JP2022025616A - Cured film and laminate, and method for producing the same - Google Patents

Abstract

To provide a cured film and a laminate, excellent in delustering properties; and to provide a method for producing the cured film.SOLUTION: Provided is a cured film formed by irradiating an active energy ray-curable composition with active energy rays, and the cured film whose surface has a wrinkle-like uneven structure, and in the cured film, the active energy ray-curable composition contains a polymer having an active group which generates radicals by irradiation with active energy rays. Provided is a method for producing the cured film, in which the active energy ray-curable composition containing the polymer having the active group that generates the radicals by irradiation with the active energy rays is irradiated with excimer light to be cured. Provided is a laminate formed by having the cured film laminated on a base material. Provided is a method for producing the laminate, in which the active energy ray-curable composition containing the polymer having the active group that generates the radicals by irradiation with the active energy rays on the base material, is laminated and cured by irradiation with the excimer light.SELECTED DRAWING: None

Description

The present invention relates to a cured film and a laminate, and a method for producing these.

In order to impart matte properties to building materials such as wallpaper, display members, decorative films, etc., the surface of the base material may be provided with fine irregularities. Further, these members may be required to have antistatic properties.
Patent Document 1 discloses a method of irradiating the surface of a biaxially oriented thermoplastic resin film used for a magnetic recording medium with excimer laser light to form fine irregularities.
Patent Document 2 describes, as a method of forming irregularities on the film surface having a hard coat layer used for an antireflection film, by irradiating a film on which a hard coat layer containing a hard coat resin and inorganic fine particles is formed with excima light. , A method of decomposing a portion of the hardcourt resin on the surface layer is disclosed.

Japanese Unexamined Patent Publication No. 4-305430 Japanese Unexamined Patent Publication No. 2014-224920

However, the method described in Patent Document 1 can only obtain a specific uneven structure in which a sufficient matting effect cannot be obtained. Further, since unevenness is directly formed on the biaxially oriented thermoplastic resin film, it is difficult to apply it to a display application or the like which is used by imparting various surface properties such as scratch resistance and antistatic property.
In the method described in Patent Document 2, only the hard coat resin of the hard coat layer is decomposed to expose the inorganic fine particles to the surface, so that the particles are easily dropped off, which hinders visibility when used for a display or the like. It may come. Further, there is a problem that the surface uneven structure is limited by the shape and distribution of particles.
An object of the present invention is to provide a cured film and a laminated body having excellent mattability, and a method for producing such a cured film and a laminated body.

The present invention has the following aspects.
[1] A cured film formed by irradiating an active energy ray-curable composition with active energy rays, which has a wrinkled uneven structure on the surface, and the curable composition is exposed to the activation energy rays. A cured film containing a polymer having an active group that generates radicals.
[2] The active group is a benzophenone group, an acetophenone group, a benzoin group, an α-hydroxyketone group, an α-aminoketone group, an α-diketone group, an α-diketone dialkylacetal group, an anthraquinone group, a thioxanthone group, and a phosphine oxide group. The cured film according to the above [1], which is at least one group selected from the group consisting of.
[3] The cured film according to the above [1] or [2], wherein the curable composition contains (meth) acrylate.
[4] The cured film according to any one of [1] to [3] above, wherein the average length (RSm) of the roughness curve element according to JIS B0601: 2013 of the uneven structure is 1 μm or more.
[5] The cured film according to any one of [1] to [4] above, wherein the arithmetic mean height (Sa) of the uneven structure defined by ISO25178 is 0.1 μm or more.
[6] The cured film according to any one of [1] to [5], wherein the average value (θa) of the local inclination angle of the uneven structure is 2 ° or more.
[7] The cured film according to any one of [1] to [6] above, wherein the surface 60 ° gloss is 50 or less.
[8] Any of the above [1] to [7], wherein the active energy ray-curable composition containing a polymer having an active group that generates radicals by irradiation with active energy rays is irradiated with excimer light and cured. The method for producing a cured film described in Kana.
[9] A laminated body in which the cured film according to any one of [1] to [7] is laminated on a substrate.
[10] The laminate according to the above [9], wherein the base material is a film.
[11] The above-mentioned [9], in which an active energy ray-curable composition containing a polymer having an active group that generates radicals by irradiation with active energy rays is laminated on a substrate and cured by irradiating with excima light. Alternatively, the method for producing a laminate according to [10].

The cured film and laminate of the present invention are excellent in matte property. According to the method for producing a cured film and a laminated body of the present invention, a cured film and a laminated body having excellent mattability can be obtained.

Hereinafter, embodiments of the present invention will be described in detail.
In the present invention, "(meth) acrylate" is a general term for acrylate or methacrylate. "(Meta) acrylic" is a general term for acrylic and methacrylic acid. "~" Indicating a numerical range means that the numerical values described before and after the numerical range are included as the lower limit value and the upper limit value.

[Cured film]
The cured film of the present invention (hereinafter, simply referred to as "cured film") is formed by irradiating an active energy ray-curable composition with active energy rays, and has a wrinkle-like uneven structure (non-smooth structure) on the surface. It has. The curable composition contains a polymer having an active group that generates radicals by irradiation with active energy rays. The cured film of the present invention is suitable as an antiglare film because it has excellent matting properties.

(Average length of roughness curve elements)
The average length of the roughness curve element in the uneven structure of the cured film is the average length of the roughness curve element according to JIS B0601: 2013 (RSm, hereinafter simply referred to as “RSm”). The evaluation length when calculating RSm is 236.87 μm. The preferred range of RSm is 1 μm or more, more preferably 5 to 120 μm, still more preferably 7 to 80 μm, particularly preferably 10 to 60 μm, and most preferably 15 to 40 μm. Within the above range, the matte property is excellent, and the visibility when used for a display or the like is excellent.

(Arithmetic mean height)
The arithmetic mean height in the uneven structure of the cured film is the arithmetic mean height (Sa, hereinafter simply referred to as “Sa”) defined in ISO25178. The evaluation length when calculating Sa is 236.87 μm. Sa is preferably in the range of 0.1 μm or more, more preferably 0.15 to 20 μm, still more preferably 0.2 to 10 μm, particularly preferably 0.3 to 5 μm, and most preferably 0.4 to 3 μm. Within the above range, the matte property is excellent, and the visibility when used for a display or the like is excellent.

(Average value of inclination angle of uneven structure)
The average value (θa, hereinafter simply referred to as “θa”) of the local inclination angle in the uneven structure of the cured film can be measured by the method described in Examples described later. The evaluation length when calculating θa was 236.87 μm. θa is preferably in the range of 2 ° or more, more preferably 2.5 ° or more, further preferably 3 ° or more, particularly preferably 3.5 ° or more, most preferably 4 ° or more, and the upper limit is 90. ° may be used. If it is in this range, it has good matteness.

(Thickness)
The thickness of the cured film (concave and convex layer) is preferably 0.1 to 100 μm, more preferably 0.2 to 20 μm, still more preferably 0.3 to 10 μm, and particularly preferably 0.3, from the viewpoint of improving the matte property. The range is ~ 7 μm. The thickness of the cured film indicates the maximum thickness of the uneven layer, and is determined by observing the cross section with an electron microscope.

(Haze)
The haze of the cured film measured by the method described in Examples described later is preferably 1% or more, more preferably 3% or more, still more preferably 5% or more, particularly preferably 10% or more, and most preferably. Is in the range of 20% or more, and the upper limit is, for example, 99%. The higher the haze, the better the matteness tends to be.
Further, particularly when used for anti-glare of various displays, the range is preferably 40% or more, more preferably 50% or more, still more preferably 60% or more, and the upper limit is, for example, 99%. Also, depending on the application, the higher the value, the more preferable the application.

(gross)
The 60 ° gloss (60 ° mirror gloss) of the surface of the cured film measured by the method described in Examples described later is preferably 50 or less, more preferably 40 or less, still more preferably 30 or less, and particularly preferably 25. Hereinafter, the range is most preferably 20 or less, and the lower the range, the more preferable. The smaller the 60 ° gloss value, the better the matte property.
Similarly, the 20 ° gloss is preferably in the range of 30 or less, more preferably 20 or less, further preferably 15 or less, particularly preferably 10 or less, and most preferably 8 or less, and the lower the value, the more preferable. The smaller the 20 ° gloss value, the better the matte property.

(Pencil hardness)
The pencil hardness of the cured film measured by the method described in Examples described later is preferably F or more, more preferably H or more, still more preferably 2H or more. Within the above range, it has excellent scratch resistance and is suitable for applications such as displays where visibility is important.
By using an active energy ray-curable composition containing a polymer having an active group that generates radicals by irradiation with active energy rays, the present inventor not only improves the matting property of the cured film, but also pencils. It was found that the hardness was improved. This is because the compatibility with other components in the curable composition is improved by incorporating the active group into the polymer as compared with the activator which is a general single molecule, and the curing of the cured film is promoted. It is presumed to be due.

[Manufacturing method of cured film and laminate]
In the cured film of the present invention and the laminate of the present invention having the same (hereinafter, simply referred to as “laminate”), for example, a coating film of a curable composition is laminated on a substrate, and the surface side (hereinafter, the coating film) of the coating film is laminated. It can be manufactured by a method of forming a cured film on the surface of the base material by irradiating the surface of the base material with active energy rays (on the opposite side of the base material).
By irradiating the surface side of the coating film of the curable composition with active energy rays, the surface side of the coating film is cured first to form a cured film. After that, when the inside of the coating film is cured, the cured film on the surface side that has been cured first buckles, so that a cured film having a wrinkle-like uneven structure is formed on the surface.

(Curable composition)
The curable composition used for forming the cured film contains a polymer having an active group that generates radicals by irradiation with active energy rays. If necessary, the curable composition may further contain an active energy ray-curable compound other than a polymer having an active group that generates radicals by irradiation with active energy rays, an organic solvent, and other components.

The present inventor has found that by containing a polymer having an active group that generates radicals by irradiation with active energy rays in the curable composition, it is possible to easily impart an uneven structure to the cured film. That is, by incorporating a polymer having an active group that generates radicals by irradiation with active energy rays into the curable composition, the formation of a concavo-convex structure can be facilitated, and the composition range of the curable composition capable of forming the concavo-convex structure. Found that it can be expanded. In addition, it has been found that the cured film can be made harder.

(Polymer having an active group that generates radicals by irradiation with active energy rays)
A polymer having an active group that generates radicals by irradiation with active energy rays (hereinafter, also referred to as “polymer (X)”) is a structure that generates radicals by irradiation with active energy rays (hereinafter, “photopolymerization start”). Any structure may be used as long as it has a "structure having sex"). As the structure having photopolymerization initiation property, various known structures can be adopted, and examples thereof include a hydrogen extraction type, an electron transfer type, and an intramolecular cleavage type.
Examples of the active group include a benzophenone group, an acetophenone group, a benzoin group, an α-hydroxyketone group, an α-aminoketone group, an α-diketone group, an α-diketone dialkylacetal group, an anthraquinone group, a thioxanthone group and a phosphine oxide group. Be done. As the α-hydroxyketone group, for example, one hydrogen atom was removed from the “hydroxyl group in 2-hydroxyethoxy” of 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-methylpropanol. The group is mentioned. As the active group, a benzophenone group, an acetophenone group, and an α-hydroxyketone group are preferable because they are less susceptible to oxygen inhibition during curing and have good surface curability when forming an uneven layer.
The active group may be present at the end of the main chain of the polymer (X) or in a unit based on the monomer constituting the polymer (X).
The polymer (X) preferably has a plurality of active groups in the molecule. As a result, the concentration of the active group near the surface of the coating film can be increased, oxygen inhibition is less likely to occur, the curability can be improved, and unevenness such as a wrinkle-like structure can be easily developed on the surface after curing.

