolymerization initiator, one kind or a mixture of two or more kinds of these can be used.

The amount of the photopolymerization initiator contained in the coating film for forming the B-stage coating film is determined from the viewpoint of curing the coating film to the B-stage state, from the viewpoint of keeping the coating film cured in the B-stage state, and after three-dimensional molding. , Select as appropriate by comprehensively considering the viewpoint of ensuring complete curing (to C stage). The blending amount of the photopolymerization initiator is from the viewpoint of curing the coating film to the B stage state with respect to 100 parts by mass of the active energy ray-curable resin, and after three-dimensional molding, it is surely completely cured (to the C stage). From this point of view, it 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 further preferably 4 parts by mass or more. On the other hand, from the viewpoint of keeping the curing of the coating film in the 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 further preferably 10 parts by mass or less.

A method for producing a B-stage coating film as a coating film having three-dimensional moldability. 1:
The method for producing a B-stage coating film as a coating film having three-dimensional moldability is one of preferred embodiments, in which (1) an active energy ray-curable resin is formed on the surface of a film substrate. It includes (b) a step of forming a wet coating film using a coating material containing 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. The active energy ray is usually 1/2 or more, preferably 1/3 or more, more preferably 1/4 or more, still more preferably 1/4 or more of the maximum absorbance of the above component (b) photopolymerization initiator using a filter. It is monochromatic so as not to include wavelengths having an absorbance of 1/5 or more, more preferably 1/6 or more, even more preferably 1/7 or more, and most preferably 1/8 or more; The manufacturing method of

In one of the preferred embodiments, the production method wet coats (1) on the surface of a film substrate with a paint containing (a) an active energy ray-curable resin and (b) a photopolymerization initiator. The step of forming a film; and (2) the step of irradiating the wet coating film with an active energy ray to bring it into a B stage state; (B) The maximum absorbance of the photopolymerization initiator is usually 1/2 or more, preferably 1/3 or more, more preferably 1/4 or more, still more preferably 1/5 or more, still more preferably 1/6 or more, and further. More preferably, it does not contain a wavelength having an absorbance of 1/7 or more, most preferably 1/8 or more; and usually 1/10 to 1/100, preferably 1/15 to 1/70, more preferably. It is monochromatic so as to include a wavelength having an absorbance of 1/20 to 1/50; it may be a method for producing a B-stage coating film.

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

The fact that the active energy ray does not include the active energy ray of a certain wavelength means that the specific energy intensity of the active energy ray at the wavelength is usually less than 5%, preferably 2% or less, more preferably 1% or less, still more preferably 0. It means that it is 5.5% or less, most preferably 0.1% or less.

The inclusion of the active energy ray of a certain wavelength means that the specific energy intensity of the active energy ray at the 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 when the energy intensity of the wavelength that the filter best transmits is 100%.

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

As the film base material used in the above step (1), the same film base material used when producing the laminated film of the present invention can be used.

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

When a component (a1) containing urethane (meth) acrylate is used as the component (a), the amount of the component (a1) in the component (a) is the same as the amount of all the components (a). As 100% by mass, from the viewpoint of improving the balance between web handleability and three-dimensional moldability, it may be usually 20% by mass or more, preferably 40% by mass or more, and more preferably 60 to 100% by mass.

As the component (a1), for example, the same component (A1) as the urethane (meth) acrylate that can be contained as a preferable component in the coating material for forming a low refractive index layer can be used. Further, the present invention is to produce a coating film having three-dimensional moldability by the same method as the method for producing a low refractive index B stage coating film of the present invention, and further to the present invention on the surface of the coating film having the three-dimensional moldability. Since the low refractive index B-stage coating film of No. 1 is formed, a preferable one as the above-mentioned component (A1) urethane (meth) acrylate is also preferably used as the above-mentioned component (a1). As the component (a1), one kind or a mixture of two or more kinds of these can be used.

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

The component (b) photopolymerization initiator to be contained in the paint (the component (a) active energy ray-curable resin and the component (b) the paint containing the photopolymerization initiator) used in the step (1) is To produce a coating film having three-dimensional moldability by the same method as the method for producing a low refractive index B-stage coating film of the present invention, and further on the surface of the coating film having three-dimensional moldability, the present invention. Since a low refractive index B stage coating film is formed, what is preferable as the above component (B) photopolymerization initiator contained in the above low refractive index layer forming paint is also preferably used as the above component (b). As the component (b), one kind or a mixture of two or more kinds of these can be used.

The blending amount of the component (b) is from the viewpoint of curing the coating film in the B stage state with respect to 100 parts by mass of the component (a), and from the viewpoint of surely completely curing (to the C stage) after three-dimensional molding. Therefore, it may be usually 0.01 part by mass or more, preferably 0.05 part by mass or more, more preferably 0.1 part by mass or more, further preferably 0.5 part by mass or more, and most preferably 1 part by mass or more. .. On the other hand, from the viewpoint of keeping the curing of the coating film in the B stage state, it is usually 20 parts by mass or less, preferably 12 parts by mass or less, more preferably 8 parts by mass or less, still more preferably 5 parts by mass or less, and most preferably 3 parts by mass. It may be:

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

Before irradiating the active energy ray in the step (2), the wet coating film formed by using the paint containing the component (a) active energy ray-curable resin and the component (b) photopolymerization initiator is applied. Pre-drying is preferred. In the pre-drying, for example, it takes about 0.5 to 10 minutes to pass the web from the inlet to the outlet in a drying furnace set to a temperature of about 23 to 150 ° C., preferably a temperature of about 50 to 120 ° C. This can be done by passing at a line speed of preferably 1 to 5 minutes.

The step (2) is a step of irradiating the wet coating film with active energy rays to bring it into a B stage state. The irradiation amount of the active energy rays is made very low by using a filter from the viewpoint of keeping the curing of the wet coating film in the B stage state.

Examples of the light source of the active energy ray include a high-pressure mercury lamp and a metal halide lamp.

The irradiation amount of the active energy rays is determined from the viewpoint of stably performing the step (2), curing the wet coating film in the B stage state, and keeping the curing of the wet coating film in the B stage state. The component (a) is appropriately selected and determined in consideration of the number of polymerizable functional groups of the active energy ray-curable resin, the type and amount of the component (b) photopolymerization initiator, and the like. The irradiation amount of the above active energy rays is usually 1 to 1000 mJ / cm ² , preferably 30 to 700 mJ / cm ^{2, and} more preferably 50 to 500 mJ / cm ² in terms of the irradiation amount when the filter is not used. It may be there.

After the above step (2), an aging process may be performed. The characteristics of the B-stage coating film can be stabilized.

