JP2022025622A - Transfer molds, transferred objects, and their manufacturing methods - Google Patents

Abstract

To provide a transfer mold with excellent matte finish, a transferred object, and a method for manufacturing the same.SOLUTION: A transfer surface has a wrinkle-like uneven structure, and an average length (RSm) of roughness curve elements according to JIS B0601:2013 of the transfer surface is 1 to 1,000 μm, and an arithmetic mean height (Sa) defined in ISO 25178 is 0.1 to 1,000 μm. A surface to be transferred has a wrinkle-like uneven structure, and the average length (RSm) of the roughness curve elements according to JIS B0601:2013 of the surface to be transferred is 1 to 1,000 μm, and the arithmetic mean height (Sa) defined in ISO 25178 is 0.1 to 1,000 μm.SELECTED DRAWING: None

Description

The present invention relates to a transfer type and an object to be transferred, and a method for producing them.

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.
Patent Document 1 describes hairline processing on a film for transfer foil when manufacturing decorative sheets for building materials, various parts of home appliances such as refrigerators and washing machines, various parts of OA products such as personal computers, and packaging containers by molding. , A method of providing a fine uneven shape by sandblasting, satin finishing, or the like is disclosed.
Patent Document 2 discloses a method of dispersing acrylic particles in a resin binder as a method of forming surface irregularities of a light diffusing film used in a backlight unit of a liquid crystal display.
Patent Document 3 discloses a method for forming surface irregularities by phase separation to prevent anti-Newton's rings.

Japanese Unexamined Patent Publication No. 2004-231727 Japanese Unexamined Patent Publication No. 7-218705 Japanese Unexamined Patent Publication No. 2011-2820

However, the unevenness forming method described in Patent Document 1 cannot obtain a sufficient matting effect. Further, in the sandblasting process, the sand remaining in the film may cause a quality problem.
In the method described in Patent Document 2, acrylic particles may fall off during use, which may hinder visibility when used for a display or the like.
In the method described in Patent Document 3, since a concavo-convex structure is formed by using compounds that are incompatible with each other, the components are not uniform in the layer forming the concavo-convex structure. Therefore, the hardness and scratch resistance are locally non-uniform, and there are places where their performance is inferior, and since the strength is non-uniform, there is also a drawback that they are easily partially chipped in the transfer process. In addition, there is a drawback that the refractive index also changes in the plane depending on the material used. In addition, if a polymer that does not contribute to curing is used, there is a drawback that the hardness and scratch resistance of the entire uneven structure are lowered, which makes it unsuitable for transfer applications.
Further, in the case of the phase separation method, it is necessary to use a material having a highly polar functional group such as cellulose esters in order to make them incompatible with each other. However, the dimensional stability is inferior, which makes it unsuitable for transfer applications.
Further, due to the characteristic of phase separation, there is a drawback that a mold release agent cannot be added due to leveling, and a mold release layer must be provided for transfer (a two-layer structure is formed).

An object of the present invention is to provide a transfer type and a transferred product having excellent mattability, and a method for producing them.

The present invention has the following aspects.
[1] The transfer surface has a wrinkle-like uneven structure, and the average length (RSm) of the roughness curve element according to JIS B0601: 2013 of the transfer surface is 1 to 1000 μm, and is defined by ISO25178. Arithmetic mean height (Sa) is 0.1-1000 μm, transfer type.
[2] The transfer type according to the above [1], wherein the average value (θa) of the local inclination angles of the transfer surface is 2 ° or more.
[3] The transfer type according to the above [1] or [2], wherein the 60 ° gloss of the transfer surface is 50 or less.
[4] The transfer type according to any one of the above [1] to [3], wherein the transfer surface is a cured film of a curable composition.
[5] The transfer type according to the above [4], wherein the curable composition contains (meth) acrylate.
[6] The transfer type according to the above [4] or [5], which has the cured film on a substrate.
[7] The transfer type according to the above [6], wherein the substrate is a film.
[8] The method for producing a transfer type according to the above [6] or [7], wherein the curable composition is laminated on a substrate and cured by irradiating with vacuum ultraviolet rays.
[9] The surface to be transferred has a wrinkle-like uneven structure, and the average length (RSm) of the roughness curve element according to JIS B0601: 2013 of the surface to be transferred is 1 to 1000 μm, and is defined by ISO25178. Arithmetic mean height (Sa) to be transferred is 0.1 to 1000 μm.
[10] The object to be transferred according to the above [9], wherein the average value (θa) of the local inclination angles of the surface to be transferred is 2 ° or more.
[11] The transferred product according to the above [9] or [10], wherein the 60 ° gloss of the surface to be transferred is 50 or less.
[12] The product to be transferred according to any one of the above [9] to [11], wherein the surface to be transferred is a cured film of a curable composition.
[13] The transferred product according to the above [12], wherein the curable composition contains (meth) acrylate.
[14] The transferred product according to the above [12] or [13], which has the cured film on a substrate.
[15] The transfer material according to the above [14], wherein the substrate is a film.
[16] The transferred object according to any one of [9] to [15], wherein the wrinkled uneven structure of the transfer type transfer surface according to any one of [1] to [7] is copied as a negative pattern. How to make things.

