JP2022025617A - Cured film and laminate, and method for producing the same - Google Patents

Abstract

To provide a cured film and a laminate, excellent in delustering properties; and to provide a method for producing the cured film and the laminate.SOLUTION: Provided is a cured film whose surface has an uneven structure derived from phase separation, and in the cured film, the uneven structure includes a wrinkle-like uneven structure formed by the recess and/or protrusion thereof. Provided is a method for producing the cured film, in which a curable composition to be separated in phase is irradiated with vacuum ultraviolet rays to be cured after the cured composition is separated in phase and the uneven structure is formed on the surface thereof. Provided is a laminate formed by having the cured film laminated on a base material. Provided is a method for producing the laminate, in which the curable composition to be separated in phase is laminated on the base material, and is irradiated with vacuum ultraviolet rays after the uneven structure by phase separation is formed.SELECTED DRAWING: None

Description

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

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

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

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

The present invention has the following aspects.
[1] A cured film having a concavo-convex structure derived from phase separation on the surface, wherein the concavo-convex structure includes a wrinkled concavo-convex structure formed by the concave and / or convex portions.
[2] The cured film according to the above [1], which is a cured film obtained by curing a curable composition in which the cured film is phase-separated.
[3] The cured film according to the above [1] or [2], wherein the average length (RSm) of the roughness curve element according to JIS B0601: 2013 of the uneven structure is 1 μm or more.
[4] The cured film according to any one of [1] to [3], wherein the arithmetic mean height (Sa) of the uneven structure defined by ISO25178 is 0.1 μm or more.
[5] The cured film according to any one of [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 [1] to [5] above, wherein the surface 60 ° gloss is 50 or less.
[7] The cured film according to any one of [2] to [6] above, wherein the phase-separating curable composition contains (meth) acrylate.
[8] 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. ] To [7].
[9] 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. 2] The cured film according to any one of [8].
[10] The cured film according to any one of [2] to [9] above, wherein the phase-separating curable composition contains two types of compounds having SP values separated by 1.0 or more.
[11] The cured film according to any one of [1] to [10] above, wherein the curable composition for phase separation is phase-separated to form an uneven structure on the surface, and then cured by irradiating with vacuum ultraviolet rays. Production method.
[12] A laminated body in which the cured film according to any one of the above [1] to [10] is laminated on the base material.
[13] The laminate according to the above [12], wherein the base material is a film.
[14] The method for producing a laminated body according to the above [12] or [13], wherein a curable composition for phase separation is laminated on a substrate, a concavo-convex structure is formed by phase separation, and then vacuum ultraviolet rays are irradiated. ..

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

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

[Cured film]
The cured film of the present invention (hereinafter, simply referred to as "cured film") has an uneven structure derived from phase separation on the surface. The cured film of the present invention is suitable as an antiglare film because it has excellent matting properties.

(Average length of roughness curve elements)
The average length of the roughness curve element in the uneven structure of the cured film is the average length of the roughness curve element according to JIS B0601: 2013 (RSm, hereinafter simply referred to as “RSm”). The evaluation length when calculating RSm was 236.87 μm. The preferred range of RSm is 1 μm or more, more preferably 2 to 100 μm, still more preferably 3 to 60 μm, particularly preferably 4 to 50 μm, and most preferably 5 to 35 μm. Within the above range, the matte property is excellent, and the visibility when used for a display or the like is excellent.

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

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

(Thickness)
The thickness of the cured film (concave and convex layer) is preferably in the range of 0.1 to 100 μm, more preferably 1 to 80 μm, still more preferably 2 to 50 μm, and particularly preferably 4 to 30 μm from the viewpoint of improving the matte property. .. The thickness of the cured film indicates the maximum thickness of the uneven layer, and is determined by observing the cross section with an electron microscope.