As the polymer (X), a polymer having a unit based on a monomer having an active group is preferable from the viewpoint of introducing a plurality of active groups into the molecule.
Examples of the monomer having an active group include compounds having an active group and a radically polymerizable group. Examples of the radically polymerizable group include the same as described above.
As the monomer having an active group, a (meth) acrylic acid ester having an active group is preferable from the viewpoint of easiness of synthesizing the polymer (X) and easiness of adjusting the amount of the active group introduced. Examples of the monomer having an active group include 4-methacryloyloxybenzophenone and 2- [4- (2-hydroxy-2-methyl-1-oxopropyl) phenoxy] ethyl methacrylate.

The polymer (X) preferably has a unit based on a monomer having an alkyl group having 4 or more carbon atoms in addition to a unit based on a monomer having an active group. If the polymer (X) has this unit, the polymer (X) tends to segregate on the surface side of the coating film when the coating film of the curable polymer composition is formed. When the polymer (X) segregates on the surface side of the coating film, the curing reaction inside the coating film (base material layer side) is less likely to be subject to oxygen inhibition, and the curability is improved. For example, it can be cured with a low exposure amount, and even a thin film that tends to be susceptible to oxygen inhibition can be cured satisfactorily.
The alkyl group having 4 or more carbon atoms may be linear, branched or cyclic. The cyclic alkyl group may be monocyclic or polycyclic. From the viewpoint of more effectively segregating the polymer (X) on the surface of the coating film, the alkyl group is preferably linear.
The carbon number of the alkyl group having 4 or more carbon atoms is preferably in the range of 4 to 30, more preferably in the range of 6 to 20, and further preferably in the range of 4 to 30, from the viewpoint of more effectively segregating the polymer (X) on the surface of the coating film. It is preferably in the range of 12-18.

Examples of the monomer having an alkyl group having 4 or more carbon atoms include a compound having an alkyl group having 4 or more carbon atoms and a radically polymerizable group. From the viewpoint of easy adjustment of the introduction amount, a (meth) acrylic acid ester having an alkyl group having 4 or more carbon atoms is preferable.
Examples of the monomer having an alkyl group having 4 or more carbon atoms include butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and octyl. (Meta) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate, myristyl (meth) ) Acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, tridecyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, tricyclodecane (meth) acrylate, dicyclopentanyl Examples thereof include (meth) acrylate, isobornyl (meth) acrylate, and adamantyl (meth) acrylate.
Among these, it is preferable to contain a (meth) acrylic acid ester having a linear alkyl group having 4 or more carbon atoms. The (meth) acrylic acid ester having a linear alkyl group having 4 or more carbon atoms is preferably one in which the number of carbon atoms of the alkyl group is in the above-mentioned preferable range, and considering the ease of production and the like, 2-. Ethylhexyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, and stearyl (meth) acrylate are more preferable, and stearyl (meth) acrylate is particularly preferable.
One of these (meth) acrylic acid esters may be used alone, or two or more thereof may be used in combination.

The polymer (X) is added to a unit based on a monomer having an alkyl group having 4 or more carbon atoms, or has 4 carbon atoms, from the viewpoint of segregating the polymer (X) on the surface of the coating film more effectively. Instead of the above-mentioned unit based on the monomer having an alkyl group, it may have a unit based on a monomer containing a fluorine atom or a silicon atom.
As the monomer containing a fluorine atom, a (meth) acrylic acid ester containing a fluorine atom is preferable, and a (meth) acrylic acid ester having a perfluoroalkyl group is more preferable. The perfluoroalkyl group preferably has 4 or more carbon atoms.
The monomer containing a silicon atom is preferably a (meth) acrylic acid ester having a polydimethylsiloxane chain.

The polymer (X) may further have a unit based on the monomer having a hydrogen donating functional group, if necessary. In particular, when a hydrogen abstraction type is included as the active group, it is preferable to include a unit based on a monomer having a hydrogen donating functional group. When the polymer (X) has this unit, the curable polymer composition can be effectively cured from the surface of the coating film, the curability can be improved, and unevenness can be easily formed. ..
Examples of the hydrogen donating functional group include a hydroxyl group, an amino group, a mercapto group, an amide group and the like. Among these, a hydroxyl group, an amino group or an amide group is preferable from the viewpoint that the curing reaction can be promoted particularly efficiently, the curability can be improved, or unevenness can be easily formed.
Examples of the monomer having a hydrogen-donating functional group include a compound having a hydrogen-donating functional group and a radically polymerizable group, and the ease of synthesizing the compound and the amount of the hydrogen-donating functional group introduced can be adjusted. From the viewpoint of ease, a (meth) acrylic acid ester having a hydrogen donating functional group is preferable.
Examples of the monomer having a hydrogen donating functional group include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 6-hydroxyhexyl (meth) acrylate. , 8-Hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, monobutylhydroquilfumarate, monobutylhydroxyitaconate and other hydroxyl group-containing monomers; N, N- Dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-vinylcaprolactam, N-vinylpyrrolidone, N-isopropyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylate, 2-[( Butylamino) carbonyl] oxy] ethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylamide, N, N-diethylaminopropyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylate, N, N -Dimethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, (meth) acryloylmorpholine, vinyl Examples thereof include an amino group such as acetoamide or an amide group-containing monomer. Among these, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, (N, N-) are excellent in the effect of promoting curing when used in combination with an active group. Dimethylacrylamide, N, N-dimethylaminoethyl (meth) acrylate and N, N-diethylaminoethyl (meth) acrylate are preferable, and N, N-diethylaminoethyl (meth) acrylate is more preferable in that unevenness is easily increased. These compounds may be used alone or in combination of two or more.

The polymer (X) may further have a unit based on a monomer other than the above, if necessary. Examples of other monomers include compounds having a radically polymerizable group and having no active group, an alkyl group having 4 or more carbon atoms, a fluorine atom and a hydrogen donating functional group.
Other monomers include, for example, carboxyl group-containing monomers such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, citraconic acid and salts thereof; methyl (meth) acrylate, ethyl (meth). ) (Meta) acrylates such as acrylates and propyl (meth) acrylates; Nitrogen-containing monomers such as (meth) acrylonitrile; styrene compounds such as styrene, α-methylstyrene, divinylbenzene and vinyltoluene, vinyl propionate, vinyl acetate and the like. Vinyl esters; silicon-containing monomers such as γ-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane; phosphorus-containing vinyl-based monomers; vinyl halides such as vinyl chloride and billidene chloride; conjugated diene such as butadiene.

The content of the active group per 1 g of the polymer (X) is preferably 0.1 to 3.5 mmol / g, more preferably 0.3 to 3.0 mmol / g, still more preferably 0.5 to 2. It is in the range of 7 mmol / g, particularly preferably 1.0 to 2.5 mmol / g. When the content of the active group is within the above range, the curability is more excellent and the unevenness can be formed more effectively.
The ratio of the units based on the monomer having an active group to the total mass of all the units constituting the polymer (X) is preferably 1 to 90% by mass, more preferably 10 to 80% by mass, and further preferably 20. It is in the range of about 70% by mass, particularly preferably 30 to 60% by mass. When the ratio of the unit based on the monomer having an active group is within the above range, the curability can be improved and the unevenness can be formed more effectively.

The ratio of the units based on the monomer having an alkyl group having 4 or more carbon atoms to the total mass of all the units constituting the polymer (X) is preferably 80% by mass or less, more preferably 1 to 70% by mass. It is more preferably in the range of 5 to 60% by mass, and particularly preferably in the range of 8 to 50% by mass. When the ratio of the unit based on the monomer having an alkyl group having 4 or more carbon atoms is within the above range, the curability can be improved and the unevenness can be formed more effectively.

The ratio of the units based on the monomer having a hydrogen donating functional group to the total mass of all the units constituting the polymer (X) is preferably 80% by mass or less, more preferably 1 to 60% by mass, still more preferably. Is in the range of 3 to 50% by mass, particularly preferably 5 to 40% by mass. When the ratio of the unit based on the monomer having a hydrogen donating functional group is within the above range, the curability can be improved and the unevenness can be formed more effectively.

The weight average molecular weight (Mw) of the polymer (X) is preferably in the range of 1000 to 100,000, more preferably 3,000 to 50,000, and even more preferably 5,000 to 30,000. When Mw is within the above range, the coatability and curability of the curable polymer composition are improved, and the ease of forming irregularities is improved.
Mw of the polymer (X) is a standard polystyrene-equivalent value measured by gel permeation chromatography (GPC). Detailed measurement conditions are as described in Examples described later.

The glass transition temperature (Tg) of the polymer (X) is preferably in the range of −30 to 150 ° C., more preferably 0 to 120 ° C., and even more preferably 25 to 100 ° C. When Tg is within the above range, the curability can be improved and the ease of forming irregularities can be improved.
The polymer (X) can be obtained, for example, by polymerizing a monomer component containing a monomer having an active group. The monomer component may be a monomer having an alkyl group having 4 or more carbon atoms, a monomer containing a fluorine atom, a monomer having a hydrogen donating functional group, and other monomers, if necessary. Any one or more of the above may be further contained.

Polymerization is typically carried out in the presence of a polymerization initiator. At the time of polymerization, a chain transfer agent may be used in combination, if necessary. Examples of the polymerization method include known methods such as solution polymerization, suspension polymerization, bulk polymerization, and emulsion polymerization. Among them, solution polymerization is preferable because it is easy to operate and has high productivity.

The content of the polymer (X) in the curable composition is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, still more preferably, with respect to the non-volatile content (all components excluding the solvent). Is in the range of 1.0% by mass or more, particularly preferably 2.0% by mass or more, and most preferably 3.0% by mass or more. The upper limit is not particularly limited and may be 100% by mass, but when the hardness of the cured film is taken into consideration, it is preferably 50% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less, and particularly preferably 15. It is in the range of mass% or less, most preferably 10 mass% or less. The higher the content, the better the formation of surface irregularities of the cured film.
The non-volatile content of the curable composition is the total mass of components other than the solvent such as an organic solvent. The non-volatile content of the curable composition can be measured by a conventionally known method, for example, the weight when 1 g of the composition is spread and heated at 100 ° C. for 1 hour to volatilize the organic solvent. Measured by change.

(Active energy ray-curable compound other than polymer (X))
The active energy ray-curable composition is an active energy ray-curable compound other than the polymer (X) in order to easily form an uneven structure of a cured film, improve scratch resistance, and improve hardness (hereinafter,). , Also referred to as "compound (Y)") is also a preferable form. Examples of the compound (Y) include (meth) acrylate. The (meth) acrylate is not particularly limited, and is a monofunctional (meth) acrylate, a bifunctional (meth) acrylate, a trifunctional or higher functional (meth) acrylate, and a commercially available active energy ray-curable resin material. Alternatively, in addition to these, those to which other components are further added can be used as long as the object of the present embodiment is not impaired.
As the (meth) acrylate, monofunctional or bifunctional (meth) acrylate is preferable from the viewpoint of easily forming a wrinkle-like uneven structure. In order to increase the hardness and scratch resistance of the cured film, a polyfunctional (meth) acrylate having three or more functionalities is generally preferable. However, according to the study of the present inventor, it has been found that it may be difficult to form a wrinkle-like uneven structure depending on the type of polyfunctional (meth) acrylate having three or more functionalities. However, it has been found that when used in combination with the polymer (X), a concavo-convex structure is easily formed even when a trifunctional or higher functional (meth) acrylate is used. Therefore, according to the present invention, by using a polyfunctional (meth) acrylate having three or more functionalities, it is possible to easily achieve both the formation of an uneven structure and the hardness of the cured film.

