JP7567255B2 - Cured film and laminate, and methods for producing the same - Google Patents

Description

The present invention relates to a cured film and a laminate, as well as a method for producing the same.

In order to impart a matte finish to building materials such as wallpaper, display members, decorative films, and other members, fine irregularities are sometimes imparted to the surface of a substrate. In addition, these members are sometimes required to have antistatic properties.
Patent Document 1 discloses a method for forming fine projections and recesses by irradiating the surface of a biaxially oriented thermoplastic resin film used in a magnetic recording medium with excimer laser light.
Patent Document 2 discloses a method for forming irregularities on the surface of a film having a hard coat layer used in an antireflection film, in which a film having a hard coat layer containing a hard coat resin and inorganic fine particles is irradiated with excimer light to decompose the hard coat resin portion of the surface layer.

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

However, the method described in Patent Document 1 can only obtain a specific uneven structure that does not provide a sufficient matte effect. In addition, since the unevenness is formed directly on the biaxially oriented thermoplastic resin film, it is difficult to apply the method to display applications in which various surface properties such as scratch resistance and antistatic properties are imparted.
In the method described in Patent Document 2, only the hard coat resin of the hard coat layer is decomposed to expose inorganic fine particles on the surface, so that the particles tend to fall off, which may impair visibility when used in a display, etc. In addition, there is a problem that the surface uneven structure is limited by the shape and distribution of the particles.
An object of the present invention is to provide a cured film and a laminate having excellent matte properties, and a method for producing such a cured film and a laminate.

The present invention has the following aspects.
[1] A cured film having a concave-convex structure on its surface resulting from phase separation, the concave-convex structure including a wrinkled concave-convex structure formed by the concaves and/or convexities.
[2] The cured film according to [1] above, which is obtained by curing a curable composition that undergoes phase separation.
[3] The cured film according to [1] or [2], wherein the uneven structure has a mean length (RSm) of roughness curve elements according to JIS B0601:2013 of 1 μm or more.
[4] The cured film according to any one of [1] to [3] above, wherein the uneven structure has an arithmetic mean height (Sa) defined by ISO 25178 of 0.1 μm or more.
[5] The cured film according to any one of the above [1] to [4], wherein the average value (θa) of the local inclination angle of the uneven structure is 2° or more.
[6] The cured film according to any one of the above [1] to [5], wherein the 60° gloss of the surface is 50 or less.
[7] The cured film according to any one of [2] to [6] above, wherein the phase-separating curable composition contains a (meth)acrylate.
[8] The cured film according to any one of [2] to [7] above, wherein the phase-separating curable composition contains a compound having at least one polar group selected from a hydroxyl group, an amino group, an amide group, a sulfonyl group, a phosphate ester group, and a thiol group.
[9] The cured film according to any one of [2] to [8] above, wherein the phase-separating curable composition contains a compound that does not contain at least one polar group selected from a hydroxyl group, an amino group, an amide group, a sulfonyl group, a phosphate ester group, and a thiol group.
[10] The cured film according to any one of the above [2] to [9], wherein the phase-separating curable composition contains two types of compounds whose SP values are separated by 1.0 or more.
[11] The method for producing a cured film according to any one of the above [1] to [10], comprising: subjecting a phase-separating curable composition to phase separation to form a concave-convex structure on a surface thereof; and then curing the composition by irradiating the composition with vacuum ultraviolet light.
[12] A laminate comprising a substrate and the cured film according to any one of [1] to [10] above laminated thereon.
[13] The laminate according to [12] above, wherein the substrate is a film.
[14] The method for producing a laminate according to [12] or [13] above, comprising laminating a curable composition that undergoes phase separation on a substrate to form a relief structure by phase separation, and then irradiating the substrate with vacuum ultraviolet rays.

The cured film and laminate of the present invention have excellent matt properties. According to the manufacturing method of the cured film and laminate of the present invention, a cured film and laminate with excellent matt properties can be obtained.

Hereinafter, an embodiment of the present invention will be described in detail.
In the present invention, "(meth)acrylate" is a general term for acrylate or methacrylate. "(meth)acrylic" is a general term for acrylic and methacrylic. The "to" symbol indicating a range of values means that the values before and after the symbol are included as the lower and upper limits.

[Cured film]
The cured film of the present invention (hereinafter simply referred to as "cured film") has an uneven surface structure resulting from phase separation. The cured film of the present invention has excellent matte properties and is therefore suitable as an anti-glare film.

(average length of roughness curve element)
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 (RSm, hereinafter also simply referred to as "RSm") according to JIS B0601:2013. The evaluation length when calculating RSm was 236.87 μm. The preferred range of RSm is 1 μm or more, more preferably 2 to 100 μm, even more preferably 3 to 60 μm, particularly preferably 4 to 50 μm, and most preferably 5 to 35 μm. When within the above range, excellent matte properties are obtained, and excellent visibility is obtained when used in a display or the like.

(arithmetic mean height)
The arithmetic mean height of the uneven structure of the cured film is the arithmetic mean height (Sa, hereinafter also simply referred to as "Sa") defined in ISO25178. The evaluation area for calculating Sa was 177.86 μm × 236.87 μm. Sa is preferably 0.1 μm or more, more preferably 0.15 to 20 μm, even more preferably 0.2 to 10 μm, particularly preferably 0.3 to 5 μm, and most preferably in the range of 0.4 to 3 μm. When it is in the above range, it has excellent matte properties and excellent visibility when used in a display or the like.

(Average value of the inclination angle of the uneven structure)
The average value of the local inclination angle (θa, hereinafter also simply referred to as "θa") in the uneven structure of the cured film can be measured by the method described in the Examples described later. The evaluation length for calculating θa was 236.87 μm. θa is preferably 2° or more, more preferably 4° or more, even more preferably 5° or more, particularly preferably 7° or more, and most preferably 10° or more, and the upper limit may be 90°. When it is in this range, it has good matte properties.

(Thickness)
From the viewpoint of improving the matte property, the thickness of the cured film (concave-convex layer) is preferably in the range of 0.1 to 100 μm, more preferably 1 to 80 μm, further preferably 2 to 50 μm, and particularly preferably 4 to 30 μm. The thickness of the cured film indicates the maximum thickness of the concave-convex layer, and is determined by cross-sectional observation using an electron microscope.

(Gross)
The 60° gloss (60° specular gloss) of the surface of the cured film measured by the method described in the Examples below is preferably 50 or less, more preferably 30 or less, even more preferably 20 or less, particularly preferably 15 or less, and most preferably 12 or less, with the lower the better. The smaller the 60° gloss value, the better the matte property.
Similarly, the 20° gloss is preferably 20 or less, more preferably 10 or less, further preferably 5 or less, and particularly preferably 2 or less, with the lower the better. The smaller the 20° gloss value, the more excellent the matte property.

(Pencil hardness)
The pencil hardness of the cured film measured by the method described in the Examples below is preferably F or more, more preferably H or more, and further preferably 2H or more. When the hardness is in the above range, the film has excellent scratch resistance and is suitable for applications where visibility is important, such as displays.

[Method for producing cured film and laminate]
The cured film of the present invention and the laminate of the present invention having the same (hereinafter simply referred to as "laminate") can be produced, for example, by a method in which a coating film of a curable composition that undergoes phase separation is laminated on a substrate to form a concave-convex structure due to phase separation, and then active energy rays are irradiated from the surface side of the coating film (the side opposite to the substrate) to form a cured film on the surface of the substrate.
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 coating. Then, when the inside of the coating film is cured, the cured coating on the surface side that has cured first buckles, so that a cured film having a wrinkled uneven structure on the surface is formed. That is, in addition to the uneven structure due to phase separation, a wrinkled uneven structure is formed on the surface of the cured film, so that the matte property is improved.

(Phase-separating curable composition)
The phase-separating curable composition used to form the cured film contains an active energy ray curable compound. The curable composition may further contain a compound containing at least one polar group selected from a hydroxyl group, an amino group, an amide group, a sulfonyl group, a phosphate ester group, and a thiol group, as necessary. The curable composition may further contain a compound not containing the polar group, as necessary. The curable composition may further contain an organic solvent, a photopolymerization initiator, and other components, as necessary.

Examples of active energy ray curable compounds include (meth)acrylates. There are no particular limitations on the (meth)acrylates, and a mixture of one or more monofunctional (meth)acrylates, bifunctional (meth)acrylates, and polyfunctional (meth)acrylates, products commercially available as active energy ray curable resin materials, or products to which other components have been added as long as the purpose of this embodiment is not impaired can be used. Among these, monofunctional or bifunctional (meth)acrylates are preferred from the viewpoint of ease of forming a wrinkled uneven structure. Furthermore, for applications requiring scratch resistance, bifunctional (meth)acrylates are more preferred. The use of polyfunctional (meth)acrylates is a preferred form in that scratch resistance and hardness are improved, but depending on the compound used, it may be difficult to form a wrinkled uneven structure, so attention must be paid to the type of compound used and the blending ratio.

Examples of bifunctional polyfunctional (meth)acrylates include alkanediol di(meth)acrylates such as 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, tricyclodecanedimethylol di(meth)acrylate, bisphenol-modified di(meth)acrylates such as bisphenol A ethylene oxide-modified di(meth)acrylate and bisphenol F ethylene oxide-modified di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, urethane di(meth)acrylate, and epoxy di(meth)acrylate. Among these, in consideration of the ease of forming a wrinkled uneven structure, a structure without branches is preferable, alkyl diol di(meth)acrylate is more preferable, and alkyl diol di(meth)acrylate having 4 to 18 carbon atoms is even more preferable.