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

The paint for forming a B-stage coating film will be described. Examples of the active energy ray-curable resin of the component (a) include those exemplified in the description of the coating material for forming a 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.

Examples of the component (a1) include those described as the component (A1) urethane (meth) acrylate that can be contained as a preferable component in the coating material for forming a low refractive index layer.

The polystyrene-equivalent number average molecular weight (Mn) obtained from the GPC curve of the above component (a1) measured by GPC is usually 1000 or more, preferably 1600 or more, and more preferably 2000 or more from the viewpoint of three-dimensional moldability. It's okay. 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) obtained from the GPC curve of the component (a1) measured by GPC may be usually 2000 or more, preferably 4000 or more, from the viewpoint of three-dimensional moldability. On the other hand, from the viewpoint of coatability, it may be usually 100,000 or less, preferably 50,000 or less.

The GPC measurement method is described above.

The number of (meth) acryloyl groups possessed by the above component (a1) is per 1000 of polystyrene-equivalent number average molecular weight (Mn) obtained from the GPC curve, and the web handleability (the coating film becomes a transfer roll or the like during web handling). From the viewpoint of (difficulty of scratches and poor appearance due to contact), the number may be usually 2 or more, preferably 3 or more. From the viewpoint of surface hardness, scratch resistance, and chemical resistance after complete curing (in the C stage), the number may be more preferably 6 or more. On the other hand, from the viewpoint of three-dimensional moldability, the number may be usually 20 or less, preferably 12 or less, and more preferably 10 or less.

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

When a component (a1) containing the component (a1) is used as the component (a), the blending amount of the component (a1) is such that the total amount of the component (a) is 100% by mass, and the effect of using the component (a1). From the viewpoint of surely obtaining, it may be usually 10% by mass or more, preferably 40% by mass or more, more preferably 70% by mass or more, and further preferably 80 to 100% by mass.

As the component (a) active energy ray-curable resin, it is preferable to use a resin containing (a2) mercaptoalkyl glycol uryls. Three-dimensional moldability in B stage; Web handleability (difficulty of scratches and appearance defects due to contact of the coating film with transfer rolls during web handling); and after complete curing (in C stage) Surface hardness, scratch resistance, and chemical resistance; can be improved in a well-balanced manner.

The number of mercaptoalkyl groups contained in the component (a2) may be preferably 2 to 4, more preferably 4 from the viewpoint of surely obtaining the effect of using the component (a2).

Examples of the component (a2) include mercaptoalkyl glycol uryls having two mercaptoalkyl groups in one molecule, such as 1,3-bis (3-mercaptopropyl) glycoluryl; 1,3,4,6. Mercaptoalkyl glycol uryls having 4 mercaptoalkyl groups in one molecule, such as -tetrakis (2-mercaptoethyl) glycol uryl and 1,3,4,6-tetrakis (3-mercaptopropyl) glycol uryl; etc. Can be given.

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

When the component (a) containing the component (a2) is used, the blending ratio of the component (a2) is such that the total of the components (a) is 100% by mass, and the effect of using the component (a2). From the viewpoint of surely obtaining, it may be usually 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more, still more preferably 4% by mass or more. 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 further preferably 10% by mass or less.

As the active energy ray-curable resin of the component (a), it is more preferable to use one containing the urethane (meth) acrylate of the component (a1) and the mercaptoalkyl glycol urils of the component (a2). 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) can be further improved in a well-balanced manner.

When the component (a) containing the component (a1) and the component (a2) is used, the sum of the blending amount of the component (a1) and the blending amount of the component (a2) is set to 100% by mass. The blending amount of the component (a1) is usually 99 to 80% by mass (blending amount of the component (a2) 1 to 20% by mass), preferably 98 to 85% by mass (blending amount of the component (a2) 2 to 2). 15% by mass), more preferably 97 to 88% by mass (3 to 12% by mass of the above component (a2)), still more preferably 96 to 90% by mass (4 to 10% by mass of the above component (a2)). %).

When a component (a1) containing the component (a1) and the component (a2) is used as the component (a), the sum of the blending amount of the component (a1) and the blending amount of the component (a2) is the sum of the blending amount of the component (a2). ) Is 100% by mass, and is usually 80 from the viewpoint of the balance of three-dimensional moldability in the B stage; and surface hardness, scratch resistance, and chemical resistance after complete curing (in the C stage). It may be mass% or more, preferably 90% by mass or more, more preferably 95% by mass or more, and further preferably 98 to 100% by mass.

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

As the component (b) photopolymerization initiator contained in the B-stage coating film forming paint, 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 moldability. Therefore, what is preferable as the photopolymerization initiator of the component (B) to be contained in the coating material for forming a low refractive index layer is also preferably used as the component (b).

When the low refractive index layer forming paint is applied on the surface of the coating film having three-dimensional moldability to form the low refractive index B stage coating film, the blending amount of the component (b) is From the viewpoint of curing the coating film to the B stage state and surely completely curing (to the C stage) after three-dimensional molding with respect to 100 parts by mass of the above component (a), usually 0.01 part by mass or more. It may be preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, still more preferably 0.5 parts by mass or more, and most preferably 1 part by mass or more. On the other hand, from the viewpoint of keeping the curing of the coating film in the B stage state, it is usually 20 parts by mass or less, preferably 12 parts by mass or less, more preferably 8 parts by mass or less, still more preferably 5 parts by mass or less, and most preferably 3 parts by mass. It may be:

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

The above component (c) thermal polymerization initiator is a compound that generates active species such as radicals by heating. The component (c) functions to cure the coating film to the B stage state.

Examples of the component (c) thermal polymerization initiator include 2,2'-azobisisobutyronitrile (2,2'-azobis (2-methylpropionitrile)) and 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-methylpropionic acid) dimethyl, 1,1'-azobis (methyl cyclohexanecarboxylic acid), 2,2'-azobis (n-butyl-2-methylpropionamide), 2,2'-azobis (2-methylpropionamidine) dihydrochloride, dimethyl 1,1-azobis (1-cyclohexanecarboxylate), and Azobisisobuty such as 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride; benzoyl peroxide, tert-butylhydroperoxide, cumenehydroperoxide, di-tert-butylperoxide, and Organic peroxides such as dicumylperoxide; benzenesulfonic acid esters such as cyclohexyl p-toluenesulfonate; benzyl (4-hydroxyphenyl) methylsulfonium hexafluoroantimonate, (4-hydroxyphenyl) methyl (2-methylbenzyl) Examples thereof include sulfonium salts such as sulfonium hexafluoroantimonate and diphenyl (methyl) sulfonium tetrafluoroborate; and dicyandiamide;

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

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

The blending amount of the above component (c) is from the viewpoint of curing the coating film to the B stage state, from the viewpoint of keeping the curing of the coating film in the B stage state, and stably keeping the coating film in the B stage state until three-dimensional molding is performed. It may be selected as appropriate in consideration of the viewpoint to be retained. The blending amount of the component (c) is usually 0.001 part by mass or more, preferably 0.005 part by mass or more, from the viewpoint of curing the coating film in the B stage state with respect to 100 parts by mass of the component (a). , More preferably 0.01 parts by mass or more, still more preferably 0.02 parts by mass or more. On the other hand, from the viewpoint of keeping the curing of the coating film in the B stage state and from the viewpoint of stably holding the coating film in the B stage state until three-dimensional molding is performed, it is usually 1 part by mass or less, preferably 0.5 part by mass or less. , More preferably 0.3 parts by mass or less, further preferably 0.2 parts by mass or less, and most preferably 0.1 parts by mass or less.