Examples of the trifunctional or higher functional (meth) acrylate include dipentaerythritol hexa (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, and tri. Ethyleneoxide-modified (meth) acrylates such as trimethylolpropane tri (meth) acrylate, ethylene oxide-modified dipentaerythritol hexa (meth) acrylate, and ethylene oxide-modified pentaerythritol tetra (meth) acrylate, isocyanuric acid ethylene oxide-modified tri (meth) acrylate. , Ε-caprolactone-modified tris (acroxyethyl) isocyanurate-modified tri (meth) acrylate, pentaerythritol triacrylate hexamethylenediisocyanate urethane prepolymer, pentaerythritol triacrylate toluenediisocyanate urethane prepolymer, dipentaerythritol pentaacrylate Examples thereof include urethane acrylates such as hexamethylene diisocyanate urethane prepolymer. Among these, ethylene oxide-modified type and trifunctional (meth) acrylate are preferable in consideration of the ease of forming a wrinkled uneven structure. Further, considering the hardness and scratch resistance of the cured film, it is preferable to contain (meth) acrylate having 6 or more functionalities, and examples thereof include dipentaerythritol hexa (meth) acrylate and ethylene oxide-modified dipentaerythritol hexa (meth) acrylate. Further, a modified type of dipentaerythritol hexa (meth) acrylate such as ethylene oxide modification is more preferable because it is easier to form irregularities.

Examples of the bifunctional polyfunctional (meth) acrylate include 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and 1, Alcandiol di (meth) acrylates such as 9-nonandiol di (meth) acrylates and tricyclodecanedimethylol di (meth) acrylates, bisphenol A ethylene oxide-modified di (meth) acrylates, bisphenol F ethylene oxide-modified di (meth). Examples thereof include bisphenol-modified di (meth) acrylate such as acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, urethane di (meth) acrylate, and epoxy di (meth) acrylate. Among these, considering the ease of forming a wrinkled uneven structure, a structure without branching is preferable, an alkyldiol di (meth) acrylate is more preferable, and an alkyldiol di (4 to 18 carbon atoms) having 4 to 18 carbon atoms is preferable. Meta) acrylate is more preferred.

Examples of the active energy ray-curable monofunctional (meth) acrylate include methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate. , Cyclohexyl (meth) acrylate, alkyl (meth) acrylate such as isobornyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate and other hydroxyalkyl (meth) acrylate, methoxyethyl Aromas such as alkoxyalkyl (meth) acrylates such as (meth) acrylate, ethoxyethyl (meth) acrylate, methoxypropyl (meth) acrylate and ethoxypropyl (meth) acrylate, benzyl (meth) acrylate and phenoxyethyl (meth) acrylate. Amino group-containing (meth) acrylates such as (meth) acrylate, diaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, methoxyethylene glycol (meth) acrylate, phenoxypolyethylene grease (meth) acrylate, phenylphenol ethylene oxide modification. Examples thereof include ethylene oxide-modified (meth) acrylates such as (meth) acrylates, glycidyl (meth) acrylates, and tetrahydrofurfuryl (meth) acrylates.

The curable composition may contain an active energy ray-curable compound other than the (meth) acrylate. Examples of such a compound include vinyl compounds such as (meth) acrylic acid, styrene, vinyl halide and vinyl acetate, and diene compounds such as vinylidene halide, 1,3-butadiene, isoprene and chloroprene.

When the compound (Y) is blended in the curable composition, the content thereof is preferably 5 to 99.99% by mass, more preferably 30 to 99.9% by mass, still more preferably, based on the non-volatile content. It is in the range of 40 to 99% by mass, particularly preferably 50 to 98% by mass, and most preferably 60 to 97% by mass. In the above range, a wrinkled uneven structure is likely to be formed, and a cured film having excellent hardness can be formed.
In particular, in applications where it is necessary to improve the hardness and scratch resistance of the cured film, it is preferable that the content of the trifunctional or higher polyfunctional (meth) acrylate is high, and the content of the trifunctional or higher polyfunctional (meth) acrylate is high. The amount is preferably 5% by mass or more, more preferably 30% by mass or more, still more preferably 60% by mass or more, particularly preferably 80% by mass or more, and the upper limit is 99.99% by mass with respect to the non-volatile content. It is a range.
Further, in applications where hardness is more important, it is preferable to blend a polyfunctional (meth) acrylate having 6 or more functionalities, and the content in that case is preferably 5% by mass or more with respect to the non-volatile content, more preferably. Is 10% by mass or more, more preferably 20% by mass or more, and the upper limit is in the range of 99.99% by mass.

(resin)
Various resins other than the polymer (X) can be further blended in the curable composition for the purpose of improving the adhesion to the substrate, for example, acrylic resin, polyester resin, polyurethane resin, polyvinyl resin. Examples thereof include conventionally known resins such as. Among these, acrylic resin is particularly preferable in that it is excellent in transparency and affinity with the polymer (X) and the compound (Y).
When the resin is contained in the curable composition, the content thereof is preferably 50% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less, and particularly preferably 10 with respect to the non-volatile content. It is in the range of mass% or less. The smaller the content, the higher the hardness of the cured film tends to be.

(particle)
It is also possible to add particles to the curable composition in order to further improve the matting property due to the wrinkle-like uneven structure of the cured film. The particles are not particularly limited, and for example, inorganic particles such as silica, hollow silica, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, calcium phosphate, magnesium phosphate, kaolin, aluminum oxide, zirconium oxide, titanium oxide, acrylic resin, and the like. Examples thereof include organic particles such as styrene resin, urea resin, phenol resin, epoxy resin and benzoguanamine resin. The inorganic particles may be particles surface-modified with a silane coupling agent having a reactive group such as a (meth) acryloyl group. The organic particles are preferably a crosslinked type for maintaining the shape, and more preferably crosslinked acrylic resin particles and crosslinked styrene resin particles. Two or more kinds of these particles may be used in combination.
The average primary particle diameter of the particles is preferably in the range of 0.01 to 30 μm, more preferably 0.05 to 10 μm, still more preferably 0.1 to 5 μm, and particularly preferably 0.5 to 3 μm. In the range, it is excellent in improving the matte property.
When the particles are blended, the content thereof is preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably 20% by mass, based on the non-volatile content in the curable composition from the viewpoint of improving the matting property. It is in the range of 10% by mass or less, particularly preferably 8% by mass or less.

(Photopolymerization initiator)
A photopolymerization initiator may be added to promote the curability of the curable composition. The molecular weight of the photopolymerization initiator is preferably 1000 or less. Specific examples include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin phenyl ether, benzyl diphenyl disulfide, dibenzyl, diacetyl, anthraquinone, naphthoquinone, 3,3'-dimethyl-4-. methoxybenzophenone, benzophenone, p, p'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, pivaloyl in ethyl ether, benzyl dimethyl ketal, 1,1-dichloro acetophenone, p-t-butyl Dichloroacetophenone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-diethylthioxanthone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-dichloro-4-phenoxyacetophenone, Phenylglycioxylate, α-hydroxyisobutylphenone, dibenzosparone, 1- (4-isopropylphenyl) -2-hydroxy-2-methyl-1-propanol, 2-methyl- [4- (methylthio) phenyl] -2- Examples thereof include morpholino-1-propanone, tribromophenyl sulfone and tribromomethylphenyl sulfone. These photopolymerization initiators may be used alone or in combination of two or more.
When the photopolymerization initiator is blended, the content thereof is preferably 20% by mass or less, more preferably 10% by mass or less, still more preferably 10% by mass, based on the non-volatile content, from the viewpoint of promoting curability and hardness of the cured film. It is in the range of 8% by mass or less, particularly preferably 5% by mass or less.

(Leveling agent)
In order to improve the appearance of the cured film, a leveling agent can be added to the curable composition. Examples of the leveling agent include an acrylic leveling agent, a silicone-based leveling agent, and a fluorine-based leveling agent. These leveling agents may be used alone or in combination of two or more.
When a leveling agent is blended, the content thereof is preferably 10% by mass or less, more preferably 8% by mass or less, still more preferably 5% by mass or less, based on the non-volatile content, from the viewpoint of improving the appearance of the cured film. Is in the range of.

(Various additives)
The curable composition includes various types of polymerization accelerators such as compounds containing thiol groups, antifouling agents, plasticizers, surfactants, antioxidants, ultraviolet absorbers and the like, as long as the effects of the present invention are not impaired. Additives may be added.

(Organic solvent)
An organic solvent may be added to the curable composition, if necessary, for the purpose of improving workability when the curable composition is applied to the substrate.
Examples of the organic solvent include aromatic solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone, acetone, methyl isobutyl ketone and cyclohexanone; diethyl ether, isopropyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether and ethylene glycol diethyl ether. , Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, anisole, phenetol and other ether solvents; ethyl acetate, butyl acetate, isopropyl acetate, ethylene glycol diacetate and other ester solvents; dimethylformamide, diethylformamide, N-methyl Examples thereof include amide-based solvents such as pyrrolidone; cellosolve-based solvents such as methyl cellosolve, ethyl cellosolve and butyl cellosolve; alcohol-based solvents such as methanol, ethanol, propanol, isopropanol and butanol; halogen-based solvents such as dichloromethane and chloroform; and the like. One of these organic solvents may be used alone, or two or more of them may be used in combination. Of these organic solvents, ester-based solvents, ether-based solvents, alcohol-based solvents, and ketone-based solvents are preferable because they can easily improve workability in coating.
When an organic solvent is added to the curable composition, the content thereof is preferably 10 parts by mass or more and 1900 parts by mass or less, preferably 40 parts by mass, with respect to 100 parts by mass of the non-volatile content, from the viewpoint of improving operability in the coating operation. More than 400 parts by mass is more preferable.

(Formation of coating film)
Examples of the method for forming a coating film of the curable composition include a method of applying the curable composition on the surface of a base material or an article to form a coating film and drying it if necessary. The method of coating is not particularly limited, but for example, known methods such as a dip coating method, an air knife coating method, a curtain coating method, a spin coating method, a roller coating method, a bar coating method, a wire bar coating method, a gravure coating method, and a spray coating method are known. Method can be mentioned.
When the curable composition contains an organic solvent, it is preferable to heat-dry it in advance before irradiating it with active energy rays. By heating and drying in advance, the solvent in the coating film can be effectively removed. The drying temperature for heat drying is preferably 30 ° C. or higher and 200 ° C. or lower, and more preferably 40 ° C. or higher and 150 ° C. or lower. The drying time is preferably 0.01 minutes or more and 30 minutes or less, and more preferably 0.1 minutes or more and 10 minutes or less.

(Irradiation of active energy rays)
The coating film of the curable composition formed on the surface of the base material or the article is irradiated with active energy rays to form a cured film, and a laminated body in which the cured film is laminated on the base material or the article is formed. As the active energy rays, those having high energy capable of effectively curing the surface of the coating film (those having a short wavelength) are preferable, and vacuum ultraviolet rays (ultraviolet rays having a wavelength of 200 nm or less) are more preferable. Among the vacuum ultraviolet rays, excimer light having a half width of 50 nm or less is the most suitable. Examples of the excimer light include argon excimer light (126 nm), krypton excimer light (146 nm), xenon excimer light (172 nm), and argon / fluorine excimer light (193 nm). Among these, xenon excimer light is preferable in consideration of ease of use, the formation of an effective uneven structure on the cured film, the curability of the curable composition, and the like.

When vacuum ultraviolet rays are used, the integrated amount of light to be irradiated is preferably 1 to 3000 mJ / cm ² , more preferably 3 to 1000 mJ / cm ² , still more preferably 5 to 500 mJ / cm ² , and particularly preferably 10 to 100 mJ / cm ² . Is in the range of. The illuminance is preferably in the range of 1 to 500 mW / cm ² , more preferably 2 to 300 mW / cm ² , and even more preferably 3 to 100 mW / cm ² .
Further, as the atmosphere at the time of vacuum ultraviolet irradiation, it is preferable to perform it in an environment with little oxygen such as a nitrogen atmosphere. The oxygen concentration in the atmosphere is preferably in the range of 10% or less, more preferably 5% or less, still more preferably 3% or less, and particularly preferably 1% or less.