Examples of monofunctional (meth)acrylates include alkyl (meth)acrylates such as methyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, and isobornyl (meth)acrylate, hydroxyalkyl (meth)acrylates such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and hydroxybutyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, methoxypropyl (meth)acrylate, and ethoxypropyl (meth)acrylate. Examples of such alkoxyalkyl (meth)acrylates include benzyl (meth)acrylate and other aromatic (meth)acrylates such as phenoxyethyl (meth)acrylate, diaminoethyl (meth)acrylate and other amino group-containing (meth)acrylates such as diethylaminoethyl (meth)acrylate, and other ethylene oxide-modified (meth)acrylates such as methoxyethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, and phenylphenol ethylene oxide-modified (meth)acrylate, glycidyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, and (meth)acrylic.

Examples of trifunctional or higher polyfunctional (meth)acrylates include ethylene oxide-modified (meth)acrylates such as dipentaerythritol hexa(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethylene oxide-modified dipentaerythritol hexa(meth)acrylate, and ethylene oxide-modified pentaerythritol tetra(meth)acrylate. Examples of suitable urethane acrylates include isocyanuric acid modified tri(meth)acrylates such as isocyanuric acid ethylene oxide modified tri(meth)acrylates and ε-caprolactone modified tris(acryloxyethyl)isocyanurate, and urethane acrylates such as pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymers, pentaerythritol triacrylate toluene diisocyanate urethane prepolymers, and dipentaerythritol pentaacrylate hexamethylene diisocyanate urethane prepolymers. Among these, ethylene oxide modified types and trifunctional (meth)acrylates are preferred in terms of the ease of forming a wrinkled uneven structure.

The uneven structure caused by phase separation is a structure in which a composition made of materials with different compatibility undergoes phase separation during the process of application, drying, and curing, resulting in an uneven surface. Conventionally known materials can be used as the material that causes phase separation. A composition made of materials with different polarities is preferable, as it is particularly easy to form by a method of coating a film. For example, a combination of a compound (X) containing at least one polar group selected from a hydroxyl group, an amino group, an amide group, a sulfonyl group, a phosphate ester group, and a thiol group and a compound (Y) containing no such polar group can be mentioned. In addition, in order to maintain the uneven shape formed and use it for various applications, it is preferable to use a curable composition for hard coating.

Compound (X) containing at least one polar group selected from hydroxyl, amino, amide, sulfonyl, phosphate, and thiol groups is characterized by hydrogen bonding, which allows the formation of an uneven structure due to phase separation. Among these hydrogen-bonding groups, hydroxyl, amino, and amide groups are preferred because they are more likely to form an uneven structure due to phase separation, and hydroxyl, amino, and amide groups are more preferred from the standpoint of stability when materials are mixed and ease of uneven formation, with hydroxyl groups being particularly preferred. It is also possible for the compound to have not one type of polar group, but multiple types.

In addition, in consideration of the ease of forming a concave-convex structure by phase separation, it is preferable that compound (X) is a polymeric compound rather than a low molecular weight compound. As polymeric compounds, (meth)acrylic polymers, polyvinyl alcohols, and celluloses are preferred because they can introduce a larger number of polar groups, and (meth)acrylic polymers are more preferred in terms of being able to introduce various functional groups and making it easier to control performance.

To further increase the hardness of the cured film having the uneven structure, it is preferable to include a carbon-carbon unsaturated bond in the compound (X). The hardness of the cured film to be formed can be adjusted by adjusting the content of the carbon-carbon unsaturated bond. Note that the carbon-carbon unsaturated bond means a carbon-carbon double bond or a carbon-carbon triple bond, and is preferably a carbon-carbon double bond, and more preferably the carbon-carbon double bond is a (meth)acryloyl group, and particularly considering the reactivity of the carbon-carbon unsaturated bond, is even more preferably an acryloyl group.

In the (meth)acrylic polymer, compound (X) containing at least one polar group selected from hydroxyl, amino, amide, sulfonyl, phosphate, and thiol groups can be prepared by copolymerizing a (meth)acrylate monomer containing such a polar group with another (meth)acrylate monomer, or by reacting an acid or base with the epoxy group portion of a polymer obtained by copolymerizing an epoxy group-containing (meth)acrylate with another (meth)acrylate monomer to generate hydroxyl groups. The method of using glycidyl (meth)acrylate is particularly useful because it is easy to control the amount of hydroxyl groups.

Examples of (meth)acrylates containing epoxy groups include glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, and 3,4-epoxycyclohexylmethyl (meth)acrylate. Among these, glycidyl (meth)acrylate is preferred, with glycidyl acrylate being particularly preferred, in consideration of its good reactivity and ease of use as a material.

When a hydroxyl group is introduced using a (meth)acrylate containing an epoxy group, the proportion of the (meth)acrylate containing an epoxy group in the (meth)acrylate polymer is preferably 10% by mass or more, more preferably 30% by mass or more, even more preferably 50% by mass or more, and particularly preferably 80% by mass or more, with the upper limit being 100% by mass. By using within this range, it becomes easier to control the polarity of the polymer, and it becomes easier to form an uneven structure due to phase separation.

Compounds used in the (meth)acrylate polymer containing epoxy groups to form hydroxyl groups include acids and bases, but considering the stability of the (meth)acrylate polymer, acids are preferred, and among them, carboxylic acids are particularly preferred. Among carboxylic acids, the use of (meth)acrylic acid is more preferred because it is possible to introduce double bonds. Among (meth)acrylic acids, acrylic acid is the most suitable, considering the reactivity of the epoxy group with the carboxylic acid and the reactivity of the introduced double bond. It is also a preferred embodiment to use a hydroxycarboxylic acid such as lactic acid to introduce more hydroxyl groups. Furthermore, it is also possible to react two or more types of carboxylic acids with the epoxy group to form two or more types of structures.

The amount of epoxy groups to be reacted is usually 1% by mass or more, preferably 20% by mass or more, more preferably 50% by mass or more, and even more preferably 80% by mass or more, and may be up to 100% by mass. By reacting within this range, hydroxyl groups are generated, resulting in a form that is easy to form unevenness due to phase separation.

(Meth)acrylamide monomers for incorporating an amide group into compound (X) include (meth)acryloylmorpholine, hydroxylmethyl(meth)acrylamide, hydroxylethyl(meth)acrylamide, dimethyl(meth)acrylamide, diethyl(meth)acrylamide, and N-isopropyl(meth)acrylamide. Considering ease of introduction, acrylamide monomers are more preferred than methacrylamide monomers. Furthermore, among the above, in consideration of the stability of the polymer and the strength of polarity, (meth)acryloylmorpholine is particularly preferred, and acryloylmorpholine is even more preferred. Furthermore, these (meth)acrylamide monomers may be used alone or in combination of two or more.

In addition, when a (meth)acrylic polymer is used as the compound (X), various polymerizable (meth)acrylates can be used in addition to the above-mentioned compound groups. For example, alkyl (meth)acrylate monomers such as (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, stearyl (meth)acrylate, phenoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, methoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and dicyclopentenyloxyethyl (meth)acrylate;
(meth)acrylate monomers having a fluoroalkyl group, such as perfluorohexylethyl (meth)acrylate, 1H,1H,7H-dodecafluoroheptyl (meth)acrylate, and 1H,1H,9H-hexadecafluorononyl (meth)acrylate;
(meth)acrylate monomers having an amino group, such as N,N-diethylaminoethyl (meth)acrylate and N,N-dimethylaminoethyl (meth)acrylate;
(meth)acrylate monomers having a hydroxyl group, such as 2-hydroxypropyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and 1,6-hexanediol mono(meth)acrylate;
Examples of raw materials other than the (meth)acrylic acid derivatives include hydrocarbon monomers having a vinyl group, such as styrene, p-chlorostyrene, p-methoxystyrene, divinylbenzene, N-vinylpyrrolidone, N-vinylcaprolactam, acrylonitrile, ethylene glycol divinyl ether, pentaerythritol divinyl ether, 1,6-hexanediol divinyl ether, trimethylolpropane divinyl ether, ethylene oxide-modified hydroquinone divinyl ether, ethylene oxide-modified bisphenol A divinyl ether, pentaerythritol trivinyl ether, dipentaerythritol hexavinyl ether, and ditrimethylolpropane polyvinyl ether.

The raw material used is not limited to one type, and two or more types may be used in combination to prepare the (meth)acrylic polymer, and it is preferable to use two or more types in combination to prepare the (meth)acrylic polymer.

The polymerization conditions for producing the (meth)acrylic polymer are not particularly limited, and a known method can be appropriately selected. Usually, the reaction for obtaining the (meth)acrylic polymer is a radical polymerization reaction, and the (meth)acrylic polymer can be obtained by polymerizing the raw material monomers in an organic solvent in the presence of a radical polymerization initiator.

Examples of organic solvents include ketone-based solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; alcohol-based solvents such as ethanol, methanol, isopropyl alcohol, and isobutanol; ether-based solvents such as ethylene glycol dimethyl ether and propylene glycol monomethyl ether; ester-based solvents such as ethyl acetate, propylene glycol monomethyl ether acetate, and 2-ethoxyethyl acetate; and aromatic hydrocarbon solvents such as toluene. These organic solvents may be used alone or in combination of two or more.

Examples of radical polymerization initiators include organic peroxides such as benzoyl peroxide and di-t-butyl peroxide, and azo compounds such as 2,2'-azobisbutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile). These radical polymerization initiators may be used alone or in combination of two or more.

The polymerization temperature is usually 20 to 150°C, preferably 50 to 100°C. The polymerization time is usually 1 to 72 hours, preferably 3 to 36 hours.

The reaction conditions between the epoxy group and the carboxylic acid compound are not particularly limited, and a known method can be appropriately selected. The reaction may be carried out without or in the presence of a catalyst. Examples of the catalyst include tertiary amines such as triethylamine and benzyldimethylamine, ammonium salts such as tetraethylammonium chloride and tetrabutylammonium bromide, phosphines such as triphenylphosphine and tributylphosphine, and phosphonium salts such as tetrabutylphosphonium bromide and tetrabutylphosphonium iodide. The amount of the catalyst used is usually 0.5% by mass or more, preferably 1.0% by mass or more, and usually 5.0% by mass or less, preferably 3.5% by mass or less, based on the weight of the polymer.