(gross)
The 60 ° gloss (60 ° mirror gloss) of the surface of the cured film measured by the method described in Examples described later is preferably 50 or less, more preferably 30 or less, still more preferably 20 or less, and particularly preferably 15 or less. Hereinafter, the range is most preferably 12 or less, and the lower the range, the more preferable. The smaller the 60 ° gloss value, the better the matte property.
Similarly, the 20 ° gloss is preferably in the range of 20 or less, more preferably 10 or less, still more preferably 5 or less, particularly preferably 2 or less, and the lower the value, the more preferable. The smaller the 20 ° gloss value, the better the matte property.

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

[Manufacturing method of cured film and laminate]
In the cured film of the present invention and the laminated body of the present invention having the same (hereinafter, simply referred to as “laminated body”), for example, a coating film of a curable composition for phase separation is laminated on a substrate, and unevenness due to phase separation is achieved. After forming the structure, it can be produced by a method of forming a cured film on the surface of the base material by irradiating the surface side (opposite side of the base material) of the coating film with active energy rays.
By irradiating the surface side of the coating film of the curable composition with active energy rays, the surface side of the coating film is cured first to form a cured film. After that, when the inside of the coating film is cured, the cured film on the surface side that has been cured first buckles, so that a cured film having a wrinkle-like uneven structure is formed on the surface. That is, on the surface of the cured film, in addition to the concavo-convex structure due to phase separation, a wrinkle-like concavo-convex structure is formed on the surface, so that the matte property is improved.

(Curable composition that separates from the phase)
The phase-separated curable composition used for forming the cured film contains an active energy ray-curable compound. The curable composition can 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, if necessary. The curable composition can further contain the above-mentioned polar group-free compound, if necessary. The curable composition may further contain an organic solvent, a photopolymerization initiator and other components, if necessary.

Examples of the active energy ray-curable compound include (meth) acrylate. The (meth) acrylate is not particularly limited, and is commercially available as a mixture of one or more types of monofunctional (meth) acrylate, bifunctional (meth) acrylate, and polyfunctional (meth) acrylate, and an active energy ray-curable resin material. Or, other than these, those to which other components are further added can be used as long as the object of the present embodiment is not impaired. Among these, monofunctional or bifunctional (meth) acrylates are preferable from the viewpoint of easily forming a wrinkle-like uneven structure. Bifunctional (meth) acrylates are more preferred for applications that require scratch resistance. It is a preferable form in that the scratch resistance and hardness are improved by using the polyfunctional (meth) acrylate, but it is used because it may be difficult to form a wrinkle-like uneven structure depending on the compound used. Attention should be paid to the type of compound and the mixing ratio.

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

Examples of the monofunctional (meth) acrylate include methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and cyclohexyl (meth) acrylate. Alkyl (meth) acrylates such as isobornyl (meth) acrylates, hydroxyethyl (meth) acrylates, hydroxypropyl (meth) acrylates, hydroxyalkyl (meth) acrylates such as hydroxybutyl (meth) acrylates, methoxyethyl (meth) acrylics, ethoxy Acrylic alkyl (meth) acrylates such as ethyl (meth) acrylates, methoxypropyl (meth) acrylates and ethoxypropyl (meth) acrylates, aromatic (meth) acrylates such as benzyl (meth) acrylates and phenoxyethyl (meth) acrylates, diaminos. Amino group-containing (meth) acrylates such as ethyl (meth) acrylates and diethylaminoethyl (meth) acrylates, methoxyethylene glycol (meth) acrylates, phenoxypolyethylene grease (meth) acrylates, phenylphenol ethylene oxide-modified (meth) acrylates, etc. Examples thereof include ethylene oxide-modified (meth) acrylate, glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and (meth) acrylic.