After irradiation with vacuum ultraviolet rays, it is preferable to irradiate with active energy rays other than vacuum ultraviolet rays in order to cure the cured film to a deep part. Examples of the active energy ray include ultraviolet rays and electron beams. Examples of ultraviolet rays include ultraviolet rays having a wavelength of 200 nm or more emitted from high-pressure mercury lamps, low-pressure mercury lamps, metal halide lamps, UV-LED lamps, and the like. Examples of the electron beam include an electron beam irradiated from an EB irradiator or the like. As the active energy rays other than vacuum ultraviolet rays, ultraviolet rays are more preferable in consideration of the curability of the curable composition.

The integrated amount of ultraviolet rays to be irradiated is preferably in the range of 1 to 5000 mJ / cm ² , more preferably 50 to 3000 mJ / cm ² , still more preferably 100 to 1000 mJ / cm ² , and particularly preferably 200 to 700 mJ / cm ² . .. The illuminance is preferably in the range of 1 to 1000 mW / cm ² , more preferably 50 to 500 mW / cm ² , and even more preferably 80 to 300 mW / cm ² .

[Laminate]
The laminate of the present invention has a layer made of a base material and a layer (concave and convex layer) made of a cured film of a curable composition. The laminate may further have a primer layer between the substrate and the cured film. Further, the back surface functional layer may be provided on the surface of the base material opposite to the cured film side. A surface functional layer may be provided on the surface of the cured film opposite to the base material as long as the effects of the present invention are not impaired.

(Base material)
As the base material, known ones can be used, and examples thereof include a resin base material, a metal base material, and a paper base material. Among these, a resin base material is preferable from the viewpoint of processability. The resin base material may have a single-layer structure or a multi-layer structure having two or more layers, and is not particularly limited. It is preferable that the resin base material has a multi-layer structure of two or more layers, and each layer has a characteristic to be multifunctional.
As the resin base material, various resin films (sheets) can be used, for example, polyester film, poly (meth) acrylate film, polyolefin film, polycarbonate film, polyimide film, triacetyl cellulose film, polystyrene film, polyvinyl chloride film. , Polyvinyl alcohol film, nylon film and the like.
When developing the laminate for display applications, polyester film, poly (meth) acrylate film, polyolefin film, polycarbonate film, polyimide film, and triacetyl cellulose film are preferable. Among these, polyester films, poly (meth) acrylate films, and polyolefin films are preferable for anti-glare applications, and polyester films are more preferable in consideration of transparency, moldability, and versatility.

The polyester film may be a non-stretched film or a stretched film, and a stretched film is preferable. Among them, a uniaxially stretched film stretched in the uniaxial direction or a biaxially stretched film stretched in the biaxial direction is preferable, and a biaxially stretched film is more preferable from the viewpoint of excellent balance of mechanical properties and flatness.
The polyester constituting the polyester film that can be used as a base material may be a homopolyester or a copolymerized polyester.
The homopolyester is preferably obtained by polycondensing an aromatic dicarboxylic acid and an aliphatic glycol. Examples of the aromatic dicarboxylic acid include terephthalic acid and 2,6-naphthalenedicarboxylic acid. Examples of the aliphatic glycol include ethylene glycol, diethylene glycol, and 1,4-cyclohexanedimethanol. Aromatic dicarboxylic acid and aliphatic glycol may be used alone or in combination of two or more.
Examples of the dicarboxylic acid component of the copolymerized polyester include isophthalic acid, phthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid, and oxycarboxylic acid. Examples of the glycol component include ethylene glycol, diethylene glycol, propylene glycol, butanediol, 4-cyclohexanedimethanol, and neopentyl glycol. The dicarboxylic acid component and the glycol component may be used alone or in combination of two or more.
Examples of typical polyesters include polyethylene terephthalate and polyethylene naphthalate.
As the polyester film, in consideration of mechanical strength and heat resistance, a film formed of polyethylene terephthalate or polyethylene naphthalate is more preferable, and ease of manufacture and handleability as a surface protective film or the like are more preferable. In consideration of the above, a film formed from polyethylene terephthalate is particularly preferable.

As the poly (meth) acrylate constituting the poly (meth) acrylate film that can be used as a base material, any acrylic resin may be used as long as it has a unit based on the (meth) acrylate. Examples of the (meth) acrylate include an alkyl (meth) acrylate having an alkyl group having 1 to 4 carbon atoms such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and butyl (meth) acrylate. , Alkyl (meth) acrylates having an alkyl group having a higher number of carbon atoms can be mentioned.
Considering transparency, processability, and chemical resistance, the poly (meth) acrylate preferably contains a unit based on an alkyl (meth) acrylate having 1 to 4 carbon atoms as a main component, and is preferably a methyl (meth) acrylate. It is more preferable that the main component is at least one selected from the group consisting of units based on and ethyl (meth) acrylate-based units, and it is particularly preferable that the main component is a unit based on methyl (meth) acrylate.
It is also possible to impart properties such as flexibility by incorporating a unit based on (meth) acrylate other than the alkyl (meth) acrylate or a unit based on other monomers into the poly (meth) acrylate.
The ratio of the unit based on the alkyl (meth) acrylate having 1 to 4 carbon atoms to the total mass of the poly (meth) acrylate is preferably 50% by mass or more, more preferably 80% by mass or more.

The base material may contain particles for the purpose of imparting slipperiness, preventing scratches in each step, and improving blocking resistance.
The type of particles can be appropriately selected according to the purpose and is not particularly limited. Specific examples include inorganic particles such as silica, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, calcium phosphate, magnesium phosphate, kaolin, aluminum oxide, zirconium oxide, titanium oxide, acrylic resin, styrene resin, urea resin, and phenol. Examples thereof include organic particles such as a resin, an epoxy resin, and a benzoguanamine resin. Further, when the base material layer contains a polyester film, precipitated particles obtained by precipitating a part of a metal compound such as a catalyst in the polyester manufacturing process can also be used. Among these, silica particles and calcium carbonate particles are particularly preferable in that a small amount is likely to produce an effect.
The shape of the particles is not particularly limited, and any of spherical, lumpy, rod-shaped, flat-shaped, and the like may be used. Further, the hardness, specific gravity, color and the like are not particularly limited.
Two or more kinds of these particles may be used in combination as needed.
The average primary particle size of the particles is preferably in the range of 10 μm or less, more preferably 0.01 to 5 μm, and even more preferably 0.01 to 3 μm. When the average primary particle size is 10 μm or less, problems due to a decrease in the transparency of the base material are unlikely to occur.
The average primary particle diameter of the particles is a value of 50% (mass basis) integrated in the equivalent spherical distribution measured by the centrifugal sedimentation type particle size distribution measuring device.
When the base material contains particles, the content cannot be unequivocally determined because there is a balance with the average primary particle size of the particles, but the total mass of the base material (when the base material is composed of a plurality of layers). It is preferably in the range of 5% by mass or less, more preferably in the range of 0.0003 to 3% by mass, and further preferably in the range of 0.0005 to 1% by mass with respect to the total mass of the layer containing the particles). When the content of the particles is 5% by mass or less, problems such as falling off of the particles and deterioration of the transparency of the base material are unlikely to occur.

The base material may contain additives other than the above-mentioned particles, if necessary. As the additive, known additives such as an ultraviolet absorber, an antioxidant, an antistatic agent, a heat stabilizer, a lubricant, a dye, and a pigment can be used.
When the base material is a film, the thickness thereof is not particularly limited as long as it can be formed into a film, but is preferably in the range of 2 to 350 μm, more preferably 5 to 250 μm, and further preferably 10 to 100 μm. be.

(Primer layer)
The primer layer is appropriately provided to impart various functions between the base material and the cured film (concave and convex layer). The primer layer may have a single function or a plurality of functions, or may be composed of a plurality of layers.
In a preferred embodiment, the primer layer is an adhesion improving layer. If the adhesion between the base material and the uneven layer is insufficient, the laminate may not be usable depending on the application. By having the adhesion improving layer, the adhesion between the base material and the uneven layer is improved, and the laminated body can be used for various purposes. From the viewpoint of improving adhesion and the like, it is preferable that the adhesion improving layer contains either one or both of the resin and the compound derived from the cross-linking agent.
In another preferred embodiment, the primer layer is an antistatic layer. If the primer layer is an antistatic layer, it is possible to reduce the adhesion of dust and the like due to peeling charging and triboelectric charging to the outermost surface of the laminated body, particularly the outermost surface on the side where the uneven layer exists with respect to the base material.
To make the primer layer an antistatic layer, for example, the primer layer may contain an antistatic agent.

As the resin contained in the primer layer, a conventionally known resin can be used. Specific examples of the resin include polyester resin, acrylic resin, urethane resin, polyvinyl resin (polyvinyl alcohol, vinyl chloride-vinyl acetate copolymer, etc.) and the like. Among them, polyester resin, acrylic resin, and urethane resin are preferable in consideration of adhesion performance and coating property.
When the base material is a resin film, the resin contained in the primer layer is preferably a resin of the same type as the resin film from the viewpoint of compatibility with the base material. For example, when the base material is a polyester film, the primer layer preferably contains a polyester resin. When the base material is a poly (meth) acrylate film, the primer layer preferably contains an acrylic resin.

Examples of the polyester resin include those whose main constituents are a polyvalent carboxylic acid and a polyvalent hydroxy compound.
Examples of the polyvalent carboxylic acid include terephthalic acid, isophthalic acid, orthophthalic acid, 4,4'-diphenyldicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid and 2,6-naphthalenedicarboxylic acid. Acid, 2,7-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2-potassium sulfoterephthalic acid, 5-sodiumsulfoisophthalic acid, adipic acid, azelaic acid, sebacic acid, dodecandicarboxylic acid, glutaric acid, succinic acid Examples thereof include acids, trimellitic acids, trimesic acids, pyromellitic acids, trimellitic anhydrides, phthalic anhydrides, trimellitic acid monopotassium salts and ester-forming derivatives thereof.
Examples of the polyvalent hydroxy compound include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, and 2-methyl. -1,5-pentanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, p-xylylene glycol, bisphenol A-ethylene glycol adduct, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol , Polytetramethylene oxide glycol, dimethylolpropionic acid, glycerin, trimethylolpropane, sodium dimethylolethylsulfonate, potassium dimethylolpropionate.
One or more of each of these compounds may be appropriately selected, and the polyester resin may be synthesized by a conventional polycondensation reaction.

The acrylic resin is a polymer of a polymerizable monomer containing a (meth) acrylic monomer. Examples of the acrylic resin include homopolymers and copolymers of (meth) acrylic monomers, copolymers of (meth) acrylic monomers and polymerizable monomers other than (meth) acrylic monomers, and the like.
The acrylic resin may be a copolymer of these polymers and another polymer (for example, polyester, polyurethane, etc.). Such copolymers are, for example, block copolymers and graft copolymers. Alternatively, a polymer (in some cases, a mixture of polymers) obtained by polymerizing a polymerizable monomer in a polyester solution or dispersion is also included. Similarly, a polymer (in some cases, a mixture of polymers) obtained by polymerizing a polymerizable monomer in a solution or dispersion of polyurethane is also included. Similarly, a polymer (in some cases, a polymer mixture) obtained by polymerizing a polymerizable monomer in a solution or dispersion of another polymer is also included.
The polymerizable monomer is not particularly limited, but typical compounds include, for example, carboxyl group-containing monomers such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, and citraconic acid, and the like. Salt: 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, monobutylhydroquilfumarate, monobutylhydroxyitaconate and other hydroxyl group-containing monomers; methyl ( Alkyl (meth) acrylates such as meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate; (meth) acrylamide, Nitrogen-containing monomers such as diacetone acrylamide, N-methylol acrylamide and (meth) acrylonitrile; styrene compounds such as styrene, α-methylstyrene, divinylbenzene and vinyltoluene, vinyl esters such as vinyl propionate and vinyl acetate; γ- Silicon-containing monomers such as methacryloxypropyltrimethoxysilane and vinyltrimethoxysilane; phosphorus-containing vinyl-based monomers; vinyl halides such as vinyl chloride and billidene chloride; conjugated diene such as butadiene can be mentioned.