The step (1) is a step of forming a wet coating film on the surface of the film base material by using the coating film for forming a B-stage coating film. The step (1) is usually a step of forming a wet coating film on one surface of the film base material using the B-stage coating film forming paint.

As the film base material used in the above step (1), the same film base material used when producing the laminated film of the present invention can be used.

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

In the step (2), the wet coating film formed in the step (1) is preferably subjected to a time of 1 to 20 minutes at a temperature of 80 to 160 ° C., preferably 90 to 150 ° C., more preferably 100 to 140 ° C. Is a step of drying and curing to a B stage state by treating for 3 to 15 minutes, more preferably 4 to 10 minutes.

Although not intended to be bound by theory, the treatment time of the above step (2) is considerably shorter than the time required for completely curing (to the C stage) the coating film using the thermal polymerization initiator. Further, by the above step (3), the progress of the curing reaction due to heat is stopped. Further, in the above-mentioned B-stage coating film forming paint, the amount of the thermal polymerization initiator contained therein is considerably small, and the progress of the curing reaction should be considerably slow. Therefore, it is considered that the coating film remains in the B stage state.

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

In the step (3), the temperature of the coating film treated in the step (2) is usually cooled to 60 ° C. or lower, preferably 50 ° C. or lower, more preferably 40 ° C. or lower, and the progress of the curing reaction by heat is stopped. It is a process to make it. The step (3) is preferably performed immediately after the step (2) for the purpose of stopping the progress of the curing reaction due to heat.

The process of the above step (3) can be performed by any method. The process of the above step (3) can be performed, for example, by handling the web. The calorific value of the coating film treated in the above step (2) is usually not so large. Therefore, it can be expected that the web will be cooled sufficiently quickly and the temperature will be 60 ° C. or lower by handling the web while holding it in a transfer roll whose temperature is not controlled. The process of the above step (3) can preferably be performed by handling the web while holding it in a chill roll. The temperature of the chill roll is usually set to 60 ° C. or lower, preferably 50 ° C. or lower, more preferably normal temperature (23 ° C.) to 40 ° C. The number of the chill rolls is not limited to one, and may be two or more.

When the processing of the above step (2) is performed by passing the inside of the drying oven set to a predetermined temperature at a predetermined line speed, the processing of the above step (3) is performed on the web coming out of the drying oven. It can be carried out by handling while holding the transfer roll whose temperature is not controlled, preferably a chill roll set to a predetermined temperature.

After the above step (3), an aging process may be performed. The characteristics of the B-stage coating film can be stabilized.

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

A coating film with three-dimensional moldability that functions as a high refractive index layer:
The coating film having three-dimensional moldability may contain high refractive index particles in one of the embodiments. The coating film having three-dimensional moldability contains high refractive index particles and functions as a high refractive index layer, so that the antireflection function can be enhanced. In the 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 is determined by using the low refractive index B stage coating film of the present invention. From the viewpoint of increasing the difference in refractive index from the refractive index (RL) of the formed low refractive index layer and exhibiting a good antireflection function, it is preferably 1.55 or more, more preferably 1.6 or more. good. On the other hand, from the viewpoint of the color of the reflected light, it may be usually 2.0 or less, preferably 1.9 or less, more preferably 1.8 or less, still more preferably 1.7 or less, and most preferably 1.65 or less. ..

The refractive index (RH) is according to the method A of JIS K7142: 2008, using an Abbe refractive index meter, sodium D line (wavelength 589.3 nm), contact solution is 1-bromonaphthalene, and biaxial at the time of sample preparation. It is a value measured under the condition that the surface on the stretched polypropylene resin film side is in contact with the prism and the bar coater operating direction of the sample is the length direction of the test piece. As a sample, a coating film for forming a coating film having three-dimensional moldability was applied onto the surface of a biaxially stretched polypropylene resin film having a thickness of 20 μm, and a bar coater was used so that the thickness after curing was 2 μm. The coating film obtained by coating, drying and curing is peeled from the biaxially stretched polypropylene-based resin film and used.

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 dissimilar elements such as antimony and tin in these metal oxides. The composite oxide doped with the above; and the like can be mentioned.

As the high refractive index particles, the surface thereof is surfaced with a silane coupling agent such as vinylsilane and aminosilane; a titanate coupling agent; an aluminate coupling agent; and ethylene such as a (meth) acryloyl group, a vinyl group, and an allyl group. Organic compounds having a reactive functional group such as a sex unsaturated bond group or an epoxy group; and a surface treatment agent such as a fatty acid and a fatty acid metal salt; may be used.

The average particle size of the high-refractive index particles is appropriately determined in consideration of the viewpoint of maintaining the transparency of the coating film and the productivity when producing the high-refractive index particles. The average particle size of the high-refractive index particles is usually 1 to 300 nm, preferably 5 to 200 nm, more preferably 10 to 150 nm, and further preferably 15 to 100 nm. The method and definition of the average particle size are described above in the description of the component (B) low refractive index particles.

As the high-refractive index particles, one kind or a mixture of two or more kinds of these can be used.

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

4. Mold:
The molded product of the present invention has a low refractive index layer (C stage (completely cured) coating film) formed by 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 product of the present invention. A low refractive index formed by using the low refractive index B stage coating film of the present invention in one of the typical embodiments on the surface of the molded body of the present invention where it is exposed to direct sunlight. A layer (C stage (completely cured) coating film) is formed.

The molded product 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 the low refractive index B stage coating film (to the C stage). .. Examples of such a molded product include a film, a sheet, and a plate having a low refractive index layer (C stage (completely cured) coating film) formed by using the low refractive index B stage coating film of the present invention. After imparting a desired shape by three-dimensional molding such as vacuum molding, pneumatic molding, and press molding using the laminated film of the present invention, the low refractive index B stage coating film of the laminated film is completely cured (to C stage). In addition, the laminated film of the present invention is inserted into a mold as a skin material, and an arbitrary thermoplastic resin is injected as a core material. The composite molded product obtained by completely curing (to the C stage); etc. can be mentioned.