Examples of the trifunctional or higher polyfunctional (meth) acrylate include dipentaerythritol hexa (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropanetetra (meth) acrylate, pentaerythritol tri (meth) acrylate, and tri. Ethylene oxide-modified (meth) acrylates such as methylol propanetri (meth) acrylates, ethylene oxide-modified dipentaerythritol hexa (meth) acrylates, ethylene oxide-modified pentaerythritol tetra (meth) acrylates, isocyanuric acid ethylene oxide-modified tri (meth) acrylates. , Ε-caprolactone-modified tris (acroxyethyl) isocyanuric acid-modified tri (meth) acrylate such as isocyanurate, pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer, pentaerythritol triacrylate toluenediisocyanate urethane prepolymer, dipentaerythritol pentaacrylate. Examples thereof include urethane acrylate such as hexamethylene diisocyanate urethane prepolymer. Among these, ethylene oxide-modified type and trifunctional (meth) acrylate are preferable in consideration of the ease of forming a wrinkled uneven structure.

In the uneven structure by phase separation, a composition made of materials having different compatibility causes phase separation in the process of coating, drying, and curing, thereby forming an uneven shape on the surface. Conventionally known materials can be used as the material that causes phase separation. In particular, since it is easy to form by coating a film, a composition made of materials having different polarities is preferable. For example, 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 polar group thereof. Combinations can be mentioned. Further, in order to maintain the formed uneven shape and use it for various purposes, it is preferable to use a curable composition for a hard coat.

The characteristic of the 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 a hydrogen bond, whereby unevenness due to phase separation occurs. Structures can be formed. Among these hydrogen-bonding groups, a hydroxyl group, an amino group, and an amide group are preferable because an uneven structure is easily formed by phase separation, and the hydroxyl group, the amino group, and the amide group have stability when a material is mixed and unevenness. It is more preferable from the viewpoint of ease of formation, and a hydroxyl group is particularly preferable. It is also possible to have a plurality of types of polar groups in the compound instead of one type.

Further, considering the ease of forming an uneven structure by phase separation, the compound (X) is preferably a high molecular weight compound rather than a low molecular weight compound. As the polymer compound, (meth) acrylic polymers, polyvinyl alcohols, and celluloses are preferable because they can introduce a larger number of polar groups, and in particular, various functional groups can be introduced and the performance can be easily controlled. The (meth) acrylic polymer is more preferable.

Further, in order to increase the hardness of the cured film having an uneven structure, it is preferable to contain a carbon-carbon unsaturated bond in the above compound (X). The hardness of the cured film formed can be adjusted by the content of carbon-carbon unsaturated bonds. 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 a carbon-carbon double bond is (meth). ) It is more preferably an acryloyl group, and particularly preferably an acryloyl group in consideration of the reactivity of a carbon-carbon unsaturated bond.

In the (meth) acrylic polymer, the 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 has those polar groups. It can also be prepared by copolymerizing the contained (meth) acrylate-based monomer with another (meth) acrylate-based monomer, or the epoxy group-containing (meth) acrylate and the other (meth) acrylate-based monomer can be co-polymerized. It is also possible to react an acid, a base or the like with the epoxy group portion of the polymer obtained by the polymerization to generate a hydroxyl group. In particular, the method using glycidyl (meth) acrylate is useful because it is easy to control the amount of hydroxyl groups.

Examples of the (meth) acrylate containing an epoxy group include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, and 3,4-epoxycyclohexylmethyl (3,4-epoxycyclohexylmethyl). Examples thereof include meth) acrylate and 3,4-epoxycyclohexylmethyl (meth) acrylate. Among these, glycidyl (meth) acrylate is particularly preferable, and glycidyl acrylate is particularly preferable, in consideration of good reactivity and ease of use of the material.

When a hydroxyl group is introduced using a (meth) acrylate containing an epoxy group, the ratio of the (meth) acrylate containing an epoxy group to the (meth) acrylate polymer is preferably 10% by mass or more. The range is more preferably 30% by mass or more, further preferably 50% by mass or more, particularly preferably 80% by mass or more, and the upper limit is 100% by mass. By using it in the above range, it becomes easy to control the polarity of the polymer, and it becomes easy to form an uneven structure by phase separation.