The urethane resin is a polymer compound having a urethane bond in the molecule, and is typically synthesized by a reaction between a polyol and a polyisocyanate compound. A chain extender may be used when synthesizing the urethane resin. Examples of the polyol used to obtain the urethane resin include polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, acrylic polyols and the like. These compounds may be used alone or in combination of two or more.

The polycarbonate polyol is obtained by a reaction (dealcohol reaction) between a polyhydric alcohol and a carbonate compound. Examples of the polyhydric alcohol include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, and 1,5-. Pentandiol, 1,6-hexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10- Examples thereof include decanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, and 3,3-dimethylol heptane. Examples of the carbonate compound include dimethyl carbonate, diethyl carbonate, diphenyl carbonate and ethylene carbonate. Specific examples of the polycarbonate polyol include poly (1,6-hexylene) carbonate and poly (3-methyl-1,5-pentylene) carbonate.

Examples of the polyether polyol include polyethylene glycol, polypropylene glycol, polyethylene propylene glycol, polytetramethylene ether glycol, and polyhexamethylene ether glycol.

Examples of the polyester polyol include those obtained by reacting a polyvalent carboxylic acid or an acid anhydride thereof with a polyhydric alcohol, and those having a derivative unit of a lactone compound such as polycaprolactone.
Examples of the polyvalent carboxylic acid include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, fumaric acid, maleic acid, terephthalic acid, and isophthalic acid.
Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butanediol, 1,3-butanediol, 1,4-butanediol, and 2,3-butane. Diol, 2-methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4- Pentandiol, 2-methyl-2-propyl-1,3-propanediol, 1,8-octanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol , 2,5-dimethyl-2,5-hexanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-butyl -2-hexyl-1,3-propanediol, cyclohexanediol, bishydroxymethylcyclohexane, dimethanolbenzene, bishydroxyethoxybenzene, alkyldialkanolamine, lactonediol and the like can be mentioned.

As the polyol, polyester polyol and polycarbonate polyol are preferable, and polyester polyol is particularly preferable, in consideration of adhesion performance.

Examples of the polyisocyanate compound used to obtain a urethane resin include aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, methylene diphenyl diisocyanate, phenylenedi isocyanate, naphthalenedi isocyanate, and trizine diisocyanate; α, α, α', An aliphatic diisocyanate having an aromatic ring such as α'-tetramethylxylylene diisocyanate; an aliphatic diisocyanate such as methylene diisocyanate, propylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene diisocyanate; cyclohexane diisocyanate, methylcyclohexanediisocyanate, isophorone diisocyanate. , Dicyclohexylmethane diisocyanate, alicyclic diisocyanate such as isopropyridene dicyclohexyldiisocyanate and the like. These may be used alone or in combination of two or more.
The chain extender is not particularly limited as long as it has two or more active groups that react with the isocyanate group, and generally, a chain extender having two hydroxyl groups or amino groups can be mainly used. ..
Examples of the chain extender having two hydroxyl groups include aliphatic glycols such as ethylene glycol, propylene glycol and butanediol, aromatic glycols such as xylylene glycol and bishydroxyethoxybenzene, and esters such as neopentyl glycol hydroxypivalate. Glycol compounds such as glycol can be mentioned.
Examples of the chain extender having two amino groups include aromatic diamines such as tolylene diamine, xylylene diamine, and diphenylmethanediamine, ethylenediamine, propylenediamine, hexanediamine, 2,2-dimethyl-1,3-propanediamine. , 2-Methyl-1,5-pentanediamine, trimethylhexanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 1,8-octanediamine, 1,9-nonandiamine, 1,10-decanediamine And other aliphatic diamines, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, dicyclohexylmethanediamine, isoprovilitincyclohexyl-4,4'-diamine, 1,4-diaminocyclohexane, 1,3 -Examples include alicyclic diamines such as bisaminomethylcyclohexane.

Urethane resins are typically used in the form of dispersions or solutions. As the medium of the dispersion liquid or the solution, a solvent may be used, but water is preferable.
Examples of the aqueous dispersion or aqueous solution of the urethane resin include a forced emulsification type using an emulsifier, a self-emulsifying type in which a hydrophilic group is introduced into the structure of the urethane resin, and a water-soluble type. In particular, the self-emulsifying type in which an ionic group is introduced into the structure of the urethane resin to form an ionomer is preferable because it is excellent in storage stability of the liquid and the water resistance and transparency of the obtained primer layer.
Examples of the ionic group introduced into the structure of the urethane resin include various groups such as a carboxyl group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group and a quaternary ammonium base, but a carboxyl group is preferable. ..
The carboxyl group is preferably in the form of a salt neutralized with a neutralizing agent such as ammonia, amines, alkali metals and inorganic alkalis. Particularly preferred neutralizers are ammonia, trimethylamine and triethylamine. For the urethane resin having a carboxyl group neutralized with a neutralizing agent, the carboxyl group from which the neutralizing agent has been removed in the drying step after coating can be used as a crosslinking reaction point by the crosslinking agent. This makes it possible to improve the stability of the obtained primer layer in the state of the liquid before coating, and to improve the durability, solvent resistance, water resistance, blocking resistance and the like of the obtained primer layer.
As a method for introducing a carboxyl group into the urethane resin, various methods can be taken in each stage of the polymerization reaction. For example, a method of using a resin having a carboxyl group as a copolymerization component at the time of prepolymer synthesis, and a method of using a component having a carboxyl group as one component of a polyol, a polyisocyanate compound, a chain extender and the like can be mentioned. In particular, a method of using a carboxyl group-containing diol and introducing a desired amount of carboxyl group according to the amount of this component charged is preferable. For example, a carboxyl group-containing diol can be copolymerized with a diol used for synthesizing a urethane resin.
Examples of the carboxyl group-containing diol include dimethylolpropionic acid, dimethylolbutanoic acid, bis- (2-hydroxyethyl) propionic acid, and bis- (2-hydroxyethyl) butanoic acid, and these carboxyl groups are neutralizing agents. Examples include neutralized salt.

In order to make the primer layer stronger and improve the performance such as adhesion, it is preferable that the primer layer contains a compound derived from a cross-linking agent.
As the cross-linking agent, known materials can be used, and examples thereof include melamine compounds, isocyanate compounds, oxazoline compounds, epoxy compounds, carbodiimide compounds, silane coupling compounds, hydrazide compounds, and aziridine compounds. Among them, melamine compounds, isocyanate compounds, epoxy compounds, oxazoline compounds, carbodiimide compounds, and silane coupling compounds are preferable, and from the viewpoint of further improving adhesion and durability, melamine compounds, oxazoline compounds, and isocyanate compounds are preferable. And epoxy compounds are more preferable, and melamine compounds, oxazoline compounds and isocyanate compounds are particularly preferable. These cross-linking agents may be used alone or in combination of two or more. Adhesion and durability may be further improved by using two or more types together.

The melamine compound is a compound having a melamine skeleton in the compound, for example, an alkyrylated melamine derivative, a compound obtained by reacting an alkyrylated melamine derivative with an alcohol to partially or completely etherify, and a compound thereof. Examples include mixtures. Examples of the alcohol used for etherification include methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butanol, and isobutanol. The melamine compound may be either a monomer or a multimer of a dimer or more, or a mixture thereof may be used. Further, a melamine cocondensed with urea or the like can be used, or a catalyst can be used to increase the reactivity of the melamine compound. As the melamine compound, a compound having a hydroxyl group is preferable in consideration of reactivity with various compounds.

The isocyanate-based compound is a compound having an isocyanate derivative structure typified by an isocyanate compound or a blocked isocyanate compound.
Examples of the isocyanate compound include aromatic isocyanate compounds such as tolylene diisocyanate, xylylene diisocyanate, methylene diphenyldiisocyanate, phenylenedi isocyanate and naphthalene diisocyanate; aromatic rings such as α, α, α', α'-tetramethylxylylene diisocyanate. Lipid isocyanate compounds such as methylene diisocyanate, propylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene diisocyanate; cyclohexanediisocyanate, methylcyclohexanediisocyanate, isophorone diisocyanate, methylenebis (4-cyclohexylisocyanate), isopropi. Examples thereof include alicyclic isocyanate compounds such as redendicyclohexyldiisocyanate. Further, polymers and derivatives such as burettes, isocyanurates, uretdiones, and carbodiimide-modified compounds of these isocyanate compounds can also be mentioned. These may be used alone or in combination of two or more. Among the above isocyanate compounds, an aliphatic isocyanate compound or an alicyclic isocyanate compound is preferable to an aromatic isocyanate compound from the viewpoint of avoiding yellowing due to ultraviolet rays.
Examples of the blocked isocyanate compound include those in which the isocyanate group of the isocyanate compound is blocked with a blocking agent. Examples of the blocking agent include phenolic compounds such as heavy sulfites, phenol, cresol and ethylphenol, alcoholic compounds such as propylene glycol monomethyl ether, ethylene glycol, benzyl alcohol, methanol and ethanol, dimethyl malonate and diethyl malonate. , Methyl isobutanoyl acetate, methyl acetoacetate, ethyl acetoacetate, acetylacetone and other active methylene compounds, butyl mercaptan, dodecyl mercaptan and other mercaptan compounds, ε-caprolactam, δ-valerolactam and other lactam compounds, diphenylaniline, aniline , Amine compounds such as ethyleneimine, acid amide compounds such as acetanilide and acetate amide, and oxime compounds such as formaldehyde, acetaldoxime, acetone oxime, methyl ethyl ketone oxime and cyclohexanone oxime. These may be used alone or in combination of two or more.
As the blocked isocyanate compound, an isocyanate compound blocked with an active methylene compound is preferable from the viewpoint that the primer layer is not easily destroyed.
The isocyanate compound may be used alone, or may be used as a mixture or a bond with various polymers. In the sense of improving the dispersibility and crosslinkability of the isocyanate compound, it is preferable to use a mixture or a bond with a polyester resin or a urethane resin.

The oxazoline compound is a compound having an oxazoline group in the molecule. As the oxazoline compound, a polymer containing an oxazoline group is preferable. The polymer containing an oxazoline group can be obtained by polymerization of an addition-polymerizable oxazoline group-containing monomer alone or with another monomer.
Examples of the additive-polymerizable oxazoline group-containing monomer include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, and 2-isopropenyl-2. -Oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline can be mentioned. These may be used alone or in combination of two or more. Among these, 2-isopropenyl-2-oxazoline is suitable because it is easily available industrially.
The other monomer is not particularly limited as long as it is a monomer copolymerizable with the addition-polymerizable oxazoline group-containing monomer, and is, for example, an alkyl (meth) acrylate (as the alkyl group, a methyl group, an ethyl group, or an n-propyl group). , Isobutyl group, n-butyl group, isobutyl group, t-butyl group, 2-ethylhexyl group, cyclohexyl group) and other (meth) acrylates; acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, Unsaturated carboxylic acids such as styrene sulfonic acid and salts thereof (sodium salt, potassium salt, ammonium salt, tertiary amine salt, etc.); unsaturated nitriles such as acrylonitrile and methacrylonitrile; (meth) acrylamide, N-alkyl ( Meta) acrylamide, N, N-dialkyl (meth) acrylamide, (alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, 2-ethylhexyl Unsaturated amides such as groups (groups, cyclohexyl groups, etc.); vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; α-olefins such as ethylene and propylene; vinyl chloride, vinylidene chloride and vinyl fluoride. Halogen-containing α, β-unsaturated monomers such as; α, β-unsaturated aromatic monomers such as styrene, α-methylstyrene, etc. may be mentioned. These may be used alone or in combination of two or more.
The amount of oxazoline groups per 1 g of the oxazoline compound is preferably in the range of 0.5 to 10 mmol / g, more preferably 1 to 9 mmol / g, still more preferably 3 to 8 mmol / g, and particularly preferably 4 to 6 mmol / g. .. When the amount of the oxazoline group is within the above range, the durability of the coating film is improved and the adhesion can be easily adjusted.