The transfer type and the transfer material of the present invention are excellent in matting property. According to the method for producing a transfer type and a transferred product of the present invention, a transfer type and a transferred product having excellent matting properties 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.

[Transfer type]
The transfer type of the present invention has a wrinkled uneven structure on the transfer surface, the average length (RSm) of the roughness curve elements according to JIS B0601: 2013 of the transfer surface is 1 to 1000 μm, and ISO25178. The arithmetic mean height (Sa) defined in is 0.1 to 1000 μm. As a result, the transfer type has a matte property. The transfer type of the present invention is suitable for producing an antiglare film because it has excellent matting properties.

In the transfer type, it is preferable that the uneven structure on the surface is due to a cured film in consideration of durability and ease of manufacture.

(Thickness of transfer type)
The thickness of the layer forming the transfer-type uneven structure (thickness of the cured film (concave and convex layer)) is preferably 0.1 to 100 μm, more preferably 0.2 to 20 μm, still more preferably 0.3 to 10 μm, and particularly. It is preferably in the range of 0.3 to 7 μm. When the thickness of the cured product is within the above range, it is easy to achieve the desired 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.

(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 to 1000 μm, preferably 1.5 to 150 μm, 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. be. Within the above range, the matte property is excellent, the visibility and scratch resistance when the transferred material is used for a display or the like are also excellent, and the performance is well-balanced.

(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 is 177.60 μm × 236.87 μm. Sa is 0.1 to 1000 μm, preferably 0.1 to 100 μm, 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. It is in the range of 4 to 3 μm. Within the above range, the matte property is excellent, the visibility and scratch resistance when the transferred material is used for a display or the like are also excellent, and the performance is well-balanced.

(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 7 ° or more, particularly preferably 10 ° or more, most preferably 12 ° or more, and the upper limit may be 90 °. The higher θa, the better the matte property.

(Haze)
When the transfer type has a cured film, the haze of the cured film measured by the method described in Examples described later is preferably 1% or more, more preferably 3% or more, still more preferably 5% or more. It is particularly preferably in the range of 10% or more, most preferably in the range of 20% or more, and the upper limit is, for example, 99%. When the haze is at least the above lower limit value, it is easy to improve the matte property.
Further, particularly when used for anti-glare of various displays, the range is preferably 40% or more, more preferably 50% or more, still more preferably 60% or more, and the upper limit is, for example, 99%. Also, depending on the application, the higher the value, the more preferable the application. If it is at least the above lower limit value, it is easy to assume that the antiglare property is good.

(gross)
The 60 ° gloss (60 ° mirror gloss) of the transfer surface 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. The range is most preferably 11 or less, and the lower the range, the more preferable. When it is not more than the above upper limit value, the matte property is excellent.
Similarly, the 20 ° gloss is preferably in the range of 30 or less, more preferably 20 or less, still more preferably 10 or less, particularly preferably 5 or less, most preferably 2 or less, and the lower the value, the more preferable. When it is not more than the above upper limit value, the matte property is excellent.

(Total light transmittance)
When searching for defects in the portion of the transfer type uneven structure, it is preferable to have transparency. 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%). Within the above range, the transparency is excellent.

(Pencil hardness)
The pencil hardness of the transfer surface 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 is possible to obtain a transferred material which is excellent in scratch resistance, excellent in scratch prevention in the process before and after transfer, and has few defects due to transfer type scratches.

[Transfer type manufacturing method]
An example of the transfer type of the present invention is a cured film, and examples thereof include a cured product of a curable composition containing an active energy ray-curable compound.
The transfer type of the present invention can be produced, for example, by laminating a curable composition on a substrate and irradiating it with vacuum ultraviolet rays to cure it. The curable composition preferably contains an active energy ray-curable compound. By irradiating the curable composition with active energy rays, the surface side of the coating film of the curable composition is first cured to form a cured film. After that, when the inside of the coating film is cured, the cured coating film on the surface side buckles to form a cured film having wrinkle-like irregularities on the surface. The curable composition and the method for producing a cured film using the curable composition will be described in detail later.