Using the laminated film of the present invention (coating film is B stage), a three-dimensional molding method is applied to give a three-dimensional shape, and then the low refractive index B stage coating film of the laminated film is completely cured (to C stage). ), An example in the case of vacuum molding will be described with respect to the method for producing the molded product of the present invention.

FIG. 6 is a conceptual diagram showing an example of a vacuum forming apparatus. First, as shown in FIG. 6A, the laminated film (coating film is B stage) 1 is heated by using a heating device 2 such as an infrared heater to soften it. Next, the laminated film 1 is removed from the heating device 2 and quickly covered with the molding die 3 (FIG. 6 (b)). At this time, the molding die 3 may be preheated. Subsequently, the space 4 between the laminated film 1 and the molding die 3 is depressurized, the laminated film 1 is brought into close contact with the molding die 3, the shape of the molding die 3 is transferred to the laminated film 1, and the molded body 5 (coating) is formed. The film obtains the B stage) (Fig. 2 (c)). The mold 3 may be cooled before the molded product 5 is released from the mold 3. Subsequently, the molded product of the present invention can be produced by completely curing (to the C stage) the low refractive index B stage coating film of the molded product 5 using an arbitrary active energy ray irradiation device.

The pressure in the space 4 may be preferably 10 KPa or less, more preferably 1 KPa or less, from the viewpoint of sufficiently adhering the air between the B-stage coating film laminated film 1 and the molding die 3 without leaving air. The adhesion increases as the pressure in the space 4 decreases, but reducing the pressure increases the cost at an accelerating rate, and considering the mechanical strength of the laminated film 1, practically, the space 4 has an adhesive force. The lower limit of the pressure may be about ^{10-5 KPa.}

The irradiation amount of the active energy rays is appropriately selected and determined from the viewpoint of making the irradiation amount necessary and sufficient for completely curing (to the C stage) the low refractive index B stage coating film. The dose of the active energy rays, usually 10 to 10000 mJ / cm ^2, preferably 200~2000mJ / cm ^2, more preferably a 300~700mJ / cm ^2.

The molded product of the present invention has a low refractive index layer (C stage (completely cured) coating film) formed by using the low refractive index B stage coating film of the present invention and an arbitrary substrate in one of the embodiments. It may be a thing. In the molded product of the embodiment, the substrate is used instead of the molding die 3, the laminated film 1 is adhered to and integrated with the substrate, and then the low refractive index B stage coating film is completely cured (to the C stage). Can be manufactured by

Since the molded body of the present invention has preferable properties as described above, articles used in places exposed to direct sunlight, for example, display face plates of image display devices such as car navigation systems and digital signage, and automobiles. It can be suitably used as an instrument panel of.

Since the molded product of the present invention has preferable properties as described above, it can be suitably used as an article (including a member of the article). Examples of the above-mentioned articles include image display devices such as liquid crystal displays, plasma displays, and electroluminescence displays, and members such as display face plates, transparent conductive substrates, and housings; televisions, personal computers, and tablet-type information devices. , Smartphones, and members such as their housings and display face plates; and further, refrigerators, washing machines, cupboards, clothes racks, and the panels that compose them; building windows and doors; vehicles, vehicle windows, windshields, etc. , Roof windows, instrument panels, etc .; head-up displays, electronic signs, and protective plates thereof; show windows; solar cells, and members such as their housings and front plates; and the like.

Hereinafter, the present invention will be described with reference to Examples, but the present invention is not limited thereto.

Measurement method (a) Three-dimensional moldability:
A molding die (see FIG. 7; front view, height (h) 10 mm, surroundings) in which the laminated film (coating film is B stage) was preheated using an infrared heater and then preheated to 130 ° C. The radius of curvature (R) of the curved portion (R) is 16.25 mm. The plan view of FIG. 7B, the diameter of the outer circumference (φ) is 90 mm.) The surfaces are spread and covered so as to be on the molding die side, and after waiting for 30 seconds, the space between the laminated film and the molding die is ^{reduced to a pressure of 1.0 × 10 -3} KPa, and the above. The shape of the molding die was transferred to the laminated film to obtain a molded body (the coating film was B stage). The B-stage coating film of the molded body is irradiated with a high-pressure mercury lamp type ultraviolet irradiation device under ^{the condition of an integrated light amount of 600 mJ / cm 2} , and completely cured (to the C stage) to form a molded body (coating film). Obtained C stage). The appearance of the molded product (the coating film was C stage) was visually observed and evaluated according to the following criteria.
A: No cracks, cracks, or poor appearance were observed.
B: No cracks or cracks were observed. However, when I looked through the light up close, there was a slight cloudiness.
C: Slight cracks and cracks were observed in the surrounding curved part.
D: Cracks and cracks were observed overall.

(B) Tack-free test (index of web handleability):
After preheating the laminated film (coating film is B stage) at 80 ° C. for 6 minutes, latex gloves (Okamoto Co., Ltd.'s "Latex Disposable NEO GT1351M (Product)" are placed on the low refractive index B stage coating film surface of the laminated film. Name) ”) was placed, and after placing a weight of 500 g on it, 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 irradiating the light incident angle of the fluorescent lamp at various angles, and evaluated according to the following criteria.
A: No trace of contact with latex gloves was observed.
B: The part where the latex gloves were in contact had a slight cloudiness when looking through the light up close, and I managed to distinguish it.
C: The transparency of the part in contact with the latex glove was clearly reduced, and it could be easily identified.
D: It was confirmed that the surface of the coating film was roughened by the contact with the latex gloves.

Technically, the above-mentioned test (b) tack-free test is considered to be an index of web handleability (difficulty of scratches and appearance defects due to contact of the coating film with a transfer roll or the like during web handling). Needless to say, when the above test (b) tack-free test is at a low level, it should be protected by a protective film after forming a low refractive index B stage coating film and before the coating film comes into contact with a transfer roll or the like. stomach.

In the following tests (c) to (nu), the laminated film (coating film is B stage) was ^{irradiated with ultraviolet rays having an integrated light intensity of 600 mJ / cm 2} , and the coating film was made into a C stage coating film (completely cured). The one 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) is measured using the turbidity meter "NDH2000 (trade name)" of Nippon Denshoku Industries Co., Ltd. It was measured.

(D) Haze:
According to JIS K7136: 2000, the haze (unit:%) of the laminated film (coating film is C stage) was measured using a turbidity meter "NDH2000 (trade name)" of Nippon Denshoku Industries Co., Ltd.