The reaction temperature is usually 20 to 200°C, preferably 50 to 150°C. The reaction time is usually 1 to 72 hours, preferably 3 to 20 hours.

The weight average molecular weight (Mw) of the (meth)acrylic polymer should be appropriately selected depending on the application of the curable composition, but is usually 5,000 or more, preferably 7,000 or more, more preferably 9,000 or more, and usually 200,000 or less, preferably 100,000 or less, more preferably 70,000 or less, and even more preferably 50,000 or less. If it is within the above range, it becomes easier to form unevenness due to phase separation on the surface after application. The weight average molecular weight (Mw) of the (meth)acrylic polymer can be determined as a polystyrene standard converted value using gel permeation chromatography (GPC). Specific measurement conditions are shown in the examples below.

From the viewpoint of improving the scratch resistance of the cured film formed, the (meth)acrylic polymer of compound (X) preferably has a (meth)acryloyl equivalent (amount of (meth)acryloyl groups introduced) of 0.1 mmol/g or more, more preferably 0.5 mmol/g or more, even more preferably 1.0 mmol/g or more, particularly preferably 2.0 mmol/g or more, and most preferably 2.5 mmol/g or more. From the viewpoint of preventing gelation, the (meth)acryloyl equivalent is preferably 10.0 mmol/g or less, more preferably 8.0 mmol/g or less, and particularly preferably 6.0 mmol/g or less. The (meth)acryloyl equivalent is calculated based on the raw materials used, and it is preferable to select the reaction of the epoxy group and the carboxylic acid so that the (meth)acryloyl equivalent is in the above range.

Examples of compounds (Y) that do not contain hydroxyl groups, amino groups, amide groups, sulfonyl groups, phosphate ester groups, or thiol groups include (meth)acrylic polymers and various (meth)acrylates. In other words, it is also possible to use the active energy ray-curable compounds described above as compound (Y).

In the present invention, the term "(meth)acrylic polymer" refers to a polymer synthesized from a raw material containing (meth)acrylic acid and/or a (meth)acrylic acid derivative, and is used to include a polymer obtained by further modifying this polymer. As long as the polymer uses at least one raw material ((meth)acrylate monomer) containing (meth)acrylic acid or a (meth)acrylic acid derivative, there is no particular limitation on the other raw materials. For example, the polymer may be a copolymer using a known polymerizable monomer such as a hydrocarbon monomer having a vinyl group other than a (meth)acrylate monomer. In addition, the term "(meth)acrylic acid derivative" refers to a compound having a structure similar to that of (meth)acrylic acid, such as a metal salt of (meth)acrylic acid, a (meth)acrylic acid ester, or an (meth)acrylic acid amide.

Examples of (meth)acrylic polymers include those formed from the above-mentioned (meth)acrylates that do not contain hydroxyl groups, amino groups, amide groups, sulfonyl groups, phosphate ester groups, or thiol groups, and monomers that undergo polymerization reactions with these.

Examples of (meth)acrylates that do not contain hydroxyl groups, amino groups, amide groups, sulfonyl groups, phosphate ester groups, or thiol groups include the (meth)acrylates described above. When used as compound (Y), it is preferable that the polarity is low, so it is preferable to use compounds with few or no hydrogen bonding groups such as ethers, such as ethylene oxide structures.

Compound (X) and compound (Y) are compounds for phase separation. Therefore, from the viewpoint of solubility parameters (SP values, Solubility Parameter), it is preferable that the difference between the two is large.

The SP value of compound (X) is preferably 15.1 or more, more preferably 16.0 to 22.0, even more preferably 16.5 to 20.0, and particularly preferably 17.0 to 19.5. By using it within this range, it is possible to achieve both the ease of forming an uneven structure by phase separation and coatability.

The SP value of compound (Y) is preferably 15.0 or less, more preferably 7.0 to 14.5, even more preferably 8.0 to 14.0, and particularly preferably in the range of 9.0 to 13.5. By using compound (Y) within this range, it becomes easier to form an uneven structure due to phase separation with compound (X).

The difference in SP value between compound (X) and compound (Y) is preferably 0.5 or more, more preferably 1.0 to 9.0, even more preferably 2.0 to 8.0, and particularly preferably 3.0 to 7.0. If the difference is within this range, it becomes easier to form an uneven structure due to phase separation.

The mass ratio of the total amount of compound (X) to the total amount of compound (Y) is preferably in the range of 10:90 to 80:20, more preferably 12:88 to 60:40, particularly preferably 15:85 to 50:50, and most preferably 20:80 to 40:60. By setting it in this range, it becomes easier to form an uneven structure due to phase separation.

The content of the active energy ray-curable compound is preferably in the range of 5 to 99 mass %, more preferably 25 to 95 mass %, and further preferably 35 to 70 mass %, based on the nonvolatile content. When in the above range, an uneven structure due to phase separation and a wrinkled uneven structure are easily formed, and a cured film having excellent hardness can be formed.
The non-volatile content of the curable composition is the total mass of components other than the solvent such as the organic solvent, etc. The non-volatile content of the curable composition can be measured by a conventionally known method, for example, by measuring the change in weight when 1 g of the composition is spread and heated at 100° C. for 1 hour to volatilize the organic solvent.

When a compound (X) containing at least one polar group selected from a hydroxyl group, an amino group, an amide group, a sulfonyl group, a phosphate ester group, and a thiol group is used in forming a cured film, the content of the resin in the curable composition is preferably in the range of 1 to 95% by mass, more preferably 5 to 70% by mass, and even more preferably 10 to 60% by mass, based on the non-volatile content. When in the above range, it becomes easier to form an uneven structure due to phase separation.

In forming a cured film, when a (meth)acrylic polymer is used as compound (Y) that does not contain at least one polar group selected from hydroxyl groups, amino groups, amide groups, sulfonyl groups, phosphate ester groups, and thiol groups, the content of the resin in the curable composition is preferably 80% by mass or less, more preferably 1 to 70% by mass, and even more preferably 3 to 30% by mass, based on the non-volatile content. When within the above range, an uneven structure due to phase separation is easily formed.

(particle)
In order to further improve the matte property due to the wrinkled uneven structure of the cured film, it is also possible to blend particles into the curable composition. The particles are not particularly limited, and examples thereof include inorganic particles such as silica, hollow silica, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, calcium phosphate, magnesium phosphate, kaolin, aluminum oxide, zirconium oxide, and titanium oxide, and organic particles such as acrylic resin, 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 crosslinked type in order to maintain their shape, and crosslinked acrylic resin particles and crosslinked styrene resin particles are more preferred. Two or more of these particles may be used in combination.
The average primary particle size of the particles is preferably in the range of 0.01 to 30 μm, more preferably 0.05 to 10 μm, further preferably 0.1 to 5 μm, and particularly preferably 0.5 to 3 μm. When the average primary particle size is in this range, the matte property is excellently improved.
When particles are blended, the content thereof is preferably 30% by mass or less, more preferably 20% by mass or less, further preferably 10% by mass or less, and particularly preferably 8% by mass or less, based on the non-volatile content in the curable composition, from the viewpoint of improving matte properties.

(Photopolymerization initiator)
A photopolymerization initiator may be added to promote the curing 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, pivaloin ethyl ether, benzyl dimethyl ketal, 1,1-dichloroacetophenone, and p-t-butyl dichloroacetophenone. Examples of the photopolymerization initiator include phenone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-diethylthioxanthone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-dichloro-4-phenoxyacetophenone, phenyl glyoxylate, α-hydroxyisobutylphenone, dibenzosparone, 1-(4-isopropylphenyl)-2-hydroxy-2-methyl-1-propanone, 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propanone, tribromophenyl sulfone, and tribromomethylphenyl sulfone. These photopolymerization initiators may be used alone or in combination of two or more.
When a photopolymerization initiator is blended, the content thereof is preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 8% by mass or less, and particularly preferably 5% by mass or less, based on the non-volatile content, from the viewpoints of promoting curability and the hardness of the cured film.

(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 acrylic leveling agents, silicone leveling agents, and fluorine leveling agents. 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, and even more preferably 5% by mass or less, based on the nonvolatile content, from the viewpoint of improving the appearance of the cured film.

(Various additives)
The curable composition may contain various additives, such as a polymerization accelerator such as a compound containing a thiol group, an antifouling agent, an antistatic agent, a plasticizer, a surfactant, an antioxidant, and an ultraviolet absorber, within the scope of not impairing the effects of the present invention.

(Organic Solvent)
For the purpose of improving the workability when applying the curable composition to a substrate, an organic solvent may be added to the curable composition as necessary.
Examples of organic solvents include aromatic solvents such as toluene and xylene; ketone-based solvents such as methyl ethyl ketone, acetone, methyl isobutyl ketone, and cyclohexanone; ether-based solvents such as diethyl ether, isopropyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, anisole, and phenetole; ester-based solvents such as ethyl acetate, butyl acetate, isopropyl acetate, and ethylene glycol diacetate; amide-based solvents such as dimethylformamide, diethylformamide, and N-methylpyrrolidone; 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. These organic solvents may be used alone or in combination of two or more. Among these organic solvents, ester-based solvents, ether-based solvents, alcohol-based solvents and ketone-based solvents are preferred in that they can easily improve workability during coating.
When an organic solvent is blended in the curable composition, the content thereof is preferably from 10 parts by mass to 1,900 parts by mass, and more preferably from 40 parts by mass to 400 parts by mass, per 100 parts by mass of nonvolatile matter, from the viewpoint of improving operability in a coating operation.