Examples of the compound used for the (meth) acrylate polymer containing an epoxy group for forming a hydroxyl group include an acid and a base, but an acid is preferable in consideration of the stability of the (meth) acrylate polymer, and among them, a carboxylic compound is particularly preferable. It is preferably an acid. Among the carboxylic acids, by further using (meth) acrylic acid, it is possible to introduce a double bond, which is a more preferable form. Among the (meth) acrylic acids, acrylic acid is most suitable in consideration of the reactivity of the epoxy group and the carboxylic acid and the reactivity of the introduced double bond. It is also a preferable form to use a hydroxycarboxylic acid such as lactic acid in order to introduce more hydroxyl groups. Further, it is also possible to react two or more kinds of carboxylic acids with an epoxy group in order to form two or more kinds of structures.

The epoxy group to be reacted is usually in the range of 1% by mass or more, preferably 20% by mass or more, more preferably 50% by mass or more, still more preferably 80% by mass or more, and the upper limit may be 100% by mass. .. By reacting in this range, hydroxyl groups are generated, and it becomes a form in which irregularities due to phase separation are easily formed.

Examples of the (meth) acrylamide-based monomer for containing the amide group in the compound (X) include (meth) acryloylmorpholin, hydroxylmethyl (meth) acrylamide, hydroxylethyl (meth) acrylamide, dimethyl (meth) acrylamide, and diethyl (meth). ) Acrylamide, N-isopropyl (meth) acrylamide and the like. Considering the ease of introduction, an acrylamide monomer is preferable to a methacrylamide monomer. Among the above, (meth) acryloyl morpholine is particularly preferable, and acryloyl morpholine is more preferable, in consideration of the stability and the strength of polarity of the polymer. Further, these (meth) acrylamide-based monomers may be used alone or in combination of two or more.

When a (meth) acrylic polymer is used as the compound (X), various (meth) acrylates that can be polymerized can be used in addition to the above-mentioned compound group. For example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, stearyl (meth) acrylate, phenoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, methoxyethyl (meth). ) Alkyl (meth) acrylate monomers such as acrylate, butoxyethyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate;
Perfluorohexyl ethyl (meth) acrylate, 1H, 1H, 7H-dodecafluoroheptyl (meth) acrylate, 1H, 1H, 9H-hexadecafluorononyl (meth) acrylate and other (meth) acrylate monomers having a fluoroalkyl group;
A (meth) acrylate monomer having an amino group such as N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate;
(Meta) acrylate monomer having a hydroxyl group such as 2-hydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 1,6-hexanediol mono (meth) acrylate;
Raw materials other than (meth) acrylic acid derivatives include styrene, p-chlorostyrene, p-methoxystyrene, divinylbenzene, N-vinylpyrrolidone, N-vinylcaprolactam, acrylonitrile, ethylene glycol divinyl ether, pentaerythritol divinyl ether, 1, It has a vinyl group such as 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. Hydrocarbon-based monomers can be mentioned.

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

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 a (meth) acrylic polymer is a radical polymerization reaction, and a (meth) acrylic polymer can be obtained by polymerizing a raw material monomer in the presence of a radical polymerization initiator in an organic solvent. can.

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

Examples of the radical polymerization initiator include organic peroxides such as benzoyl peroxide and dit-butyl peroxide, 2,2'-azobisbutyronitrile, and 2,2'-azobis (2,4-dimethyl). Examples thereof include azo compounds such as valeronitrile) 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.

Further, the reaction conditions between the epoxy group and the carboxylic acid compound described above are not particularly limited, and a known method can be appropriately selected. The reaction may be carried out without a catalyst or in the presence of a catalyst, and the catalysts include tertiary amines such as triethylamine and benzyldimethylamine, ammonium salts such as tetraethylammonium chloride and tetrabutylammonium bromide, and triphenylphosphine. Examples thereof include phosphines such as 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, based on the weight of the polymer. It is as follows.