The epoxy compound is a compound having an epoxy group in the molecule. Examples of the epoxy compound include a condensate of epichlorohydrin and a compound having a hydroxyl group or an amino group (ethylene glycol, polyethylene glycol, glycerin, polyglycerin, bisphenol A, etc.), and examples thereof include polyepoxy compounds, diepoxy compounds, and the like. There are monoepoxy compounds, glycidylamine compounds and the like. Examples of the polyepoxy compound include sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, triglycidyltris (2-hydroxyethyl) isocyanate, glycerol polyglycidyl ether, and trimethylolpropane. Polyglycidyl ether can be mentioned. Examples of the diepoxy compound include neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, resorcin diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, and polypropylene glycol di. Examples thereof include glycidyl ether and polytetramethylene glycol diglycidyl ether. Examples of the monoepoxy compound include allyl glycidyl ether, 2-ethylhexyl glycidyl ether, and phenyl glycidyl ether. Examples of the glycidylamine compound include N, N, N', N'-tetraglycidyl-m-xylylenediamine and 1,3-bis (N, N-diglycidylamino) cyclohexane.

The carbodiimide-based compound is a compound having one or more carbodiimide structure or carbodiimide derivative structure in the molecule. As the carbodiimide-based compound, a polycarbodiimide-based compound having two or more carbodiimide structures or carbodiimide derivative structures in the molecule is more preferable from the viewpoint of the strength of the primer layer.
The carbodiimide-based compound can be synthesized by a known method, and a condensation reaction of a diisocyanate compound is generally used. The diisocyanate compound is not particularly limited, and any aromatic or aliphatic type can be used. For example, tolylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, phenylenedi isocyanate, naphthalenedi isocyanate, hexamethylene diisocyanate, etc. Examples thereof include trimethylhexamethylene diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, dicyclohexyldiisocyanate, and dicyclohexylmethane diisocyanate.
In order to improve the water solubility and water dispersibility of the polycarbodiimide compound, a surfactant may be added as long as the effect of the present invention is not lost, or a quaternary ammonium salt of a polyalkylene oxide or a dialkylaminoalcohol may be added. , Hydrophilic monomers such as hydroxyalkyl sulfonates may be added.

The silane coupling compound is an organic silicon compound having an organic functional group and a hydrolyzing group such as an alkoxy group in one molecule. Examples of the silane coupling compound include 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane. Propyl group-containing compounds such as 2- (3,4-epyloxycyclohexyl) ethyltrimethoxysilane, vinyl group-containing compounds such as vinyltrimethoxysilane and vinyltriethoxysilane, p-styryltrimethoxysilane, p-styryltriethoxysilane Such as styryl group-containing compounds, 3- (meth) acryloxylpropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxy. (Meta) acryloyl group-containing compounds such as propylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N- 2- (Aminoethyl) -3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, Amino group-containing compounds such as 3-triethoxysilyl-N- (1,3-dimethylbutylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, Isocyanurate group-containing compounds such as tris (trimethoxysilylpropyl) isocyanurate and tris (triethoxysilylpropyl) isocyanurate, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane. , 3-Mercapto group-containing compounds such as mercaptopropylmethyldiethoxysilane.
Among the above compounds, the silane coupling compound contains an epoxy group-containing silane coupling compound, a double bond-containing silane coupling compound such as a vinyl group or a (meth) acrylic group, and an amino group from the viewpoint of the strength of the primer layer. Silane coupling compounds are preferred.

These cross-linking agents react in the drying process and the film forming process to improve the performance of the primer layer. It can be inferred that an unreacted product of the cross-linking agent, a compound after the reaction, or a mixture thereof is present as the compound derived from the cross-linking agent in the formed primer layer.

The antistatic agent contained in the primer layer is not particularly limited, and a known antistatic agent can be used. For example, a compound having an ammonium group, a polyether compound, a compound having a sulfonic acid group, and betaine. Examples include compounds and conductive organic polymers.
The primer layer may contain particles for blocking and improving slipperiness.
The primer layer may be a defoaming agent, a coating property improving agent, a thickener, an organic lubricant, an ultraviolet absorber, an antioxidant, a foaming agent, a dye, as necessary, as long as the gist of the present invention is not impaired. It may contain an additive such as a pigment.

The proportion of the resin in 100% by mass of the primer layer is, for example, 5% by mass or more, preferably 10 to 99% by mass, more preferably 20 to 95% by mass, and further preferably 30 to 90% by mass. When the ratio of the resin is within the above range, the adhesion performance and the appearance of the primer layer are more excellent.
The proportion of the compound derived from the cross-linking agent in 100% by mass of the primer layer is, for example, 80% by mass or less, preferably 0.5 to 65% by mass, more preferably 3 to 50% by mass, and further preferably 5 to 40% by mass. It is a range. When the ratio of the compound derived from the cross-linking agent is within the above range, the adhesion performance and the strength of the primer layer are more excellent.
The thickness of the primer layer cannot be unconditionally determined because it depends on the material used for the primer layer and the performance to be expressed, but it is preferably 0.001 to 10 μm, more preferably 0.01 to 4 μm, and further preferably 0. It is in the range of 02 to 1 μm.
The primer layer can be formed by a known method.

(Surface functional layer)
The surface functional layer is a layer provided to impart various functions to the surface of the cured film (concave and convex layer) opposite to the base material layer. Examples of the surface functional layer include an antifouling layer, an antistatic layer, a refractive index adjusting layer (antireflection layer, low reflection layer, etc.), an infrared absorption layer, an ultraviolet absorption layer, and a color correction layer. The surface functional layer may have a single function or a plurality of functions, or may be composed of a plurality of layers.

The antifouling layer is provided to improve the antifouling performance by imparting water repellency and oil repellency to the cured film. As the material used for the antifouling layer, conventionally known materials such as a silicone compound, a fluorine compound, and a long-chain alkyl group-containing compound can be used. Among these, a silicone compound or a fluorine compound is preferable for exhibiting stronger antifouling performance, and a fluorine compound or a long-chain alkyl group-containing compound is preferable from the viewpoint of not contaminating the partner with which the antifouling layer comes into contact.

Examples of the silicone compound are compounds having a silicone structure in the molecule, and examples thereof include alkyl silicones such as dimethyl silicone and diethyl silicone, and phenyl silicone and methyl phenyl silicone having a phenyl group. As the silicone, those having various functional groups can also be used, for example, an ether group, a hydroxyl group, an amino group, an epoxy group, a carboxylic acid group, a halogen group such as fluorine, a perfluoroalkyl group, various alkyl groups and various types. Examples thereof include a hydrocarbon group such as an aromatic group. As other functional groups, silicones having a vinyl group and hydrogen silicones in which a hydrogen atom is directly bonded to a silicon atom are also common, and both are used in combination to form an addition type (type by an addition reaction between a vinyl group and a hydrogensilane). It can also be used as. Further, a method of introducing a double bond such as an acryloyl group and reacting at the double bond portion is also preferable.
Further, as the silicone compound, modified silicone such as acrylic graft silicone, silicone graft acrylic, amino-modified silicone, and perfluoroalkyl-modified silicone can also be used. Considering heat resistance and stain resistance, it is preferable to use a curable silicone resin, and any of the curable reaction types such as condensation type, addition type, and active energy ray curable type can be used as the curable type.

The fluorine compound is a compound containing a fluorine atom. As the fluorine compound, an organic fluorine compound is preferably used, and examples thereof include a perfluoroalkyl group-containing compound, a polymer of an olefin compound containing a fluorine atom, and an aromatic fluorine compound such as fluorobenzene. From the viewpoint of releasability, a compound having a perfluoroalkyl group is preferable. Further, as the fluorine compound, a compound containing a long-chain alkyl compound as described later can also be used.
Examples of the compound having a perfluoroalkyl group include perfluoroalkyl (meth) acrylate, perfluoroalkylmethyl (meth) acrylate, 2-perfluoroalkylethyl (meth) acrylate, and 3-perfluoroalkylpropyl (meth) acrylate. , 3-Perfluoroalkyl-1-methylpropyl (meth) acrylate, 3-perfluoroalkyl-2-propenyl (meth) acrylate and other perfluoroalkyl group-containing (meth) acrylates and polymers thereof, perfluoroalkylmethylvinyl ether , 2-Perfluoroalkyl ethyl vinyl ether, 3-perfluoropropyl vinyl ether, 3-perfluoroalkyl-1-methylpropyl vinyl ether, 3-perfluoroalkyl-2-propenyl vinyl ether and other perfluoroalkyl group-containing vinyl ethers and their polymers. Can be mentioned. Considering heat resistance and stain resistance, it is preferably a polymer. The polymer may be a single compound alone or a polymer of a plurality of compounds. Further, from the viewpoint of antifouling property, the perfluoroalkyl group preferably has 3 to 11 carbon atoms. Further, it may be a polymer with a compound containing a long-chain alkyl compound as described later.

The long-chain alkyl compound is a compound having a linear or branched alkyl group having a carbon atom number of usually 6 or more, preferably 8 or more, and more preferably 12 or more. Examples of the alkyl group include a hexyl group, an octyl group, a decyl group, a lauryl group, an octadecyl group, a behenyl group and the like. Examples of the compound having an alkyl group include various long-chain alkyl group-containing polymer compounds, long-chain alkyl group-containing amine compounds, long-chain alkyl group-containing ether compounds, and long-chain alkyl group-containing quaternary ammonium salts. .. Considering heat resistance and stain resistance, a polymer compound is preferable. Further, from the viewpoint of effectively obtaining antifouling property, a polymer compound having a long-chain alkyl group in the side chain is more preferable.
The polymer compound having a long-chain alkyl group in the side chain can be obtained by reacting a polymer having a reactive group with a compound having an alkyl group capable of reacting with the reactive group. Examples of the reactive group include a hydroxyl group, an amino group, a carboxyl group, and an acid anhydride group. Examples of the compound having these reactive groups include polyvinyl alcohol, polyethyleneimine, polyethyleneamine, a reactive group-containing polyester resin, and a reactive group-containing poly (meth) acrylic resin. Among these, polyvinyl alcohol is preferable in consideration of antifouling property and ease of handling.
Examples of the compound having an alkyl group capable of reacting with the above-mentioned reactive group include long-chain alkyl group-containing isocyanates such as hexyl isocyanate, octyl isocyanate, decyl isocyanate, lauryl isocyanate, octadecyl isocyanate and behenyl isocyanate, hexyl chloride and octyl chloride. , Isocyanate, lauryl chloride, octadecyl chloride, behenyl chloride and the like, long-chain alkyl group-containing acid chlorides, long-chain alkyl group-containing amines, long-chain alkyl group-containing alcohols and the like. Among these, long-chain alkyl group-containing isocyanates are preferable, and octadecyl isocyanates are particularly preferable, in consideration of releasability and ease of handling.
Further, the polymer compound having a long-chain alkyl group in the side chain can also be obtained by a polymer of a long-chain alkyl (meth) acrylate or a copolymerization of the long-chain alkyl (meth) acrylate with another vinyl group-containing monomer. .. Examples of the long-chain alkyl (meth) acrylate include hexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, octadecyl (meth) acrylate, and behenyl (meth) acrylate. ..