(Formation of coating film)
Examples of the method for forming a coating film of the curable composition include a method in which the curable composition is applied onto a surface of a substrate or an article to form a coating film, and then dried as necessary. The coating method is not particularly limited, and examples thereof include known methods such as dip coating, air knife coating, curtain coating, spin coating, roller coating, bar coating, wire bar coating, gravure coating, and spray coating.
When the curable composition contains an organic solvent, it is preferable to heat-dry the composition before irradiating the composition with active energy rays. By heating and drying the composition beforehand, the solvent in the coating film can be effectively removed. The drying temperature of the heat-drying is preferably 30° C. or more and 200° C. or less, more preferably 40° C. or more and 150° C. or less. The drying time is preferably 0.01 minutes or more and 30 minutes or less, more preferably 0.1 minutes or more and 10 minutes or less.

(Irradiation with active energy rays)
The coating film of the curable composition formed on the surface of the substrate or article is irradiated with active energy rays to form a cured film, and a laminate in which the cured film is laminated on the substrate or article is formed. As the active energy rays, those with high energy (short wavelength) that can effectively cure the surface of the coating film are preferable, and vacuum ultraviolet rays (ultraviolet rays with a wavelength of 200 nm or less) are more preferable. Among the vacuum ultraviolet rays, excimer light with a half-width of 50 nm or less is optimal. Examples of 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 ability to form an effective uneven structure in the cured film, and the curability of the curable composition.

When vacuum ultraviolet rays are used, the cumulative amount of light to be irradiated is preferably in the range of 1 to 3000 mJ/cm ² , more preferably 3 to 1000 mJ/cm ² , even more preferably 5 to 500 mJ/cm ² , and particularly preferably 10 to 100 mJ/cm ^2. 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 .
In addition, the vacuum ultraviolet irradiation is preferably performed in an environment with a low oxygen content, such as a nitrogen atmosphere. The oxygen concentration in the atmosphere is preferably 10% or less, more preferably 5% or less, further preferably 3% or less, and particularly preferably 1% or less.

[Laminate]
The laminate of the present invention has a layer made of a substrate and a layer (uneven 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. In addition, a back functional layer may be provided on the surface of the substrate opposite to the cured film side. As long as the effect of the present invention is not impaired, a surface functional layer may be provided on the surface of the cured film opposite to the substrate.

(Substrate)
The substrate may be a known one, for example, a resin substrate, a metal substrate, or a paper substrate. Among these, the resin substrate is preferred from the viewpoint of processability. The resin substrate may be a single-layer structure or a multi-layer structure of two or more layers, and is not particularly limited. It is preferred that the resin substrate is a multi-layer structure of two or more layers, each layer having its own characteristics, and multi-functional.
As the resin substrate, various resin films (sheets) can be used, for example, a polyester film, a poly(meth)acrylate film, a polyolefin film, a polycarbonate film, a polyimide film, a triacetyl cellulose film, a polystyrene film, a polyvinyl chloride film, a polyvinyl alcohol film, and a nylon film.
When the laminate is used for a display, polyester films, poly(meth)acrylate films, polyolefin films, polycarbonate films, polyimide films, and triacetyl cellulose films are preferred. Among these, polyester films, poly(meth)acrylate films, and polyolefin films are preferred for anti-glare applications, and polyester films are more preferred in terms of transparency, formability, 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 one direction or a biaxially stretched film stretched in two directions 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 the substrate may be either a homopolyester or a copolymer polyester.
The homopolyester is preferably one obtained by polycondensation of 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. The aromatic dicarboxylic acid and the aliphatic glycol may each be used alone or in combination of two or more.
Examples of the dicarboxylic acid component of the copolymer 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 each be used alone or in combination of two or more.
Representative examples of polyester include polyethylene terephthalate and polyethylene naphthalate.
As the polyester film, from among the above, films formed from polyethylene terephthalate and polyethylene naphthalate are more preferable in consideration of mechanical strength and heat resistance, and from the viewpoint of ease of production and handleability for applications such as surface protection films, films formed from polyethylene terephthalate are particularly preferable.

The poly(meth)acrylate constituting the poly(meth)acrylate film that can be used as the substrate may be any poly(meth)acrylate having a unit based on (meth)acrylate, and various acrylic resins can be used. Examples of the (meth)acrylate include alkyl (meth)acrylates having an alkyl group with 1 to 4 carbon atoms, such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and butyl (meth)acrylate, and alkyl (meth)acrylates having an alkyl group with a larger number of carbon atoms.
In consideration of transparency, processability, and chemical resistance, the poly(meth)acrylate preferably contains as a main component a unit based on an alkyl(meth)acrylate having 1 to 4 carbon atoms, more preferably contains as a main component at least one selected from the group consisting of units based on methyl(meth)acrylate and units based on ethyl(meth)acrylate, and particularly preferably contains as a main component a unit based on methyl(meth)acrylate.
It is also possible to impart properties such as flexibility to the poly(meth)acrylate by incorporating units based on (meth)acrylates other than alkyl (meth)acrylates or units based on other monomers.
The proportion of units based on alkyl (meth)acrylate having 1 to 4 carbon atoms relative to the total mass of the poly(meth)acrylate is preferably 50% by mass or more, more preferably 80% by mass or more.

The substrate may contain particles for the purposes of imparting slipperiness, preventing scratches during each process, 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, and titanium oxide, and organic particles such as acrylic resin, styrene resin, urea resin, phenol resin, epoxy resin, and benzoguanamine resin. Furthermore, when the base layer includes a polyester film, precipitated particles obtained by precipitating a part of a metal compound such as a catalyst during the polyester manufacturing process can also be used. Among these, silica particles and calcium carbonate particles are preferred because they are particularly effective in small amounts.
The shape of the particles is not particularly limited, and any of spherical, block, rod-like, flat, etc. is acceptable. There are also no particular limitations on the hardness, specific gravity, color, etc.
Two or more kinds of these particles may be used in combination, if necessary.
The average primary particle size of the particles is preferably 10 μm or less, more preferably 0.01 to 5 μm, and even more preferably 0.01 to 3 μm. If the average primary particle size is 10 μm or less, problems due to a decrease in the transparency of the substrate are unlikely to occur.
The average primary particle size of the particles is the cumulative 50% (mass basis) value in the equivalent sphericity distribution measured by a centrifugal sedimentation type particle size distribution measuring device.
When the substrate contains particles, the content of the particles is not necessarily limited since it depends on the average primary particle diameter of the particles, but is preferably 5% by mass or less, more preferably in the range of 0.0003 to 3% by mass, and even more preferably in the range of 0.0005 to 1% by mass, based on the total mass of the substrate (the total mass of the layers containing the particles when the substrate is composed of multiple layers). If the particle content is 5% by mass or less, defects such as particle dropout and reduced transparency of the substrate are unlikely to occur.

The substrate may contain additives other than the above-mentioned particles as necessary. Examples of the additives that can be used include known additives such as ultraviolet absorbers, antioxidants, antistatic agents, heat stabilizers, lubricants, dyes, and pigments.
When the substrate is a film, the thickness is not particularly limited as long as it is within a range that allows film formation, but is preferably in the range of 2 to 350 μm, more preferably 5 to 250 μm, and even more preferably 10 to 100 μm.

(Primer layer)
The primer layer is appropriately provided between the substrate and the cured film (concave-convex layer) in order to impart various functions. The primer layer may be a single layer having a single or multiple functions, or may be composed of multiple layers.
In a preferred embodiment, the primer layer is an adhesion improving layer. If the adhesion between the substrate 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 substrate and the uneven layer is improved, and the laminate can be used for various applications. From the viewpoint of improving adhesion, it is preferable that the adhesion improving layer contains either one or both of a resin and a compound derived from a crosslinking agent.
In another preferred embodiment, the primer layer is an antistatic layer. When the primer layer is an antistatic layer, adhesion of dust and the like due to peeling electrification or frictional electrification can be reduced to the outermost surface of the laminate, particularly to the outermost surface on the side where the uneven layer is present relative to the substrate.
In order to make the primer layer an antistatic layer, for example, an antistatic agent may be contained in the primer layer.

The resin contained in the primer layer may be a conventionally known resin. Specific examples of the resin include polyester resin, acrylic resin, urethane resin, polyvinyl resin (polyvinyl alcohol, vinyl chloride-vinyl acetate copolymer, etc.), etc. Among these, polyester resin, acrylic resin, and urethane resin are preferred in consideration of adhesion performance and coating properties.
When the substrate is a resin film, the resin contained in the primer layer is preferably the same type of resin as that of the resin film from the viewpoint of affinity with the substrate. For example, when the substrate is a polyester film, the primer layer preferably contains a polyester resin. When the substrate is a poly(meth)acrylate film, the primer layer preferably contains an acrylic resin.

The polyester resin may be one whose main components are a polyvalent carboxylic acid and a polyvalent hydroxy compound.
Examples of polyvalent carboxylic acids include terephthalic acid, isophthalic acid, orthophthalic acid, 4,4'-diphenyldicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2-potassium sulfoterephthalic acid, 5-sodium sulfoisophthalic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, glutaric acid, succinic acid, trimellitic acid, trimesic acid, pyromellitic acid, trimellitic anhydride, phthalic anhydride, trimellitic acid monopotassium salt, and ester-forming derivatives thereof.
Examples of polyhydric hydroxy compounds include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 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, and potassium dimethylolpropionate.
One or more of these compounds may be appropriately selected and subjected to a conventional polycondensation reaction to synthesize a polyester resin.