(E) Minimum reflectance:
Using the spectrophotometer "SolidSpec-3700 (trade name)" of Shimadzu Corporation and the reflection unit "absolute reflectance measuring device incident angle 5 ° (trade name)", follow the instructions of the spectrophotometer above and follow the instructions of the spectrophotometer. Under the condition of normal reflection (the reflection unit is installed in front of the integrating sphere), a black adhesive sheet is laminated on the surface of the laminated film (the coating film is C stage) opposite to the surface on the low reflectance layer side. The lowest reflectance is the lowest reflectance (unit:%) from the spectrum obtained by smoothing the reflectance spectrum of visible light (wavelength 380 to 780 nm) measured as a test piece. Read as. The black adhesive sheet is a black acrylic adhesive masterbatch "Black-OT" of Regino Color Industry Co., Ltd. on one side of a biaxially stretched polyethylene terephthalate resin film "E5431 (trade name)" having a thickness of 25 μm of Toyo Boseki Co., Ltd. -1338 (trade name) "20 parts by mass and Fujikura Kasei Co., Ltd. adhesive" LKU-01 (trade name) "100 parts by mass are mixed, and an applicator is used so that the thickness after drying becomes 35 μm. Obtained by painting. The L * value obtained by measuring the color from the surface of the adhesive layer of the black adhesive sheet was 3.13. The L * value is XYZ in accordance with JIS Z 8722: 2009, using the spectrophotometer "CM600d" of Konica Minolta Japan Co., Ltd., under standard light D65 illumination, geometric condition c, and a component that causes mirror reflection. It was obtained by measuring the coordinates and converting them into L * a * b * coordinates.

(F) Go board test (coating film adhesion):
According to JIS K5600-5-6: 1999, make 100 squares (1 square = 1 mm x 1 mm) of notches in the grid from the low refractive index layer side of the laminated film (coating film is C stage), and then apply the adhesion test tape. It was pasted on a grid, squeezed with a finger, and then peeled off. The evaluation criteria were in accordance with Table 1 of the above JIS standards.
Category 0: The edges of the cut are perfectly smooth and there is no peeling on any grid.
Category 1: Small peeling of the coating at the intersection of cuts. The cross-cut portion is clearly not affected by more than 5%.
Category 2: The coating is peeling off along the edges of the cut and / or at the intersection. The cross-cut area is clearly affected by more than 5% but not more than 15%.
Category 3: The coating film is partially or wholly peeled off along the edges of the cut, and / or various parts of the eye are partially or wholly peeled off. The cross-cut area is clearly affected by more than 15% but not more than 35%.
Category 4: The coating film has undergone large peeling partially or wholly along the edge of the cut, and / or some eyes have been partially or wholly peeled off. The cross-cut area is clearly affected by more than 35% but not more than 65%.
Category 5: When the degree of peeling exceeds Category 4.

(G) Water contact angle (initial water contact angle):
By a method calculated from the width and height of water droplets (see JIS R 3257: 1999), an automatic contact angle meter "DSA20 (trade name)" manufactured by KRUSS was used to obtain a laminated film (coating film is C stage). The water contact angle (unit: degree) on the surface of the low refractive index layer was measured.

(H) Pencil hardness:
According to JIS K5600-5-4: 1999, under the conditions of test length 25 mm and load 750 g, low refractive index of laminated film (coating film is C stage) using pencil "Uni (trade name)" of Mitsubishi Pencil Co., Ltd. The surface of the rate layer was measured. Whether or not a scar was generated was determined 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 with a size of 150 mm in length and 50 mm in width and collected so that the machine direction of the laminated film (coating film is C stage) is the vertical direction of the test piece, and the low refraction of the laminated film (coating film is C stage) is obtained. Place it on a JIS L0849: 2013 clock meter type tester (friction tester type 1) so that the rate layer is on the surface, and place the friction terminals of the tester on a four-layer gauze (Kawamoto Sangyo Co., Ltd. medical type 1). Cover with gauze), set it so that it comes into contact with the test piece, place a load of 500 g, and rub the coated surface of the test piece 250 times reciprocating under the conditions of a friction terminal movement distance of 60 mm and a speed of 1 reciprocation / second. The presence or absence of scratches was determined by visually observing the friction points of the test piece at a position 50 cm away from the fluorescent lamp under the fluorescent lamp. When no scratches were found, the same part of the test piece was rubbed 250 times back and forth, and then the work of visual observation was repeated. It was evaluated according to the following criteria.
A: No scratches are found even after 1000 round trips.
B: No scratches are observed after 750 round trips, but scratches can be observed after 1000 round trips.
C: No scratches are observed after 500 round trips, but scratches can be observed after 750 round trips.
D: No scratches are observed after 250 round trips, but scratches can be observed after 500 round trips.
E: The scratch can be recognized after 250 round trips.

(N) Chemical resistance:
Tested by mixing 20 ml of Johnson & Johnson sunscreen "Neutrogena Ultra Sheer Dry Touch Sunblock (trade name)" with 10 drops of Pilot Ink Red (trade name), Pilot's red ink. It was made into a liquid. A paper wiper (Nippon Paper Crecia Co., Ltd.) that collects a test piece with a size of 100 mm x 100 mm from a laminated film (coating film is C stage) and cuts it to a size of 30 mm x 40 mm on the surface of the low refractive index layer of the test piece. "Kimwipe (trade name)") was spread out, and 10 drops of the test solution were uniformly dropped onto the paper wiper using a dropper. After dripping, air bubbles between the paper wiper and the test piece were removed using a tweezers, the paper wiper and the test piece were brought into close contact with each other, and then the temperature was 80 ° C. (humidity was not controlled). After storing in the environment for 4 hours, the paper wiper containing the test solution on the test piece is removed, and the test piece is wiped with a water-soaked paper wiper and then wiped dry with a dry paper wiper. Then, the test solution adhering to the surface of the test piece was removed. Then, the test piece was visually observed by a person with corrected visual acuity of 1.0 with the naked eye or using a loupe (10 times), and evaluated according to the following criteria.
A: No cracks were observed even when the loupe was used. No difference in color tone was observed between the portion of the surface of the low refractive index layer of the laminated film that was in contact with the test solution and the portion that was not in contact with the test solution.
B: No cracks were observed even when the loupe was used. However, there was a difference in color tone between the portion of the surface of the low refractive index layer of the laminated film that was in contact with the test solution and the portion that was not in contact with the test solution (the contacted portion was reddish as compared with the non-contacted portion). .).
C: No cracks were observed with the naked eye. However, when using the loupe, cracks were observed.
D: Cracks were also observed with the naked eye.