The content of the above-mentioned antifouling material for exhibiting the antifouling performance in the surface functional layer cannot be unequivocally determined because it depends on the material used, but in the case of a silicone compound or a fluorine compound, it is usually 0.01. It is in the range of mass% or more, more preferably 0.1% by mass or more, still more preferably 0.2% by mass or more, and the upper limit may be 100% by mass. When a long-chain alkyl group-containing compound is used, it is usually in the range of 0.1% by mass or more, preferably 1% by mass or more, more preferably 3% by mass or more, and the upper limit is 100% by mass. It doesn't matter. By using it in the above range, it can have effective antifouling performance.

As the antistatic agent used when forming the antistatic layer as the surface functional layer, various conventionally known antistatic agents can be used. Further, for example, a method of introducing a double bond such as an acryloyl group into a compound having an ammonium group and reacting at the double bond portion is also preferable.

Examples of the refractive index adjusting layer include a high refractive index layer, a low refractive index layer, and a laminate thereof.
Conventionally known materials can be used as the material of the refractive index adjusting layer for the purpose of increasing the refractive index, and for example, an aromatic-containing material such as a benzene structure, a bisphenol A structure, a melamine structure, and a fluorene structure can be used. Condensations such as naphthalene, anthracene, phenanthrene, naphthalene, benzo [a] anthracene, benzo [a] phenanthrene, pyrene, benzo [c] phenanthrene, and perylene structures, which are considered to be compounds having high refractive index among aromatic compounds. Metals such as cyclic aromatic compounds, zirconium oxide, titanium oxide, zinc oxide, tin oxide, antimon oxide, yttrium oxide, indium oxide, cerium oxide, ATO (antimon tin oxide), ITO (indium tin oxide) Examples thereof include metal-containing compounds such as oxides and metal chelate compounds such as titanium chelate and zirconium chelate, compounds containing sulfur elements, and compounds containing halogen elements.
The metal oxide is preferably used in the state of particles because there is a concern that the adhesion may be deteriorated depending on the usage mode, and the average primary particle diameter thereof is preferably 100 nm or less from the viewpoint of coating appearance and the like. The range is preferably 50 nm or less, more preferably 25 nm or less.
As the material of the refractive index adjusting layer for the purpose of lowering the refractive index, conventionally known materials can be used, and examples thereof include acrylic resin and urethane resin having a low refractive index. Further, in particular, a compound in which a fluorine atom is incorporated in a resin, for example, a fluororesin, a compound containing a fluororesin in the main species skeleton, and a compound containing a perfluoroalkyl group in the side chain can be mentioned. Further, examples of the inorganic material include hollow silica particles, fluorine atom-containing inorganic compounds such as magnesium fluoride and calcium fluoride, and hollow particles and nanoporous particles thereof.

The thickness of the surface functional layer is preferably 5 times or less, more preferably 2 times or less, the height from the concave portion to the convex portion of the concave-convex structure of the cured film. The smaller this magnification is, the less likely it is that the matting performance of the cured film will deteriorate. The thickness of the surface functional layer cannot be unequivocally determined because it depends on the height from the concave portion to the convex portion of the concave-convex structure of the cured film, but it is usually 0.001 to 3 μm, preferably 0.005 to 2 μm, and more preferably 0. The range is 01 to 1 μm, more preferably 0.02 to 0.5 μm, and particularly preferably 0.03 to 0.2 μm. By using it in the above range, it is possible to achieve both the expression of the function by the surface functional layer and the matte property of the cured film.
The surface functional layer can be formed by a known method.

(Back function layer)
The back surface functional layer is a layer provided to impart various functions to the surface of the base material layer opposite to the cured film (concave and convex layer). Examples of the back surface functional layer include an adhesive layer, an antistatic layer, a refractive index adjusting layer, and an anti-blocking layer. The back surface functional layer may have a single function or a plurality of functions, or may be composed of a plurality of layers.

The adhesive layer is provided to join the laminated body to various adherends. The antistatic layer is provided to prevent the adhesion of dust and the like due to peeling and triboelectric charging on the outermost surface of the laminated body, particularly the outermost surface on the side opposite to the uneven layer side of the base material layer, and defects due to the adhesion. The refractive index adjusting layer is provided, for example, in order to improve the total light transmittance of the laminated body. The anti-blocking layer is provided to reduce blocking of the laminate.
Examples of the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer include known pressure-sensitive adhesives such as acrylic, polyester, urethane, and rubber. Among them, an acrylic pressure-sensitive adhesive is preferable in consideration of versatility.
The components forming the antistatic layer and the refractive index adjusting layer are the same as those described in the surface functional layer.

The thickness of the back surface functional layer cannot be unequivocally determined because it depends on the material used for the back surface functional layer and the performance to be developed, but is, for example, 0.001 to 30 μm. When the back surface functional layer is an adhesive layer, it is preferably 0.01 to 30 μm, more preferably 0.1 to 20 μm. When the back surface functional layer is an antistatic layer, it is preferably 0.001 to 10 μm, more preferably 0.01 to 5 μm.
The back surface functional layer can be formed by a known method.

(Formation of front surface functional layer and back surface functional layer)
The front surface functional layer and the back surface functional layer are, for example, coated on a predetermined surface with a liquid prepared by using the above-mentioned series of components as a solution or a dispersion of a solvent and having a solid content concentration of about 0.1 to 80% by mass as a guide. It can be formed by drying and curing.
Examples of coating methods include gravure coat, reverse roll coat, die coat, air doctor coat, blade coat, rod coat, bar coat, curtain coat, knife coat, transfer roll coat, squeeze coat, impregnation coat, kiss coat, and spray coat. , Conventionally known coating methods such as a calendar coat and an extruded coat can be mentioned.
The drying and curing conditions for forming the front surface functional layer and the back surface functional layer are not particularly limited, but the drying of the solvent such as water used in the coating liquid is usually 50 to 150 ° C., preferably 50 to 150 ° C. It is in the range of 80 to 130 ° C., more preferably 90 to 120 ° C. As a guideline for the drying time, it is in the range of 3 to 200 seconds, preferably 5 to 120 seconds. Further, in order to improve the strength of the front surface functional layer and the back surface functional layer, it is preferable to perform heat treatment in the range of usually 150 to 270 ° C., preferably 170 to 230 ° C., and more preferably 180 to 210 ° C. after drying. As a guideline for the heat treatment time, it is in the range of 3 to 200 seconds, preferably 5 to 120 seconds. Such heat treatment is suitable when the laminate is a film.

(Total light transmittance)
The laminate is preferably transparent. The total light transmittance measured by the method described in Examples described later is preferably 50% or more, more preferably 60% or more, further preferably 70% or more, particularly preferably 80% or more, and most preferably 90%. The above range is preferable, and the higher the range, the more preferable (the upper limit is 100%).

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples as long as the gist thereof is not exceeded.
The measurement method and evaluation method used in the present invention are as follows.

(1) Extreme viscosity of polyester 1 g of polyester from which components incompatible with polyester have been removed is precisely weighed, 100 ml of a mixed solvent of phenol / tetrachloroethane = 50/50 (weight ratio) is added and dissolved, and the measurement is carried out at 30 ° C. did.

(2) Average primary particle diameter (d50: μm)
The value of 50% integrated (weight basis) in the equivalent spherical distribution measured using the centrifugal sedimentation type particle size distribution measuring device SA-CP3 manufactured by Shimadzu Corporation was taken as the average primary particle size.

(3) Weight average molecular weight (Mw) of the polymer (X)
The weight average molecular weight (Mw) of the acrylic polymer was measured using gel permeation chromatography (GPC) "HLC-8120" (manufactured by Tosoh Corporation). As the column, TSKgel G5000HXL * GMHXL-L (manufactured by Tosoh Corporation) was used. Further, as standard polystyrene, a calibration curve was prepared using F288 / F80 / F40 / F10 / F4 / F1 / A5000 / A1000 / A500 (manufactured by Tosoh Corporation) and styrene. The measurement was carried out at a column oven temperature of 40 ° C. using 100 μl of a solution in which the polymer was dissolved in tetrahydrofuran so as to have a concentration of 0.4%. The weight average molecular weight (Mw) was calculated in terms of standard polystyrene.

(4) Measurement of glass transition temperature (Tg) 5 mg of a sample is enclosed in an aluminum pan, and a differential scanning calorimeter (EXSTAR DSC6200 manufactured by Seiko Instruments) is used in a nitrogen atmosphere at a rate of 10 ° C. per minute. The temperature was raised and lowered from −100 ° C. to 250 ° C., from 250 ° C. to −100 ° C., and from −100 ° C. to 250 ° C., and the inflection point at the second temperature rise was defined as the glass transition temperature (Tg).

(5) RSm, Sa and tilt angle (θa)
Using a surface shape measurement system (Hitachi High-Tech Science, Inc. scanning white interference microscope "VS1330"), the surface shape of the surface of the cured film of 177.60 μm × 236.87 μm was measured by the optical interferometry method, and the data was obtained. An analysis was performed. The evaluation length used to calculate RSm and θa is 236.87 μm. The magnification of the objective lens at the time of measurement was set to 20 times for measurement. In this evaluation, the presence or absence of wrinkled uneven structure was also confirmed.
The processing conditions used for data analysis are as follows.
Surface correction: 4th order interpolation: Complete interpolation Filter: Medium 3 × 3 pixels Boundary processing: Symmetrical expansion to interpolate edges Trimming: None

(6) Total light transmittance / haze A laminated body having a cured film formed on a substrate was used as a measurement target. The total light transmittance and haze are JIS Z8722: 2009 (geometric conditions for irradiation and light reception of transmitted objects) and JIS K7361-1: 1997 (test method for total light transmittance of plastic-transparent material) JIS K7136: 2000 (plastic). -Measurement was performed using a haze meter "SH7000" manufactured by Japanese Industrial Standards Co., Ltd. in accordance with (How to obtain the haze of a transparent material).

(7) 20 ° and 60 ° gloss / matte property A laminated body having a cured film formed on a substrate was used as a measurement target. 20 ° and 60 ° gloss (20 ° and 60 ° mirror gloss) were measured using a gloss meter "VG2000" manufactured by Nippon Denshoku Kogyo Co., Ltd. in accordance with JIS Z 8741-1997. The lower the gloss value, the better the matte property.

(8) Pencil hardness JIS K5600-5-4: 1999 General paint test method-Part 5: Mechanical properties of coating film-Section 4: Scratch hardness (pencil method) was used to measure the pencil hardness of the cured film.

(9) Matte property A laminated body is installed in a room lit by a white, linear fluorescent lamp, and the distance between the fluorescent lamp and the laminated body is set to 2.5 m, and the matteness on the uneven layer side is visually observed. The sex (reflection of the fluorescent lamp) was evaluated according to the following evaluation criteria A to D. In the evaluations A to C, it is a judgment that the matte property can be confirmed.
A: The reflected image of the fluorescent lamp is strongly blurred, and the outline of the fluorescent lamp cannot be confirmed.
B: The reflected image of the fluorescent lamp is blurred, but the outline can be slightly confirmed.
C: The reflected image of the fluorescent lamp is a little blurry, and the outline can be confirmed, but it is observed in a wavy shape and appears dark white.
D: The reflected image of the fluorescent lamp is clear and the outline can be clearly confirmed, and it appears linear and white.