The acrylic resin is a polymer of a polymerizable monomer including a (meth)acrylic monomer. Examples of the acrylic resin include a homopolymer or copolymer of a (meth)acrylic monomer, and a copolymer of a (meth)acrylic monomer and a polymerizable monomer other than a (meth)acrylic monomer.
The acrylic resin may be a copolymer of such a polymer with another polymer (e.g., polyester, polyurethane, etc.). Such a copolymer is, for example, a block copolymer or a graft copolymer. Alternatively, a polymer (or a mixture of polymers, as the case may be) obtained by polymerizing a polymerizable monomer in a solution or dispersion of a polyester is also included. Similarly, a polymer (or a mixture of polymers, as the case may be) obtained by polymerizing a polymerizable monomer in a solution or dispersion of a polyurethane is also included. Similarly, a polymer (or a mixture of polymers, as the case may be) 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 particularly representative 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 salts thereof; hydroxyl group-containing monomers such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, monobutyl hydroxyl fumarate, and monobutyl hydroxy itaconate; methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethyl Examples of suitable monomers include alkyl (meth)acrylates such as diethylhexyl (meth)acrylate and lauryl (meth)acrylate; nitrogen-containing monomers such as (meth)acrylamide, diacetone acrylamide, N-methylolacrylamide and (meth)acrylonitrile; styrene-based compounds such as styrene, α-methylstyrene, divinylbenzene and vinyltoluene, vinyl esters such as vinyl propionate and vinyl acetate; silicon-containing monomers such as γ-methacryloxypropyltrimethoxysilane and vinyltrimethoxysilane; phosphorus-containing vinyl monomers; vinyl halides such as vinyl chloride and vinylidene chloride; and conjugated dienes such as butadiene.

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

Polycarbonate polyols are obtained by the reaction (de-alcoholization reaction) of polyhydric alcohols with carbonate compounds. Examples of polyhydric alcohols include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, and 3,3-dimethylolheptane. Examples of carbonate compounds include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, and ethylene carbonate. Specific examples of polycarbonate polyols include poly(1,6-hexylene) carbonate and poly(3-methyl-1,5-pentylene) carbonate.

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

Examples of polyester polyols 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 polyvalent carboxylic acids 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 polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, and 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, alkyldialkanolamines, and lactone diols.

As polyols, polyester polyols and polycarbonate polyols are preferred in terms of adhesion performance, with polyester polyols being particularly preferred.

Examples of polyisocyanate compounds used to obtain urethane resins include aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, methylene diphenyl diisocyanate, phenylene diisocyanate, naphthalene diisocyanate, and tolidine diisocyanate; aliphatic diisocyanates having an aromatic ring such as α,α,α',α'-tetramethyl xylylene diisocyanate; aliphatic diisocyanates such as methylene diisocyanate, propylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, and hexamethylene diisocyanate; and alicyclic diisocyanates such as cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and isopropylidenedicyclohexyl diisocyanate. These may be used alone or in combination of two or more.
There are no particular limitations on the chain extender as long as it has two or more active groups that react with an isocyanate group, and generally, a chain extender having two hydroxyl groups or two amino groups can be mainly used.
Examples of chain extenders having two hydroxyl groups include glycol compounds such as aliphatic glycols such as ethylene glycol, propylene glycol, and butanediol; aromatic glycols such as xylylene glycol and bishydroxyethoxybenzene; and ester glycols such as neopentyl glycol hydroxypivalate.
Examples of chain extenders having two amino groups include aromatic diamines such as tolylenediamine, xylylenediamine, and diphenylmethanediamine; aliphatic diamines such as 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-nonanediamine, and 1,10-decanediamine; and alicyclic diamines such as 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, dicyclohexylmethanediamine, isopropylidincyclohexyl-4,4'-diamine, 1,4-diaminocyclohexane, and 1,3-bisaminomethylcyclohexane.

The urethane resin is typically used in the form of a dispersion or solution. The medium for the dispersion or solution may be a solvent, but is preferably water.
The aqueous dispersion or solution of the urethane resin may be a forced emulsification type using an emulsifier, a self-emulsification type in which a hydrophilic group is introduced into the structure of the urethane resin, or a water-soluble type, etc. In particular, a self-emulsification type in which an ionic group is introduced into the structure of the urethane resin to form an ionomer is preferred, since it has excellent storage stability of the liquid and excellent water resistance and transparency of the resulting primer layer.
Examples of the ionic group to be introduced into the structure of the urethane resin include a variety of groups such as a carboxyl group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, and a quaternary ammonium salt group, with the carboxyl group being preferred.
The carboxyl group is preferably in the form of a salt neutralized with a neutralizing agent such as ammonia, amine, alkali metals, or inorganic alkalis. Particularly preferred neutralizing agents are ammonia, trimethylamine, and triethylamine. In the urethane resin having a carboxyl group neutralized with a neutralizing agent, the carboxyl group from which the neutralizing agent is removed in the drying process after application can be used as a crosslinking reaction point with a crosslinking agent. This not only provides excellent stability in the liquid state before coating, but also makes it possible to improve the durability, solvent resistance, water resistance, blocking resistance, etc. of the obtained primer layer.
As a method for introducing carboxyl groups into urethane resin, various methods can be used in each stage of polymerization reaction. For example, a method using a resin having carboxyl groups as a copolymerization component during prepolymer synthesis, or a method using a component having carboxyl groups as one component of polyol, polyisocyanate compound, chain extender, etc. is mentioned. In particular, a method using a carboxyl group-containing diol and introducing a desired amount of carboxyl groups by the amount of this component is preferred. For example, a carboxyl group-containing diol can be copolymerized with the diol used in synthesizing the urethane resin.
Examples of the carboxyl group-containing diol include dimethylolpropionic acid, dimethylolbutanoic acid, bis-(2-hydroxyethyl)propionic acid, bis-(2-hydroxyethyl)butanoic acid, and salts of these acids in which the carboxyl group has been neutralized with a neutralizing agent.

In order to make the primer layer stronger and improve its performance such as adhesion, the primer layer preferably contains a compound derived from a crosslinking agent.
As the crosslinking agent, a known material can be used, for example, a melamine compound, an isocyanate compound, an oxazoline compound, an epoxy compound, a carbodiimide compound, a silane coupling compound, a hydrazide compound, and an aziridine compound. Among them, a melamine compound, an isocyanate compound, an epoxy compound, an oxazoline compound, a carbodiimide compound, and a silane coupling compound are preferred, and from the viewpoint of further improving adhesion and durability, a melamine compound, an oxazoline compound, an isocyanate compound, and an epoxy compound are more preferred, and a melamine compound, an oxazoline compound, and an isocyanate compound are particularly preferred. These crosslinking agents may be used alone or in combination of two or more. By using two or more types in combination, adhesion and durability may be further improved.

A melamine compound is a compound having a melamine skeleton in the compound, and examples thereof include alkylolated melamine derivatives, compounds obtained by reacting an alkylolated melamine derivative with an alcohol to partially or completely etherify the derivative, and mixtures thereof. Examples of alcohols used for etherification include methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butanol, and isobutanol. The melamine compound may be either a monomer or a dimer or higher polymer, or a mixture of these may be used. Furthermore, melamine partially co-condensed with urea or the like may also be used, and a catalyst may be used to increase the reactivity of the melamine compound. Considering the reactivity with various compounds, melamine compounds having a hydroxyl group are preferable.

The isocyanate compound refers to a compound having an isocyanate derivative structure, such as an isocyanate compound or a blocked isocyanate compound.
Examples of the isocyanate compound include aromatic isocyanate compounds such as tolylene diisocyanate, xylylene diisocyanate, methylene diphenyl diisocyanate, phenylene diisocyanate, and naphthalene diisocyanate; aliphatic isocyanate compounds having an aromatic ring such as α,α,α',α'-tetramethylxylylene diisocyanate; aliphatic isocyanate compounds such as methylene diisocyanate, propylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, and hexamethylene diisocyanate; and alicyclic isocyanate compounds such as cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, methylene bis(4-cyclohexyl isocyanate), and isopropylidenedicyclohexyl diisocyanate. Further, polymers and derivatives such as biuretized products, isocyanurate products, uretdione products, and carbodiimide modified products of these isocyanate compounds are also included. These may be used alone or in combination of two or more. Among the above isocyanate compounds, aliphatic isocyanate compounds or alicyclic isocyanate compounds are preferred over aromatic isocyanate compounds from the viewpoint of avoiding yellowing due to ultraviolet rays.
Examples of the blocked isocyanate compound include compounds in which the isocyanate group of the isocyanate compound is blocked with a blocking agent. Examples of the blocking agent include bisulfites, phenol-based compounds such as phenol, cresol, and ethylphenol, alcohol-based compounds such as propylene glycol monomethyl ether, ethylene glycol, benzyl alcohol, methanol, and ethanol, active methylene-based compounds such as dimethyl malonate, diethyl malonate, isobutanoyl methyl acetate, methyl acetoacetate, ethyl acetoacetate, and acetylacetone, mercaptan-based compounds such as butyl mercaptan and dodecyl mercaptan, lactam-based compounds such as ε-caprolactam and δ-valerolactam, amine-based compounds such as diphenylaniline, aniline, and ethyleneimine, acid amide compounds such as acetanilide and acetic acid amide, and oxime-based compounds such as formaldehyde, acetaldoxime, acetoneoxime, methyl ethyl ketoneoxime, and cyclohexanoneoxime. 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 preferred from the viewpoint that the primer layer is less likely to be destroyed.
The isocyanate compound may be used alone or as a mixture or bond with various polymers. In terms of improving the dispersibility and crosslinking property of the isocyanate compound, it is preferable to use a mixture or bond with a polyester resin or a urethane resin.

The oxazoline compound is a compound having an oxazoline group in the molecule. The oxazoline compound is preferably a polymer containing an oxazoline group. The polymer containing an oxazoline group is obtained by polymerization of an addition polymerizable oxazoline group-containing monomer alone or with other monomers.
Examples of the addition-polymerizable oxazoline group-containing monomer include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, and 2-isopropenyl-5-ethyl-2-oxazoline. These may be used alone or in combination of two or more. Among these, 2-isopropenyl-2-oxazoline is preferred because it is easily available industrially.
The other monomer is not particularly limited as long as it is a monomer that can be copolymerized with the addition-polymerizable oxazoline group-containing monomer, and examples thereof include (meth)acrylates such as alkyl (meth)acrylates (the alkyl group is a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, a 2-ethylhexyl group, and a cyclohexyl group); unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, styrenesulfonic acid, and salts thereof (sodium salts, potassium salts, ammonium salts, tertiary amine salts, and the like); unsaturated nitriles such as acrylonitrile and methacrylonitrile; (meth)acrylonitrile; Examples of such monomers include unsaturated amides such as acrylamide, N-alkyl(meth)acrylamide, and N,N-dialkyl(meth)acrylamide (alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, 2-ethylhexyl, and cyclohexyl groups); 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; halogen-containing α,β-unsaturated monomers such as vinyl chloride, vinylidene chloride, and vinyl fluoride; and α,β-unsaturated aromatic monomers such as styrene and α-methylstyrene. These monomers 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, further preferably 3 to 8 mmol/g, and particularly preferably 4 to 6 mmol/g. When the amount of oxazoline groups is within the above range, the durability of the coating film is improved and the adhesion can be easily adjusted.