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 use of the curable composition, but is usually 5000 or more, preferably 7000 or more, more preferably. Is 9000 or more, usually 200,000 or less, preferably 100,000 or less, more preferably 70,000 or less, still more preferably 50,000 or less. Within the above range, unevenness due to phase separation is likely to be formed on the surface after coating. The weight average molecular weight (Mw) of the (meth) acrylic polymer can be determined by gel permeation chromatography (GPC) as a conversion value according to the polystyrene standard. Specific measurement conditions are shown in the examples below.

The (meth) acrylic polymer of compound (X) has a (meth) acryloyl equivalent (amount of (meth) acryloyl group introduced) of 0.1 mmol / g or more from the viewpoint of improving the scratch resistance of the cured film formed. It is preferably 0.5 mmol / g or more, more preferably 1.0 mmol / g or more, particularly preferably 2.0 mmol / g or more, and 2.5 mmol / g or more. The above is the most preferable. Further, 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 more preferably 6.0 mmol / g or less. Especially preferable. The (meth) acryloyl equivalent shall be calculated based on the raw material used, and it is preferable to select the reaction between the epoxy group and the carboxylic acid so that the (meth) acryloyl equivalent is within the above range.

Examples of the compound (Y) containing no hydroxyl group, amino group, amide group, sulfonyl group, phosphate ester group or thiol group include (meth) acrylic polymers and various (meth) acrylates. That is, it is also possible to use the above-mentioned active energy ray-curable compound as the compound (Y).

In the present invention, the "(meth) acrylic polymer" means a polymer synthesized from a raw material containing (meth) acrylic acid and / or a (meth) acrylic acid derivative, and this polymer is further referred to. It is used in the sense that it also includes a modified polymer. The polymer is not particularly limited as long as it is a polymer using (meth) acrylic acid or a (meth) acrylic acid derivative as at least one raw material ((meth) acrylate monomer). For example, a copolymer using a known polymerizable monomer such as a hydrocarbon-based monomer having a vinyl group other than the (meth) acrylate monomer may be used. The "(meth) acrylic acid derivative" is a compound having a structure similar to that of (meth) acrylic acid, such as a metal salt of (meth) acrylic acid, (meth) acrylic acid ester, and (meth) acrylic acid amide. It shall mean.

Examples of the (meth) acrylic polymer include the above-mentioned (meth) acrylates containing no hydroxyl group, amino group, amide group, sulfonyl group, phosphate ester group, and thiol group, and those formed from monomers that polymerize with them. Can be mentioned.

Further, examples of the (meth) acrylate containing no hydroxyl group, amino group, amide group, sulfonyl group, phosphate ester group and thiol group include the above-mentioned (meth) acrylate. Further, when used as the compound (Y), it is preferable that the polarity is low, so that a compound having few or no hydrogen bonding groups such as ether such as an ethylene oxide structure is preferable.

Compound (X) and compound (Y) are compounds for phase separation. Therefore, from the viewpoint of the solubility parameter (SP value, Solution Parameter), it is preferable that there is a large difference between the two.

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

The SP value of the compound (Y) is preferably 15.0 or less, more preferably 7.0 to 14.5, still more preferably 8.0 to 14.0, and particularly preferably 9.0 to 13.5. It is a range. By using it in the above range, it becomes easy to form a concavo-convex structure by phase separation from the compound (X).

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

The mass ratio of the total amount of the compound (X) to the total amount of the compound (Y) is preferably 10:90 to 80:20, more preferably 12:88 to 60:40, and particularly preferably 15:85 to. It is in the range of 50:50, most preferably 20:80 to 40:60. Within 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% by mass, more preferably 25 to 95% by mass, and further preferably 35 to 70% by mass with respect to the non-volatile content. In the above range, it becomes easy to form a concavo-convex structure by phase separation and a wrinkle-like concavo-convex structure, and it is possible to form a cured film having excellent hardness.
The non-volatile component of the curable composition is the total mass of components other than the solvent such as an organic solvent. The non-volatile content of the curable composition can be measured by a conventionally known method, for example, the weight when 1 g of the composition is spread and heated at 100 ° C. for 1 hour to volatilize the organic solvent. Measured by change.