Raw materials used (A) Active energy ray-curable resin:
(A1) Urethane (meth) acrylate:
(A1-1) Polyfunctional urethane (meth) acrylate "Art Resin UN-953 (trade name)" of Negami Kogyo Co., Ltd. Solid content 40% by mass, number of functional groups (number of (meth) acryloyl groups per molecule; the same applies hereinafter) 20, number average molecular weight 2000, mass average molecular weight 26000, Z average molecular weight 110,000.
(A1-2) Negami Kogyo Co., Ltd.'s polyfunctional urethane (meth) acrylate "Art Resin UN-952 (trade name)", solid content 60% by mass, number of functional groups 10, number average molecular weight 2500, mass average molecular weight 9100, Z Average molecular weight 23000.
(A1-3) Negami Kogyo Co., Ltd.'s polyfunctional urethane (meth) acrylate "Art Resin UN-954 (trade 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 Kogyo Co., Ltd.'s polyfunctional urethane (meth) acrylate "Art Resin UN-909 (trade name)", solid content 70% by mass, number of functional groups 9, number average molecular weight 1500, mass average molecular weight 13000, Z Average molecular weight 60,000.
(A1-5) Polyfunctional urethane (meta) acrylate "KRM8452 (trade name)" of Daicel Ornex Co., Ltd. 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) Polyfunctional urethane (meth) acrylate "UF-C051 (trade name)" of Kyoeisha Chemical Co., Ltd. Solid content 100% by mass, number of functional groups 2, number average molecular weight 1600, mass average molecular weight 34,000, Z average molecular weight 57,000.

(A2) Active energy ray-curable resin other than urethane (meth) acrylate:
(A2-1) "SIRIUS 501 (trade name)" of Osaka Organic Chemical Industry Co., Ltd. A copolymer having a dendrimer structure of dipentaerythritol hexaacrylate and a 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) Shikoku Kasei Kogyo Co., Ltd. 1,3,4,6-tetrakis (2-mercaptoethyl) glycoluryl "TS-G (trade name)".

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

(C) Photopolymerization initiator:
(C-1) IGM Resins α-Hydroxyalkylphenone-based photopolymerization initiator (1-hydroxycyclohexyl-phenylketone) "Omnirad 184 (trade name)".
(C-2) Acetophenone-based photopolymerization initiator from IGM Resins (2-hirodoxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propane -1-On) "Omnirad 127 (trade name)".
(C-3) Acylphosphine oxide-based photopolymerization initiator (bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide) "Omnirad 819 (trade name)" of IGM Resins.

(D) Other ingredients:
(D-1) Acryloyl group-containing fluoropolyether-based water repellent "KY-1203 (trade name)" of Shin-Etsu Chemical Co., Ltd. Solid content 20% by mass.
(D-2) Acrylic silicone leveling "NSH8430HF (trade name)" of Kusumoto Kasei Co., Ltd. Solid content 10% by mass.
(D-3) 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 manufactured by Nissan Chemical Industries, Ltd. "PGM-AC-2140Y (trade name)". Solid content 42% by mass, average particle size 15 nm.
(D-5)) CIK Nanotech Co., Ltd.'s methyl isobutyl ketone dispersion of zirconium oxide "ZRMIBK15WT% -P01 (trade name)". 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 (indicated as "PGM" in the table)
(E-2) Methyl isobutyl ketone (indicated as "MIBK" in the table)

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

(L-2-8) A coating material for forming a low refractive index layer was obtained in the same manner as in (L-1) above, except that the composition of the coating material for forming a low refractive index layer was changed as shown in Table 1. In the table, all the values in terms of solid content are shown except for the solvent ((E-1) 1-methoxy-2-propanol).

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

(P) Transparent resin film:
(P-1) A two-kind three-layer multi-manifold coextruded T-die, and a molten film with a first mirror surface roll (a roll on the side that holds the molten film and sends it to the next transfer roll) and a second mirror surface roll. Using a device equipped with a take-up machine equipped with a mechanism to press the "Calibre 301-4 (trade name)", an aromatic polycarbonate manufactured by Sumika Stylon Polycarbonate Co., Ltd., is continuously co-extruded from a co-extruded T-die, and the α1 layer is the first layer. The total thickness is 170 μm, the layer thickness of the α1 layer is 50 μm, and the layer thickness of the β layer is 70 μm. A transparent resin film having a layer thickness of 50 μm was obtained. At this time, the setting conditions were a set temperature of the T die of 300 ° C., a set temperature of the first mirror surface roll of 130 ° C.; a set temperature of the second mirror surface roll of 120 ° C., and a take-up speed of 9.5 m / min.

Example 1
(1) Corona discharge treatment was performed on both sides of the above (P-1). The wettability index was 64 mN / m on both sides.
(2) Next, a film Mayer bar type coating device is used on the surface of the above (P-1) on the α1 layer side, and the above (L-1) is applied so as to have a thickness of 100 nm after curing. After forming the wet coating film, the drying furnace set to an internal temperature of 60 ° C. is passed at a line speed at which the time required to pass from the inlet to the outlet is 1 minute to prepare the wet coating film. It was dry.
(3) Subsequently, a high-pressure mercury lamp type ultraviolet irradiation device 6 and a mirror-surface metal roll 7 having a diameter of 25.4 cm were opposed to each other, and a 365 filter (“365 filter (trade name)” of Eye Graphic Co., Ltd.) 8 was provided. The above conditions were calculated by using a curing device (FIG. 8), assuming that the temperature of the mirror surface metal roll 7 was 60 ° C., the lamp output was 80 W / cm, and the 365 filter 8 was not used, and the integrated light amount was 60 mJ / cm ^2. A laminate (web 9) having the wet coating film pre-dried on the surface on the α1 layer side of (P-1) is irradiated with ultraviolet rays on the surface of the laminate (web 9) on the wet coating film side. The treatment was carried out so as to be on the device 6 side to obtain a laminated film (the coating film was B stage). The "integrated light amount" in the table is a value calculated on the assumption that the integrated light amount of ultraviolet rays in the low refractive index B stage coating film forming step is not used in the 365 filter 8.
(4) The above tests (a) to (g) were performed. The results are shown in Table 1.

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

Examples 3-9
The same procedure as in Example 1 was carried out except that the paint shown in Table 1 was used instead of the above (L-1) as the paint for forming the low refractive index layer. The results are shown in Table 1.

By the production method of the present invention, a low refractive index B stage coating film could be industrially stably produced. By the preferred production method of the present invention, a low refractive index B-stage coating film having excellent three-dimensional moldability and web handleability could be industrially stably produced. The laminated film of the present invention had a good antireflection function, transparency, and adhesion to a film substrate after the low refractive index B stage coating film was completely cured (to C stage). Furthermore, it was considered that the antifouling property was also good from the value of the water contact angle.