An epoxy compound is a compound having an epoxy group in the molecule. Examples of epoxy compounds include condensates of epichlorohydrin and compounds having a hydroxyl group or an amino group (ethylene glycol, polyethylene glycol, glycerin, polyglycerin, bisphenol A, etc.), polyepoxy compounds, diepoxy compounds, monoepoxy compounds, glycidylamine compounds, etc. Examples of polyepoxy compounds include sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, triglycidyl tris(2-hydroxyethyl)isocyanate, glycerol polyglycidyl ether, and trimethylolpropane polyglycidyl ether. Examples of diepoxy compounds include neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, resorcinol diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and polytetramethylene glycol diglycidyl ether. Examples of monoepoxy compounds include allyl glycidyl ether, 2-ethylhexyl glycidyl ether, and phenyl glycidyl ether. Examples of glycidylamine compounds include N,N,N',N'-tetraglycidyl-m-xylylenediamine and 1,3-bis(N,N-diglycidylamino)cyclohexane.

The carbodiimide compound is a compound having one or more carbodiimide structures or carbodiimide derivative structures in the molecule. As the carbodiimide compound, from the viewpoint of the strength of the primer layer, a polycarbodiimide compound having two or more carbodiimide structures or carbodiimide derivative structures in the molecule is more preferable.
Carbodiimide compounds can be synthesized by known methods, and generally, condensation reaction of diisocyanate compounds is used. The diisocyanate compounds are not particularly limited, and both aromatic and aliphatic compounds can be used, such as tolylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, phenylene diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, dicyclohexyl diisocyanate, and dicyclohexylmethane diisocyanate.
In order to improve the water solubility or water dispersibility of the polycarbodiimide compound, a surfactant may be added, or a hydrophilic monomer such as a polyalkylene oxide, a quaternary ammonium salt of a dialkylamino alcohol, or a hydroxyalkylsulfonate may be added, within a range that does not impair the effects of the present invention.

The silane coupling compound is an organosilicon compound having an organic functional group and a hydrolyzable group such as an alkoxy group in one molecule. Examples of silane coupling compounds include epoxy group-containing compounds such as 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; vinyl group-containing compounds such as vinyltrimethoxysilane and vinyltriethoxysilane; styryl group-containing compounds such as p-styryltrimethoxysilane and p-styryltriethoxysilane; (meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, and 3-(meth)acryloxypropylmethyldiethoxysilane; (meth)acryloyl group-containing compounds such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2 -(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldiethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane and other amino group-containing compounds; isocyanurate group-containing compounds such as tris(trimethoxysilylpropyl)isocyanurate and tris(triethoxysilylpropyl)isocyanurate; and mercapto group-containing compounds such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropylmethyldiethoxysilane.
As the silane coupling compound, among the above compounds, from the viewpoint of the strength of the primer layer, epoxy group-containing silane coupling compounds, double bond-containing silane coupling compounds such as vinyl groups and (meth)acrylic groups, and amino group-containing silane coupling compounds are preferred.

These crosslinking agents react during the drying and film-forming processes, improving the performance of the primer layer. It can be assumed that the crosslinking agent-derived compounds present in the formed primer layer include unreacted crosslinking agents, reacted compounds, or mixtures thereof.

The antistatic agent contained in the primer layer is not particularly limited, and any known antistatic agent can be used. Examples of the antistatic agent include compounds having an ammonium group, polyether compounds, compounds having a sulfonic acid group, betaine compounds, and conductive organic polymers.
The primer layer may contain particles to improve blocking and slip properties.
The primer layer may contain additives such as antifoaming agents, coatability improvers, thickeners, organic lubricants, ultraviolet absorbers, antioxidants, foaming agents, dyes, and pigments, as necessary, within the scope of the present invention.

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 even more preferably 30 to 90% by mass. If the proportion 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 crosslinking 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 even more preferably 5 to 40% by mass. If the proportion of the compound derived from the crosslinking agent is within the above range, the adhesion performance and strength of the primer layer are more excellent.
The thickness of the primer layer depends on the material used in the primer layer and the performance to be achieved, so cannot be generally determined, but is preferably in the range of 0.001 to 10 μm, more preferably 0.01 to 4 μm, and even more preferably 0.02 to 1 μm.
The primer layer can be formed by a known method.

(Surface functional layer)
The surface functional layer is a layer provided on the surface of the cured film (uneven layer) opposite to the substrate layer to impart various functions. Examples of the surface functional layer include an antifouling layer, an antistatic layer, a refractive index adjustment layer (antireflection layer, low reflection layer, etc.), an infrared absorbing layer, an ultraviolet absorbing layer, and a color correction layer. The surface functional layer may be a single layer having a single or multiple functions, or may be composed of multiple layers.

The antifouling layer is provided to improve the antifouling performance by imparting water repellency and oil repellency to the cured film. Materials used for the antifouling layer include conventionally known materials such as silicone compounds, fluorine compounds, and compounds containing long-chain alkyl groups. Among these, silicone compounds and fluorine compounds are preferred for achieving stronger antifouling performance, and fluorine compounds and compounds containing long-chain alkyl groups are preferred from the viewpoint of not contaminating the object with which the antifouling layer comes into contact.

Silicone compounds refer to compounds having a silicone structure in the molecule, and examples thereof include alkyl silicones such as dimethyl silicone and diethyl silicone, and also phenyl silicone and methylphenyl silicone having a phenyl group. Silicones having various functional groups can also be used, and examples thereof include ether groups, hydroxyl groups, amino groups, epoxy groups, carboxylic acid groups, halogen groups such as fluorine, perfluoroalkyl groups, various alkyl groups, and various aromatic groups and other hydrocarbon groups. As other functional groups, silicones having vinyl groups and hydrogen silicones in which hydrogen atoms are directly bonded to silicon atoms are also common, and both can be used in combination to form silicones of addition type (types obtained by the addition reaction of vinyl groups and hydrogen silane). In addition, a method of introducing a double bond such as an acryloyl group and reacting at the double bond is also preferred.
In addition, as the silicone compound, modified silicones such as acrylic grafted silicone, silicone grafted acrylic, amino modified silicone, perfluoroalkyl modified silicone, etc. are also usable. In consideration of heat resistance and contamination, it is preferable to use a curable silicone resin, and as the type of curable type, any curing reaction type such as condensation type, addition type, active energy ray curable type, etc. can be used.

The fluorine compound is a compound containing fluorine atoms. As the fluorine compound, an organic fluorine compound is preferably used, for example, a perfluoroalkyl group-containing compound, a polymer of an olefin compound containing a fluorine atom, an aromatic fluorine compound such as fluorobenzene, etc. From the viewpoint of mold releasability, a compound having a perfluoroalkyl group is preferable. Furthermore, the fluorine compound can also be a compound containing a long chain alkyl compound as described later.
Examples of the compound having a perfluoroalkyl group include perfluoroalkyl group-containing (meth)acrylates such as perfluoroalkyl (meth)acrylate, perfluoroalkyl methyl (meth)acrylate, 2-perfluoroalkyl ethyl (meth)acrylate, 3-perfluoroalkyl propyl (meth)acrylate, 3-perfluoroalkyl-1-methylpropyl (meth)acrylate, and 3-perfluoroalkyl-2-propenyl (meth)acrylate, and polymers thereof; and perfluoroalkyl group-containing vinyl ethers such as perfluoroalkyl methyl vinyl ether, 2-perfluoroalkyl ethyl vinyl ether, 3-perfluoropropyl vinyl ether, 3-perfluoroalkyl-1-methylpropyl vinyl ether, and 3-perfluoroalkyl-2-propenyl vinyl ether, and polymers thereof. In consideration of heat resistance and contamination, a polymer is preferable. The polymer may be a single compound or a polymer of multiple compounds. In addition, from the viewpoint of antifouling properties, the perfluoroalkyl group preferably has 3 to 11 carbon atoms. Furthermore, it may be a polymer with a compound containing a long-chain alkyl compound as described below.

The long-chain alkyl compound is a compound having a straight-chain or branched alkyl group having usually 6 or more carbon atoms, preferably 8 or more, 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, and a behenyl group. 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. In addition, from the viewpoint of effectively obtaining antifouling properties, 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 polyester resin containing a reactive group, and a poly(meth)acrylic resin containing a reactive group. Among these, polyvinyl alcohol is preferred in terms of antifouling properties and ease of handling.
Examples of compounds having an alkyl group capable of reacting with the reactive group include long-chain alkyl group-containing isocyanates such as hexyl isocyanate, octyl isocyanate, decyl isocyanate, lauryl isocyanate, octadecyl isocyanate, and behenyl isocyanate, long-chain alkyl group-containing acid chlorides such as hexyl chloride, octyl chloride, decyl chloride, lauryl chloride, octadecyl chloride, and behenyl chloride, long-chain alkyl group-containing amines, and long-chain alkyl group-containing alcohols. Among these, in consideration of releasability and ease of handling, long-chain alkyl group-containing isocyanates are preferred, and octadecyl isocyanate is particularly preferred.
Furthermore, polymeric compounds having a long-chain alkyl group in the side chain can also be obtained by polymerization of a long-chain alkyl (meth)acrylate or copolymerization of a long-chain alkyl (meth)acrylate with another vinyl group-containing monomer. Examples of long-chain alkyl (meth)acrylates 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 achieving antifouling performance in the surface functional layer depends on the material used and cannot be generalized, but in the case of silicone compounds and fluorine compounds, it is usually 0.01% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.2% by mass or more, and the upper limit may be 100% by mass. In addition, when a long-chain alkyl group-containing compound is used, it is usually 0.1% by mass or more, preferably 1% by mass or more, and even more preferably 3% by mass or more, and the upper limit may be 100% by mass. By using it in the above range, effective antifouling performance can be obtained.