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 phosphoric acid ester group and a thiol group is used in the formation of the cured film, it is contained in the curable composition. The content of the resin in the above is preferably in the range of 1 to 95% by mass, more preferably 5 to 70% by mass, and further preferably 10 to 60% by mass with respect to the non-volatile content. In the above range, a concavo-convex structure due to phase separation is likely to be formed.

In the formation of the cured film, a (meth) acrylic polymer is used as the compound (Y) which 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. When used, the content of the resin in the curable composition is preferably in the range of 80% by mass or less, more preferably 1 to 70% by mass, still more preferably 3 to 30% by mass with respect to the non-volatile content. be. In the above range, a concavo-convex structure due to phase separation is likely to be formed.

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

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

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

(Various additives)
The curable composition includes a polymerization accelerator such as a thiol group-containing compound, an antifouling agent, an antistatic agent, a plasticizer, a surfactant, an antioxidant, and an ultraviolet absorber, as long as the effects of the present invention are not impaired. Various additives such as agents may be blended.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

(Haze)
The haze of the laminate measured by the method described in Examples described later is preferably 1% or more, more preferably 3% or more, still more preferably 5% or more, particularly preferably 10% or more, and most preferably. Is in the range of 20% or more, and the upper limit is, for example, 99%. The higher the haze, the better the matteness tends to be.
Further, particularly when used for anti-glare of various displays, it is preferably in the range of 40% or more, more preferably 50% or more, further preferably 60% or more, particularly preferably 70% or more, and most preferably 80% or more. Yes, the upper limit is, for example, 99%. Also, depending on the application, the higher the value, the more preferable the application.

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

(1) Extreme viscosity of polyester Weigh 1 g of polyester from which components incompatible with polyester have been removed, add 100 ml of a mixed solvent of phenol / tetrachloroethane = 50/50 (weight ratio), dissolve, and measure at 30 ° C. did.

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

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

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

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

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

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

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

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

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

(Curable composition that separates from the phase)
Each of the materials shown below was mixed in an amount (part by mass, converted to non-volatile content) shown in Table 1. Then, a mixed solvent of propylene glycol monomethyl ether (hereinafter, PGM) and methyl ethyl ketone (hereinafter, MEK) (PGM: MEK (mass ratio) 7: 3) was added so that the solid content concentration was 30% by mass, and the mixture was uniform. The phase-separated curable composition (coating liquid) used in each Example and Comparative Example was obtained by stirring until.
(Meta) acrylate (B1): 1,6-hexanediol diacrylate (bifunctional) (SP value: 9.6)
(Meta) 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.
Propyl 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) in a flask equipped with a thermometer, a stirrer and a reflux cooling tube. ), Mercaptopropyltrimethoxysilane (1.9 parts by mass), and 2,2'-azobis (2,4-dimethylvaleronitrile) (1.0 parts by mass), γ-trimethoxysilylpropanethiol (Shinetsu Chemical Industry Co., Ltd.) 1.9 parts by mass of KBM-803) manufactured by the same company was added, and the mixture was reacted at 65 ° C. for 3 hours. Then, 2,2'-azobis (2,4-dimethylvaleronitrile) (0.5 parts by mass) was further added and reacted for 3 hours, and then propylene glycol monomethyl ether (138 parts by mass) and p-methoxyphenol (13 parts by mass) were added. 0.45 parts by mass) was 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 an unsaturated double bond amount (acryloyl equivalent (acryloyl group)). Introduction amount)) 4.6 mmol / g (meth) acryloyl copolymer (C) was obtained. 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.
(Meta) Acrylic Polymer (Compound (Y)) (Y): Acrylic Copolymer "BR-80" manufactured by Mitsubishi Chemical Corporation (SP value: 13.4)
Photopolymerization Initiator (I): IGM Resins B.I. V. Omnirad 184 manufactured by the company