The materials used in the examples and comparative examples are as follows.
(Base material)
Polyester (S1): A polyethylene terephthalate homopolymer having an ultimate viscosity of 0.63 dl / g, which is obtained by using magnesium acetate tetrahydrate and tetrabutyl titanate as a polymerization catalyst.
Polyester (S2): A polyethylene terephthalate homopolymer having an ultimate viscosity of 0.64 dl / g, which is obtained by using magnesium acetate tetrahydrate, orthophosphoric acid and germanium dioxide as a polymerization catalyst.
Polyester (S3): A polyethylene terephthalate homopolymer containing 0.3% by mass of silica particles having an average primary particle diameter of 2 μm.

(Synthesis of (meth) acrylic acid ester having an active group)
(Synthesis Example 1) Synthesis of 2- [4- (2-hydroxy-2-methyl-1-oxopropyl) phenoxy] ethyl methacrylate A methacrylic anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd.) is distilled under reduced pressure to obtain a purity of 99. A fraction of 8% or more was recovered to obtain a distillate of methacrylic anhydride. The vacuum distillation was carried out by a method of gradually raising the temperature from room temperature to 90 ° C. at a pressure of 30 pa.
Separately, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-methylpropanol (manufactured by Tokyo Chemical Industry Co., Ltd.) 22.4 g (0.1 mol), and triethylamine (Tokyo Chemical Industry Co., Ltd.) 30.4 g (0.3 mol) manufactured by Methylene Chloride Tokyo Chemical Industry Co., Ltd.) was dissolved in 500 mL. 23.1 g (0.15 mol) of the distillate of the methacrylic anhydride was added dropwise thereto at room temperature, and the mixture was stirred for 12 hours.
The obtained reaction solution was washed 3 times with 500 mL of ion-exchanged water, the organic phase was concentrated, and the solvent was distilled off. The residue was purified by column chromatography (ethyl acetate / hexane = 10/90 (volume ratio)) to obtain 21.6 g of the target compound (yield 74%).
¹ It was confirmed by 1 H-NMR analysis that the obtained compound was 2- [4- (2-hydroxy-2-methyl-1-oxopropyl) phenoxy] ethyl methacrylate.
^{1 1} H NMR (300 MHz, chloroform-d): δ8.06 (d, J = 9.0 Hz, 2H), 6.96 (d, J = 9.0 Hz, 2H), 6.13 (d, J = 0) .6Hz, 1H), 5.59 (s, 1H), 4.50 (d, J = 5.1Hz, 2H), 4.29 (dd, J = 5.5, 4.1Hz, 3H), 1 .94 (dd, J = 1.6, 1.0Hz, 3H), 1.61 (s, 6H).

(Manufacturing of polymer (X))
(Production Example 1) Production of a polymer (X1) having an active group that generates radicals by irradiation with active energy rays In a flask equipped with a stirrer, a cooling tube and a thermometer, methyl isobutyl ketone (hereinafter referred to as MIBK). ) (78 parts by mass), then the inside of the flask is replaced with nitrogen and the temperature is raised to 65 ° C. 4-methacryloyloxybenzophenone (40 parts by mass), stearyl methacrylate (10 parts by mass), 2-ethylhexyl methacrylate (30 parts by mass). Parts), hydroxyethyl methacrylate (10 parts by mass), diethylaminoethyl methacrylate (10 parts by mass), 2,2'-azobis (2,4-dimethylvaleronitrile) (0.8 parts by mass), MIBK (78 parts by mass) The mixed solution of the above was added dropwise over 2 hours. After another 2 hours, in order to increase the polymerization rate, a mixed solution of azobis (2,4-dimethylvaleronitrile) (0.5 parts by mass) and MIBK (0.6 parts by mass) was added and held for 5 hours. Then, the reaction solution was cooled to 40 ° C. to obtain a MIBK solution (X1) of a polymer having an active group.
The non-volatile content of (X1) is 40% by mass, the weight average molecular weight (Mw) of the polymer in (X1) is 17200, the glass transition temperature is 48 ° C., and the content of active groups is 1.5 mmol / g. rice field.

(Production Example 2) Production of a polymer (X2) having an active group that generates radicals by irradiation with active energy rays In Production Example 1, the composition of the mixed solution was 2- [4- (2-hydroxy-2-methyl-). 1-oxopropyl) phenoxy] ethyl methacrylate (25 parts by mass), 4-methacryloyloxybenzophenone (25 parts by mass), stearyl methacrylate (10 parts by mass), 2-ethylhexyl methacrylate (30 parts by mass), diethylaminoethyl methacrylate (10 parts by mass) Parts), 2,2'-azobis (2,4-dimethylvaleronitrile) (0.8 parts by mass), and MIBK (78 parts by mass) under the same conditions as in Production Example 1. A MIBK solution (X2) of the polymer having the same was obtained.
The non-volatile content of (X2) was 40% by mass, the weight average molecular weight (Mw) of the polymer in (X2) was 19,800, and the content of the active group was 1.8 mmol / g.

(Curable composition)
Each of the materials shown below was mixed in an amount (part by mass, converted to non-volatile content) shown in Table 1. Then, a mixed solvent of propylene glycol monomethyl ether (hereinafter, PGM) and methyl ethyl ketone (hereinafter, MEK) (PGM: MEK (mass ratio) 7: 3) was added so that the solid content concentration was 30% by mass, and the mixture was uniform. The curable composition (coating liquid) used in each Example and Comparative Example was obtained by stirring until.
(Meta) acrylate (B1): Mixture of pentaerythritol triacrylate (trifunctional) and pentaerythritol tetraacrylate (tetrafunctional) (Viscoat # 300 manufactured by Osaka Organic Chemical Industry Co., Ltd.)
(Meta) Acrylate (B2): Ethoxylated Dipentaerythritol Hexa (Meta) Acrylate (Hexfunctional) (A-DPH-12E manufactured by Shin-Nakamura Chemical Co., Ltd.)
Photopolymerization Initiator (E): IGM Resins B.I. V. Omnirad 184 manufactured by the company

(Composition for forming a primer layer)
The polyester resin (P1), urethane resin (P2), melamine compound (P3), and particles (P4) shown below are polyester resin (P1) / urethane resin (P2) / melamine compound (P3) / particles (P4) (solid). (Mass ratio) = 60/25/10/5 to obtain a composition for forming a primer layer.
-Polyester resin (P1): An aqueous dispersion of a polyester resin having the following composition Monomer composition: (acid component) terephthalic acid / isophthalic acid / 5-sodiumsulfoisophthalic acid // (diol component) ethylene glycol / 1,4- Butanediol / diethylene glycol = 56/40/4 // 70/20/10 (mol%)
-Urethane resin (P2): Water dispersion of polyester urethane resin having the following composition Isophorone diisocyanate: Terephthalic acid: Isophthalic acid: Ethylene glycol: Diethylene glycol: Dimethylol propanoic acid = 12: 19: 18: 21: 25: 5 ( mol%)
-Melamine compound (P3): Hexamethoxymethylol melamine-Particles: (P4): Silica particles with an average primary particle diameter of 0.07 μm

(Polyester film base material)
A raw material obtained by mixing polyester (S1), (S2), and (S3) at a ratio of 91% by mass, 3% by mass, and 6% by mass, respectively, is used as a raw material for the outermost layer (surface layer), and polyester (S1) and (S2) are used. Raw materials mixed at a ratio of 97% by mass and 3% by mass, respectively, were used as raw materials for the intermediate layer, and each was supplied to two extruders, melted at 285 ° C., and then placed on a cooling roll set at 40 ° C. An unstretched sheet was obtained by co-extruding and cooling and solidifying in a layer structure of two types and three layers (surface layer / intermediate layer / surface layer = discharge amount of 1: 8: 1).
Next, after stretching 3.1 times in the vertical direction at a film temperature of 85 ° C. using the difference in roll peripheral speed, a composition for forming a primer layer was applied to one side of this vertically stretched film, and the film was guided to a tenter at 95 ° C. After drying for 10 seconds in the lateral direction, it was stretched 4.2 times at 120 ° C., heat-treated at 230 ° C. for 10 seconds, then relaxed by 2% in the lateral direction, and a primer layer having a thickness of 0.1 μm was placed on one side. A polyester film substrate having a thickness (after drying) of 50 μm was obtained.

[Examples 1 to 6]
The coating solution shown in Table 1 below is applied on the primer layer of the polyester film, dried at 70 ° C. for 1 minute, and exposed to excimer light (half-value width 14 nm) with xenone (wavelength 172 nm), irradiation amount 15 mJ / cm ² , illuminance 5 mW. / Cm ² (Xenon excimer 172 nm light irradiator manufactured by Ushio Denki Co., Ltd., lamp unit model: SUS05 (lamp house model: H0011, lighting power supply model: B0005), nitrogen flow (oxygen concentration 1% or less)) as shown in Table 1. UV of high-power UV device (model: US5 ^- X1802 ^- X1202) manufactured by Eye Graphics Co., Ltd. (Conveyor) was irradiated with ultraviolet rays to obtain a laminate having a cured film having a film thickness (after drying) of 5 μm.
The cured film of this laminated body had a wrinkle-like uneven structure, had good matting property, and had good pencil hardness. The evaluation results for this laminated body are shown in Table 2 below.

[Comparative Examples 1 to 3]
In Example 1, the coating liquid was produced in the same manner as in Example 1 except that the composition of the coating liquid was changed to the composition shown in Table 1, to obtain a laminate having a cured film. When the obtained laminated body was evaluated, as shown in Table 2 below, wrinkle-like unevenness was not formed and there was no matte property.

[Comparative Examples 4 and 5]
In Example 1, the composition of the coating film was changed to the composition shown in Table 1, and it was manufactured and cured in the same manner as in Example 1 except that it was cured only by ultraviolet irradiation with a high-pressure mercury lamp without using excimer light. A laminate having a film was obtained. When the obtained laminate was evaluated, as shown in Table 2 below, weak wrinkle-like irregularities were formed, but the matting property was weak.

Claims (11)

It is a cured film formed by irradiating an active energy ray-curable composition with active energy rays, and has a wrinkled uneven structure on the surface, and the curable composition generates radicals by irradiation with active energy rays. A cured film containing a polymer having an active radical. The group consisting of a benzophenone group, an acetophenone group, a benzoin group, an α-hydroxyketone group, an α-aminoketone group, an α-diketone group, an α-diketone dialkylacetal group, anthraquinone group, a thioxanthone group, and a phosphine oxide group. The cured film according to claim 1, which is at least one group selected from the above. The cured film according to claim 1 or 2, wherein the curable composition contains (meth) acrylate. The cured film according to any one of claims 1 to 3, wherein the average length (RSm) of the roughness curve element according to JIS B0601: 2013 of the uneven structure is 1 μm or more. The cured film according to any one of claims 1 to 4, wherein the arithmetic mean height (Sa) of the concave-convex structure defined by ISO 25178 is 0.1 μm or more. The cured film according to any one of claims 1 to 5, wherein the average value (θa) of the local inclination angles of the uneven structure is 2 ° or more. The cured film according to any one of claims 1 to 6, wherein the surface 60 ° gloss is 50 or less. The invention according to any one of claims 1 to 7, wherein the active energy ray-curable composition containing a polymer having an active group that generates radicals by irradiation with active energy rays is irradiated with excimer light and cured. A method for manufacturing a cured film. A laminate in which the cured film according to any one of claims 1 to 7 is laminated on a substrate. The laminate according to claim 9, wherein the base material is a film. The 9 or 10 according to claim 9 or 10, wherein an active energy ray-curable composition containing a polymer having an active group that generates radicals by irradiation with active energy rays is laminated on a substrate and cured by irradiating with excima light. Method of manufacturing a laminate of.