As the antistatic agent used when forming the antistatic layer as the surface functional layer, various conventionally known antistatic agents can be used. In addition, a method in which a double bond such as an acryloyl group is introduced into a compound having an ammonium group and the double bond is reacted is also preferred.

Examples of the refractive index adjusting layer include a high refractive index layer, a low refractive index layer, and a laminate thereof.
When the objective is to increase the refractive index, materials that are conventionally known can be used as the material for the refractive index adjusting layer. Examples of such materials include aromatic-containing compounds such as a benzene structure, a bisphenol A structure, a melamine structure, and a fluorene structure; condensed polycyclic aromatic compounds such as naphthalene, anthracene, phenanthrene, naphthacene, benzo[a]anthracene, benzo[a]phenanthrene, pyrene, benzo[c]phenanthrene, and perylene structures, which are considered to be high refractive index compounds among aromatic compounds; metal oxides such as zirconium oxide, titanium oxide, zinc oxide, tin oxide, antimony oxide, yttrium oxide, indium oxide, cerium oxide, ATO (antimony tin oxide), and ITO (indium tin oxide); metal-containing compounds such as metal chelate compounds such as titanium chelate and zirconium chelate; compounds containing a sulfur element; and compounds containing a halogen element.
Metal oxides are preferably used in the form of particles since there is a concern that their adhesion may decrease depending on the form of use, and the average primary particle diameter thereof is preferably 100 nm or less, more preferably 50 nm or less, and even more preferably 25 nm or less, from the viewpoint of coating appearance and the like.
When the refractive index adjustment layer is intended to have a low refractive index, the material of the refractive index adjustment layer can be a conventionally known material, for example, low refractive index acrylic resin or urethane resin.In addition, in particular, compounds in which fluorine atoms are incorporated in the resin, such as fluororesins, compounds containing fluororesins in the main skeleton, and compounds containing perfluoroalkyl groups in the side chain, can be mentioned.In addition, inorganic materials can be, for example, hollow silica particles, fluorine atom-containing inorganic compounds such as magnesium fluoride and calcium fluoride, and hollow particles or 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 to the convex of the uneven structure of the cured film. The smaller this ratio is, the less likely the matte performance of the cured film is to decrease. The thickness of the surface functional layer depends on the height from the concave to the convex of the uneven structure of the cured film, so it cannot be generally stated, but is usually in the range of 0.001 to 3 μm, preferably 0.005 to 2 μm, more preferably 0.01 to 1 μm, even more preferably 0.02 to 0.5 μm, and particularly preferably 0.03 to 0.2 μm. By using within the above range, it is possible to achieve both the expression of the function of the surface functional layer and the matte property of the cured film.
The surface functional layer can be formed by a known method.

(Back functional layer)
The back functional layer is a layer provided on the surface opposite to the cured film (uneven layer) of the base layer to impart various functions. Examples of the back functional layer include an adhesive layer, an antistatic layer, a refractive index adjustment layer, and an antiblocking layer. The back functional layer may be a single layer having a single or multiple functions, or may be composed of multiple layers.

The adhesive layer is provided to bond the laminate to various adherends. The antistatic layer is provided to prevent adhesion of dust and the like due to peeling charge or friction charge on the outermost surface of the laminate, particularly on the outermost surface opposite to the uneven layer side of the base layer, and to prevent defects and the like caused thereby. The refractive index adjustment layer is provided, for example, to improve the total light transmittance of the laminate. The antiblocking layer is provided to reduce blocking of the laminate.
Examples of the adhesive for forming the adhesive layer include known adhesives such as acrylic, polyester, urethane and rubber adhesives. Among these, acrylic adhesives are preferred in view of versatility.
The components forming the antistatic layer and the refractive index adjusting layer are the same as those explained for the surface functional layer.

The thickness of the back functional layer depends on the material used in the back functional layer and the performance to be achieved, and cannot be generally determined, but is, for example, 0.001 to 30 μm. When the back functional layer is an adhesive layer, the thickness is preferably 0.01 to 30 μm, more preferably 0.1 to 20 μm. When the back functional layer is an antistatic layer, the thickness 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 surface functional layer and back functional layer)
The front surface functional layer and the back surface functional layer can be formed, for example, by coating a liquid prepared by dispersing the above-mentioned components in a solution or a solvent so that the solid content is approximately 0.1 to 80% by mass onto a specified surface, followed by drying and curing.
Examples of the coating method include conventionally known coating methods such as gravure coating, reverse roll coating, die coating, air doctor coating, blade coating, rod coating, bar coating, curtain coating, knife coating, transfer roll coating, squeeze coating, impregnation coating, kiss coating, spray coating, calendar coating, and extrusion coating.
The drying and curing conditions when forming the surface functional layer and the back functional layer are not particularly limited, but the drying temperature of the solvent such as water used in the coating liquid is usually in the range of 50 to 150 ° C, preferably 80 to 130 ° C, and more preferably 90 to 120 ° C. The drying time is generally in the range of 3 to 200 seconds, preferably 5 to 120 seconds. In addition, in order to improve the strength of the surface functional layer and the back functional layer, it is preferable to perform a heat treatment after drying at a temperature of usually 150 to 270 ° C, preferably 170 to 230 ° C, and more preferably 180 to 210 ° C. The heat treatment time is generally in the range of 3 to 200 seconds, preferably 5 to 120 seconds. Such a heat treatment is suitable when the laminate is a film.

(Total light transmittance)
The laminate preferably has transparency. The total light transmittance measured by the method described in the Examples below is preferably 50% or more, more preferably 60% or more, even more preferably 70% or more, particularly preferably 80% or more, and most preferably 90% or more, and the higher the transmittance, the more preferable (the upper limit is 100%).

(Hayes)
The haze of the laminate measured by the method described in the Examples below is preferably 1% or more, more preferably 3% or more, even more preferably 5% or more, particularly preferably 10% or more, and most preferably 20% or more, with the upper limit being, for example, 99%. The higher the haze, the better the matte property tends to be.
In particular, when used for anti-glare applications in various displays, the content is preferably 40% or more, more preferably 50% or more, even more preferably 60% or more, particularly preferably 70% or more, and most preferably 80% or more, with the upper limit being, for example, 99%.

The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to the following examples as long as it does not depart from the gist of the present invention.
The measurement and evaluation methods used in the present invention are as follows.

(1) Intrinsic Viscosity of Polyester 1 g of polyester from which components incompatible with the polyester had been removed was precisely weighed, dissolved in 100 ml of a mixed solvent of phenol/tetrachloroethane = 50/50 (weight ratio), and measured at 30°C.

(2) Average primary particle diameter (d50: μm)
The cumulative 50% value (by weight) in the equivalent sphericity distribution measured using a 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 polymer (X)
The weight average molecular weight (Mw) of the acrylic polymer was measured using a gel permeation chromatography (GPC) "HLC-8120" (manufactured by Tosoh Corporation). As the column, TSKgel G5000HXL*GMHXL-L (manufactured by Tosoh Corporation) was used. In addition, a calibration curve was created using F288/F80/F40/F10/F4/F1/A5000/A1000/A500 (manufactured by Tosoh Corporation) and styrene as standard polystyrene. The measurement was performed at a column oven temperature of 40°C using 100 μl of a solution in which the polymer was dissolved in tetrahydrofuran to a concentration of 0.4%. The weight average molecular weight (Mw) was calculated in terms of standard polystyrene.

(4) SP value The SP value was measured by the following method. 0.5 g of a sample was weighed into a 100 ml beaker, and 10 ml of acetone was added to dissolve the resin. Hexane was added dropwise to the solution while stirring with a magnetic stirrer, and the amount of hexane added (vh) at the point where the solution became turbid (cloudy point) was determined. Next, the amount of deionized water added (vd) at the cloudy point when deionized water was used instead of hexane was determined. From vh and vd, the SP value was determined using the formula given in the reference: SUH, CLARKE, J. P. S. A-1, 5, 1671-1681 (1967). In addition, when the solubility parameter cannot be determined by the above method, such as when the sample is not dissolved in acetone, it is estimated by the method proposed by Fedors et al. Specifically, the value is determined by referring to "POLYMER ENGINEERING AND SCIENCE, FEBRUARY, 1974, Vol. 14, No. 2, ROBERT F. FEDORS. (pp. 147-154)".

(5) RSm, Sa and inclination angle (θa)
Using a surface shape measurement system (Hitachi High-Tech Science Corporation's scanning white light interference microscope "VS1330"), the surface shape of the cured film was measured by optical interference method in an area of 177.60 μm × 236.87 μm, and data analysis was performed. The evaluation length used to calculate RSm and θa was 236.87 μm. The magnification of the objective lens during measurement was set to 20 times. In addition, the presence or absence of a wrinkled uneven structure was also confirmed in this evaluation.
The processing conditions used for data analysis are as follows.
Surface correction: 4th order Interpolation: Fully interpolated Filter: Median 3 x 3 pixels Boundary processing: Symmetrical expansion to interpolate edges Trimming: None

(6) Total light transmittance and haze A laminate having a cured film formed on a substrate was used as the measurement subject. The total light transmittance and haze were measured using a haze meter "SH7000" manufactured by Nippon Denshoku Industries Co., Ltd. in accordance with JIS Z8722:2009 (geometric conditions of irradiation and reception of a transparent object), JIS K7361-1:1997 (test method for total light transmittance of plastic-transparent material), and JIS K7136:2000 (method of determining haze of plastic-transparent material).