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

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

[Examples 1 to 5]
The coating liquid shown in Table 1 is applied onto the primer layer of the polyester film, dried at 70 ° C. for 1 minute to form an uneven structure by phase separation, and then irradiated with ultraviolet light (half-value width 14 nm) with xenone (wavelength 172 nm). Amount 15mJ / cm ² , Illuminance 5mW / cm ² (Xenon Exima 172nm light irradiator manufactured by Ushio Denki Co., Ltd., Lamp unit model: SUS05 (Lamp house model: H0011, Lighting power supply model: B0005), Nitrogen flow (oxygen concentration 1% or less) )), The coating film consisting of the coating liquid shown in Table 1 is irradiated, and the integrated light amount is 400 mJ / cm ² and the illuminance is 200 mW / cm ² with a high-pressure mercury lamp in an air atmosphere. The UV conveyor of US5-X1802-X1202) was irradiated with ultraviolet rays to obtain a laminate having a cured film having a film thickness (after drying) shown in Table 2.
The cured film of this laminated body had a wrinkle-like uneven structure and had good matting property. The evaluation results for this laminated body are shown in Table 2 below.

[Comparative Examples 1 to 5]
In Example 1, the composition of the coating film was changed to the composition shown in Table 1, and it was manufactured and cured in the same manner as in Example 1 except that it was cured only by ultraviolet irradiation with a high-pressure mercury lamp without using excimer light. A laminate having a film was obtained. When the obtained laminate was evaluated, as shown in Table 2 below, the matting property was lower than that of the examples having the same composition and the same film thickness using excimer light.
If excimer light was not used, some pencils were insufficiently cured and the pencil hardness was low. For such a thing, we also tried to increase the amount of ultraviolet light irradiation by the high-pressure mercury lamp so that the pencil hardness would be the same as in the example, but the wrinkle-like uneven structure was not formed and the matte property was improved. The physical properties were not improved.

Claims (14)

A cured film having a concavo-convex structure derived from phase separation on the surface, wherein the concavo-convex structure includes a wrinkled concavo-convex structure formed by the concave and / or convex portions thereof. The cured film according to claim 1, which is a cured film obtained by curing a curable composition in which the cured film is phase-separated. The cured film according to claim 1 or 2, wherein the average length (RSm) of the roughness curve element according to JIS B0601: 2013 of the uneven structure is 1 μm or more. The cured film according to any one of claims 1 to 3, wherein the arithmetic mean height (Sa) of the uneven structure defined by ISO 25178 is 0.1 μm or more. The cured film according to any one of claims 1 to 4, wherein the average value (θa) of the local inclination angles of the uneven structure is 2 ° or more. The cured film according to any one of claims 1 to 5, wherein the surface 60 ° gloss is 50 or less. The cured film according to any one of claims 2 to 6, wherein the curable composition for phase separation contains (meth) acrylate. Any of claims 2 to 7, wherein the phase-separating curable composition contains 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. The cured film according to item 1. The curable composition for phase separation contains at least one polar group-free compound selected from a hydroxyl group, an amino group, an amide group, a sulfonyl group, a phosphoric acid ester group, and a thiol group, according to claims 2 to 8. The cured film according to any one of the above items. The cured film according to any one of claims 2 to 9, wherein the curable composition for phase separation contains two kinds of compounds having SP values separated by 1.0 or more. The method for producing a cured film according to any one of claims 1 to 10, wherein the curable composition to be phase-separated is phase-separated to form an uneven structure on the surface, and then cured by irradiating with vacuum ultraviolet rays. A laminate obtained by laminating the cured film according to any one of claims 1 to 10 on a substrate. The laminate according to claim 12, wherein the base material is a film. The method for producing a laminate according to claim 12 or 13, wherein a curable composition for phase separation is laminated on a substrate, a concavo-convex structure is formed by phase separation, and then vacuum ultraviolet rays are irradiated.