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

(H) Paint for forming a coating film having three-dimensional moldability (described as "paint H" in the table):
(H-1) 117 parts by mass (A1-3) (70 parts by mass in terms of solid content), 60 parts by mass (A2-1) (30 parts by mass in terms of solid content), (C-2) 1.5 A coating material for forming a coating film having three-dimensional moldability by mixing and stirring parts by mass, 2 parts by mass of (D-2) (0.2 parts by mass in terms of solid content), and 80 parts by mass of (E-2). H-1) was obtained. In the table, all the values in terms of solid content are shown except for the solvent (the above (E-2) methyl isobutyl ketone).

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

(H-3) 155 parts by mass of (A1-2) above (93 parts by mass in terms of solid content), 7 parts by mass of (A2-2) above, 7 parts by mass of (C-2) above, (D-2) 2 above. Three-dimensional by mixing and stirring parts by mass (0.2 parts by mass in terms of solid content), 0.02 parts by mass in (D-3), and 333 parts by mass in (D-5) above (50 parts by mass in terms of solid content). A coating film-forming paint (H-3) having moldability was obtained. All the values in terms of solid content are shown in the table.

Example 10
(1) Corona discharge treatment was performed on both sides of the above (P-1). The wettability index was 64 mN / m on both sides.
(2) Next, the above (H-1) is applied onto the surface of the above (P-1) on the α1 layer side using a die-type coating device so that the thickness after curing is 18 μm. After forming the wet coating film, the drying furnace set to an internal temperature of 90 ° C. is passed at a line speed at which the time required to pass from the inlet to the outlet is 2 minutes, and the wet coating film is pre-dried. bottom.
(3) Subsequently, a high-pressure mercury lamp type ultraviolet irradiation device 6 and a mirror-surfaced metal roll 7 having a diameter of 25.4 cm were opposed to each other, and a 365 filter (“365 filter (trade name)” of Eye Graphic Co., Ltd.) 8 was provided. The above conditions were calculated by using a curing device (FIG. 8), assuming that the temperature of the mirror surface metal roll 7 was 60 ° C., the lamp output was 160 W / cm, and the 365 filter 8 was not used, and the integrated light amount was 400 mJ / cm ^2. A laminate (web 9) having the wet coating film pre-dried on the surface on the α1 layer side of (P-1) is irradiated with ultraviolet rays on the surface of the laminate (web 9) on the wet coating film side. The treatment was performed so as to be on the device 6 side, and the film was cured to the B stage state.
(4) Subsequently, a film Mayer bar method is applied on the surface of the coating film having three-dimensional moldability (B stage coating film) formed on the surface on the α1 layer side of the above (P-1). After curing, the above (L-1) is applied to a thickness of 100 nm using a work equipment to form a wet coating film, and then a drying furnace set at a furnace temperature of 60 ° C. is passed from the inlet to the outlet. The wet coating film was pre-dried by passing it at a line speed in which the time required for the above-mentioned process was 1 minute.
(5) Next, a high-pressure mercury lamp type ultraviolet irradiation device 6 and a mirror-surfaced metal roll 7 having a diameter of 25.4 cm were opposed to each other, and a 365 filter (“365 filter (trade name)” of Eye Graphic Co., Ltd.) 8 was provided. Preliminary under the condition that the temperature of the mirror surface metal roll 7 is 60 ° C., the lamp output is 80 W / cm, and the integrated light amount is 150 mJ / cm ^{2 calculated by using the curing device (FIG. 8) and assuming that the 365 filter 8 is not used.} The dried wet coating film was treated so that the surface of the laminate (web 9) on the wet coating film side was on the ultraviolet irradiation device 6 side to obtain a laminated film (coating film was B stage). The "integrated light amount" in the table is a value calculated on the assumption that the integrated light amount of ultraviolet rays in the low refractive index B stage coating film forming step is not used in the 365 filter 8.
(6) The above tests (a) to (nu) were carried out. The results are shown in Table 2.

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

Example 12
(1) Corona discharge treatment was performed on both sides of the above (P-1). The wettability index was 64 mN / m on both sides.
(2) Next, after the above (H-2) is completely cured (made into C stage) by using a die-type coating device on the surface on the α1 layer side of the above (P-1). It was applied so as to have a thickness of 18 μm to form a wet coating film.
(3) Next, the drying furnace set to the furnace temperature of 130 ° C. is passed at a line speed at which the time required to pass from the inlet to the outlet is 6 minutes to dry the wet coating film and B. Hardened to the stage state.
(4) The web that came out of the drying oven was handled while being held in a chill roll set at a temperature of 25 ° C., and then wound up.
(5) Subsequently, the above (L-1) was applied on the easily peeled surface of the biaxially stretched polyethylene terephthalate resin film having a thickness of 50 μm and which had been easily peeled on one side by using a film Mayer bar type coating device. After curing, it is applied to a thickness of 100 nm to form a wet coating film, and then a drying furnace set at a furnace temperature of 60 ° C. is passed at a line speed that takes 1 minute to pass from the inlet to the outlet. The wet coating film was pre-dried.
(6) Next, a high-pressure mercury lamp type ultraviolet irradiation device 6 and a mirror-surfaced metal roll 7 having a diameter of 25.4 cm were opposed to each other, and a 365 filter (“365 filter (trade name)” of Eye Graphic Co., Ltd.) 8 was provided. Preliminary under the conditions of a curing device (FIG. 8), a temperature of the mirror metal roll 7 of 60 ° C., a lamp output of 80 W / cm, and an integrated light amount of 150 mJ / cm ^{2 calculated assuming that the 365 filter 8 is not used.} The dried wet coating film was treated so that the surface of the laminate (web 9) on the wet coating film side was on the ultraviolet irradiation device 6 side to form a low refractive index B stage coating film. The "integrated light amount" in the table is a value calculated on the assumption that the integrated light amount of ultraviolet rays in the low refractive index B stage coating film forming step is not used in the 365 filter 8.
(7) Subsequently, in the above step (6), on the surface of the coating film having three-dimensional moldability (B stage coating film) formed on the surface on the α1 layer side of the above (P-1). The formed low refractive index B stage coating film was transferred by a thermal laminating method to obtain a laminated film (the coating film was B stage).
(8) The above tests (a) to (nu) were carried out. The results are shown in Table 2.

Example 13
The same procedure as in Example 12 was carried out except that the above (H-3) was used instead of the above (H-2) as the coating film forming paint having three-dimensional moldability. The results are shown in Table 2.