(7) 20° and 60° Gloss/Matteness A laminate having a cured film formed on a substrate was used as the measurement subject. The 20° and 60° gloss (20° and 60° specular gloss) was measured using a gloss meter "VG2000" manufactured by Nippon Denshoku Industries Co., Ltd. in accordance with JIS Z 8741-1997. The lower the gloss value, the better the matteness.

(8) Pencil Hardness The pencil hardness of the cured film was measured in accordance with JIS K5600-5-4:1999 General testing methods for paints-Part 5: Mechanical properties of coating films-Section 4: Scratch hardness (pencil method).

(9) Matte Property The laminate was placed in a room illuminated by a white linear fluorescent lamp, and the distance between the fluorescent lamp and the laminate was set at 2.5 m. The matte property of the uneven layer side (reflection of the fluorescent lamp) was evaluated by visual observation according to the following evaluation criteria A to D. Evaluations A to C are judgments in which the matte property can be confirmed.
A: The reflected image of the fluorescent light is very blurred and the outline of the fluorescent light cannot be seen.
B: The reflected image of the fluorescent light is blurred, but you can faintly see the outline.
C: The reflected image of the fluorescent light is slightly blurred, and although the outline can be seen, it appears wavy and appears dark white.
D: The reflected image of the fluorescent light is clear and the outline can be clearly seen, and it appears linear and white.

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

(Phase-separating curable composition)
The materials shown below were mixed in the amounts (parts by mass, calculated as 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 became 30 mass%, and the mixture was stirred until it became uniform, to obtain a phase-separated curable composition (coating liquid) used in each of the Examples and Comparative Examples.
(Meth)acrylate (B1): 1,6-hexanediol diacrylate (bifunctional) (SP value: 9.6)
(Meth)acrylate (B2): Glycerin triacrylate (trifunctional) (SP value: 11.0)
Compound having a hydroxyl group (compound (X)) (X): a (meth)acrylic polymer produced by the method shown below.
A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with propylene glycol monomethyl ether (157 parts by mass), glycidyl methacrylate (98 parts by mass), methyl methacrylate (1.0 part by mass), ethyl acrylate (1.0 part by mass), mercaptopropyl trimethoxysilane (1.9 parts by mass), and 2,2'-azobis(2,4-dimethylvaleronitrile) (1.0 part by mass), γ-trimethoxysilylpropanethiol (KBM-803, manufactured by Shin-Etsu Chemical Co., Ltd.) (1.9 parts by mass) and reacted for 3 hours at 65 ° C. Thereafter, 2,2'-azobis(2,4-dimethylvaleronitrile) (0.5 parts by mass) was further added and reacted for 3 hours, after which propylene glycol monomethyl ether (138 parts by mass) and p-methoxyphenol (0.45 parts by mass) were added and heated to 100 ° C. Next, acrylic acid (51 parts by mass) and triphenylphosphine (3.1 parts by mass) were added and reacted at 110° C. for 6 hours to obtain a (meth)acryloyl copolymer (C) having an unsaturated double bond amount (acryloyl equivalent (amount of acryloyl group introduced)) of 4.6 mmol/g. The SP value of the obtained (meth)acryloyl copolymer (C) was 17.4, and the consumption rate of acrylic acid was 94%. The viscosity of this solution (solid content 30% by mass) at 25° C. was 100 mPa·s, and the weight average molecular weight (Mw) was 17,700.
(Meth)acrylic polymer (compound (Y)) (Y): acrylic copolymer "BR-80" (SP value: 13.4) manufactured by Mitsubishi Chemical Corporation
- Photopolymerization initiator (I): IGM Resins B. V. Manufactured by Omnirad 184

(Composition for forming primer layer)
The polyester resin (P1), urethane resin (P2), melamine compound (P3), and particles (P4) shown below were mixed in a polyester resin (P1)/urethane resin (P2)/melamine compound (P3)/particles (P4) (solid The components were mixed in a mass ratio of 60/25/10/5 to obtain a composition for forming a primer layer.
Polyester resin (P1): Aqueous dispersion of polyester resin having the following composition Monomer composition: (acid component) terephthalic acid/isophthalic acid/5-sodium sulfoisophthalic acid // (diol component) ethylene glycol/1,4- Butanediol/diethylene glycol=56/40/4//70/20/10 (mol%)
Urethane resin (P2): Aqueous dispersion of polyester-based urethane resin having the following composition: Isophorone diisocyanate: terephthalic acid: isophthalic acid: ethylene glycol: diethylene glycol: dimethylolpropanoic acid = 12: 19: 18: 21: 25: 5 ( mol%)
Melamine compound (P3): hexamethoxymethylolmelamine Particles: (P4): silica particles with an average primary particle size of 0.07 μm

(Polyester film substrate)
A raw material obtained by mixing polyesters (S1), (S2), and (S3) in proportions of 91 mass%, 3 mass%, and 6 mass%, respectively, was used as the raw material for the outermost layer (surface layer), and a raw material obtained by mixing polyesters (S1) and (S2) in proportions of 97 mass% and 3 mass%, respectively, was used as the raw material for the intermediate layer. Each of these raw materials was supplied to two extruders and melted at 285°C. After that, the raw materials were co-extruded onto a cooling roll set at 40°C in a layer structure of two types and three layers (extrusion amount of surface layer/intermediate layer/surface layer = 1:8:1), and then cooled and solidified to obtain an unstretched sheet.
Next, the film was stretched 3.1 times in the longitudinal direction at a film temperature of 85°C using the difference in roll peripheral speed, and then a composition for forming a primer layer was applied to one side of this longitudinally stretched film, which was then introduced into a tenter and dried at 95°C for 10 seconds.Then, the film was stretched 4.2 times in the transverse direction at 120°C, heat-treated at 230°C for 10 seconds, and then relaxed by 2% in the transverse direction to obtain a polyester film substrate having a thickness (after drying) of 50 μm and a 0.1 μm-thick primer layer on one side.

[Examples 1 to 5]
A coating solution shown in Table 1 was applied onto the primer layer of a polyester film and dried at 70°C for 1 minute to form an uneven structure by phase separation. The coating film made of the coating solution shown in Table 1 was then irradiated with excimer light (half width 14 nm) from xenon (wavelength 172 nm) at an irradiation dose of 15 mJ/ ^cm2 and an illuminance of 5 mW/ ^cm2 (Ushio Inc. xenon excimer 172 nm light irradiator, lamp unit type: SUS05 (lamp house type: H0011, lighting power supply type: B0005), nitrogen flow (oxygen concentration 1% or less)), and further irradiated with a high-pressure mercury lamp in an air atmosphere at an accumulated light dose of 400 mJ/ ^cm2 and an illuminance of 200 mW/ ^cm2 (I-Graphics Inc. The coating was irradiated with ultraviolet light using a UV conveyor of a high-output UV device (model: US5-X1802-X1202) to obtain a laminate having a cured film with the thickness (after drying) shown in Table 2.
The cured film of this laminate had a wrinkled uneven structure and had good matte properties. The evaluation results of this laminate are shown in Table 2 below.

[Comparative Examples 1 to 5]
A laminate having a cured film was obtained by manufacturing in the same manner as in Example 1, except that the composition of the coating solution in Example 1 was changed to the composition shown in Table 1, and curing was performed only by irradiation with ultraviolet light from a high-pressure mercury lamp without using excimer light. When the obtained laminate was evaluated, as shown in Table 2 below, it had lower matte properties compared to examples of the same composition and film thickness using excimer light.
In addition, when excimer light was not used, some of the products were insufficiently cured and had low pencil hardness. For such products, the amount of ultraviolet light irradiated by the high-pressure mercury lamp was increased to make the pencil hardness comparable to that of the examples, but the wrinkled uneven structure was not formed, and physical properties such as matte finish were not improved.

Claims (8)

a cured film obtained by curing a phase-separating curable composition, the cured film having a concave-convex structure on its surface resulting from phase separation and also having a concave-convex structure on its surface resulting from irradiation with excimer light,
The curable composition contains, for phase separation, a compound (X) containing at least one polar group selected from a hydroxyl group, an amino group, an amide group, a sulfonyl group, a phosphate group, and a thiol group, and a compound (Y) containing no polar group selected from a hydroxyl group, an amino group, an amide group, a sulfonyl group , a phosphate group, and a thiol group, and further contains at least one (meth)acrylate of a difunctional (meth)acrylate and a trifunctional (meth)acrylate,
the compound (X) is a polymeric compound having a (meth)acryloyl group and an SP value of 15.1 or more;
The compound (Y) is a (meth)acrylic polymer,
a ratio of the compound (X) to a non-volatile content in the curable composition is 10 to 62 mass%, a ratio of the compound (Y) to a non-volatile content in the curable composition is 3 to 55 mass%, and a ratio of the (meth)acrylate to a non-volatile content in the curable composition is 35 to 87 mass%,
The average value (θa) of the local inclination angle of the uneven structure is 2° or more,
The uneven structure has a mean length (RSm) of roughness curve elements according to JIS B0601:2013 of 21 μm or more. The cured film according to claim 1, wherein the arithmetic mean height (Sa) of the uneven structure as defined by ISO25178 is 0.1 μm or more. The cured film according to claim 1 or 2, wherein the 60° gloss of the surface is 50 or less. The cured film according to any one of claims 1 to 3 , wherein the phase-separating curable composition contains two types of compounds whose SP values are separated by 1.0 or more. The method for producing a cured film according to any one of claims 1 to 4 , wherein the phase-separating curable composition is subjected to phase separation to form a concave-convex structure on a surface thereof, and then cured by irradiating with excimer light. A laminate comprising a substrate and the cured film according to any one of claims 1 to 5 laminated thereon. The laminate according to claim 6 , wherein the substrate is a film. The method for producing a laminate according to claim 6 or 7 , comprising laminating the phase-separating curable composition on a substrate to form a relief structure by phase separation, and then irradiating the substrate with excimer light.