By the production method of the present invention, a low refractive index B stage coating film could be industrially stably produced. By the preferred production method of the present invention, a low refractive index B-stage coating film having excellent three-dimensional moldability and web handleability could be industrially stably produced. The laminated film of the present invention has a good antireflection function, transparency, adhesion to a film substrate, and antifouling property after the low refractive index B stage coating film is completely cured (to C stage). Was there. The preferred laminated film of the present invention also had good scratch resistance.

Examples of embodiments of the low refractive index B-stage coating of the present invention are summarized as follows.
[1].
A B-stage coating film for forming a low refractive index layer.
(A) Active energy ray-curable resin,
Formed using a paint containing (B) low refractive index particles and (C) photopolymerization initiator.
Here, the component (C) photopolymerization initiator has an absorption peak having a peak top value of maximum absorbance in the wavelength range of 220 to 280 nm; the absorbance is maximum absorbance on the longer wavelength side than the peak top of the absorption peak. The wavelength that becomes 1/2 of the maximum absorbance is 290 nm or less; the absorbance at any wavelength in the wavelength range of 290 to 400 nm is 1/2 or less of the maximum absorbance;
The 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 above component (C) photopolymerization initiator is 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hirodoxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl}- 2-Methyl-Propane-1-one, 2-Hydroxy-2-methyl-1-phenyl-Propane-1-one, 1- [4- (2-Hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl -1-Propane-1-one, 2-Methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, and 1-hydroxycyclohexyl-phenylketone with benzophenone 100: 0- One or more selected from the group consisting of a 45:55 (mass ratio) mixture; the B-stage coating for forming a low refractive index layer according to item [1] or item [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 polystyrene-equivalent number average molecular weight (Mn) obtained from the differential molecular weight distribution curve measured by gel permeation chromatography of the component (A1) urethane (meth) acrylate is 1000 or more; any of the items [1] to [4]. The B-stage coating film for forming a low refractive index layer according to item 1.
[6].
The number of (meth) acryloyl groups contained in the above component (A1) urethane (meth) acrylate is 2 to 20 per 1000 polystyrene-equivalent number average molecular weight (Mn) obtained from the differential molecular weight distribution curve measured by gel permeation chromatography. The B-stage coating film for forming a low refractive index layer according to any one of items [1] to [5].
[7].
A laminated film having 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 a film substrate, and the B-stage coating film. The above-mentioned laminated film forming a surface.
[8].
A layer of a coating film which is a laminated film and has three-dimensional moldability on at least one surface of a film base material, and B for forming a low refractive index layer according to any one of items [1] to [6]. The laminated film having a stage coating film in this order and the B stage coating film forming a surface.
[9].
A molded product having a low refractive index layer formed by 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 product molded using the laminated film according to item [7] or item [8].
[11].
An article containing the molded article according to item [9] or item [10].

It is a graph which shows the relationship between the wavelength and the specific energy intensity when monochromatic with a 365 filter. 6 is a wavelength-absorbance curve of the acetonitrile solution of the photopolymerization initiator (C-1) used in the examples. It is a wavelength-absorbance curve of the acetonitrile solution of the photopolymerization initiator (C-2) used in an Example. It is a wavelength-absorbance curve of the acetonitrile solution of the photopolymerization initiator (C-3) used in an Example. It is a GPC curve of urethane (meth) acrylate (A1-1) used in an Example. It is a conceptual diagram explaining vacuum forming. It is a front view (a) and a plan view (b) of the molding die used in an Example. It is a conceptual diagram of the ultraviolet irradiation apparatus used in an Example.

1: Laminated film 2: Heating device 3: Molding die 4: Space between the laminated film and the molding die 5: Molded body 6: Ultraviolet irradiation device 7: Mirror metal roll 8: 365 Filter 9: Web

Claims (10)

A method for producing a B-stage coating film capable of forming a low refractive index layer.
(1) On the surface of the film substrate
(A) Active energy ray-curable resin,
A step of forming a wet coating film using (B) low refractive index particles and (C) a coating material containing a photopolymerization initiator;
(2) The wet coating film is irradiated with active energy rays to bring it into a B stage state;
Here, the active energy ray is monochromatic using a filter so as not to include a wavelength having an absorbance of 1/2 or more of the maximum absorbance of the component (C) photopolymerization initiator;
The above manufacturing method.
The active energy ray is monochromatic using a filter so as to include a wavelength having an absorbance of 1/10 to 1/100 of the maximum absorbance of the component (C) photopolymerization initiator; claim 1. The manufacturing method described in.
The above filter is a 365 filter;
The above component (C) photopolymerization initiator
It has an absorbance peak with a peak top value of maximum absorbance in the wavelength range of 220 to 280 nm;
The wavelength at which the absorbance is 1/2 of the maximum absorbance on the longer wavelength side than the peak top of the absorption peak is 290 nm or less;
Absorbance is less than 1/2 of maximum absorbance at any wavelength in the wavelength range of 290-400 nm;
The manufacturing method according to claim 1 or 2.
The above 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 manufacturing method according to any one of claims 1 to 3.
The above filter is a 365 filter;
The above component (C) photopolymerization initiator is 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hirodoxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl}- 2-Methyl-Propane-1-one, 2-Hydroxy-2-methyl-1-phenyl-Propane-1-one, 1- [4- (2-Hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl -1-Propane-1-one, 2-Methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, and 1-hydroxycyclohexyl-phenylketone with benzophenone 100: 0- One or more selected from the group consisting of a 45:55 (mass ratio) mixture;
The manufacturing method according to any one of claims 1 to 4.
The production method according to any one of claims 1 to 5, wherein the component (A) active energy ray-curable resin contains (A1) urethane (meta) acrylate.
The polystyrene-equivalent number average molecular weight (Mn) obtained from the differential molecular weight distribution curve measured by gel permeation chromatography of the above component (A1) urethane (meth) acrylate is 1000 or more; any one of claims 1 to 6. The manufacturing method described in.
The number of (meth) acryloyl groups contained in the above component (A1) urethane (meth) acrylate is 2 to 20 per 1000 polystyrene-equivalent number average molecular weight (Mn) obtained from the differential molecular weight distribution curve measured by gel permeation chromatography. The production method according to any one of claims 1 to 7.
It is a manufacturing method of laminated film.
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 8 on at least one surface of a film substrate;
The above-mentioned manufacturing method including.
It is a manufacturing method of laminated film.
A step of forming a coating film having three-dimensional moldability on at least one side of a film substrate;
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 8 is formed on the surface of the coating film having three-dimensional moldability formed in the above step. The process of forming;
The above-mentioned manufacturing method including.

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