(Transfer-type curable composition)
The curable composition may further contain an organic solvent and other components in addition to the active energy ray-curable compound.

(Active energy ray-curable compound)
As the active energy ray-curable compound, (meth) acrylate is a suitable material. The (meth) acrylate is not particularly limited, and is a mixture of one or more types of monofunctional (meth) acrylate, bifunctional (meth) acrylate, and polyfunctional (meth) acrylate, and commercially available curable resin materials. Alternatively, in addition to these, those to which other components are further added can be used as long as the object of the present embodiment is not impaired. 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.

The bifunctional polyfunctional (meth) acrylate is not particularly limited, but for example, 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and 1,6-hexanediol. Alcandiol di (meth) acrylates such as di (meth) acrylates, 1,9-nonanediol di (meth) acrylates, tricyclodecanedimethylol di (meth) acrylates, bisphenol A ethylene oxide-modified di (meth) acrylates, bisphenols. Examples thereof include bisphenol-modified di (meth) acrylate such as F-ethylene oxide-modified di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, urethane di (meth) acrylate, and epoxy di (meth) acrylate.
Among these, 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.

The monofunctional (meth) acrylate is not particularly limited, and is, for example, methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (. Alkyl (meth) acrylates such as meta) acrylates, cyclohexyl (meth) acrylates and isobornyl (meth) acrylates, hydroxyethyl (meth) acrylates, hydroxypropyl (meth) acrylates, hydroxybutyl (meth) acrylates and other hydroxyalkyl (meth) acrylates. , Methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, methoxypropyl (meth) acrylate, alkoxyalkyl (meth) acrylate such as ethoxypropyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate and the like. Amino group-containing (meth) acrylates such as aromatic (meth) acrylates, diaminoethyl (meth) acrylates, diethylaminoethyl (meth) acrylates, methoxyethylene glycol (meth) acrylates, phenoxypolyethylene grease (meth) acrylates, and phenylphenols. Examples thereof include ethylene oxide-modified (meth) acrylate such as ethylene oxide-modified (meth) acrylate, glycidyl (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate.

The trifunctional or higher polyfunctional (meth) acrylate is not particularly limited, and for example, dipentaerythritol hexa (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and the like. Ethylene oxide-modified (meth) acrylates such as pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide-modified dipentaerythritol hexa (meth) acrylate, and ethylene oxide-modified pentaerythritol tetra (meth) acrylate, isocyanul. Ethylene oxide-modified tri (meth) acrylate, isocyanuric acid-modified tri (meth) acrylate such as ε-caprolactone-modified tris (acroxyethyl) isocyanurate, pentaerythritol triacrylate hexamethylenediisocyanate urethane prepolymer, pentaerythritol triacrylate toluenediisocyanate. Examples thereof include urethane acrylates such as urethane prepolymers and dipentaerythritol pentaacrylate hexamethylene diisocyanate urethane prepolymers. Among these, ethylene oxide-modified type and trifunctional (meth) acrylate are preferable in consideration of the ease of forming a wrinkled uneven structure.

Further, it is also possible to use an active energy ray-curable compound other than the (meth) acrylate in the curable composition. Examples thereof include vinyl compounds such as (meth) acrylic acid, styrene, vinyl halide and vinyl acetate, and diene compounds such as vinylidene halide, 1,3-butadiene, isoprene and chloroprene.

When an active energy ray-curable compound is used in the formation of the transfer type, the content of the compound derived from the active energy ray-curable compound in the transfer type is preferably 5% by mass or more, more preferably 30% by mass. Above, it is more preferably 40% by mass or more, particularly preferably 50% by mass or more, and most preferably 60% by mass or more. The upper limit is not particularly limited and may be 100% by mass, but is preferably in the range of 99% by mass or less, more preferably 98% by mass or less. In the above range, a wrinkle-like uneven structure can be easily formed, and a cured film having excellent hardness and scratch resistance can be formed, and an appropriate transfer type can be obtained.

(resin)
As a transfer type, it is also possible to use various resins for the purpose of improving the adhesion to the base material. As the resin, various conventionally known resins can be used, and examples thereof include acrylic resin, polyester resin, polyurethane resin, and polyvinyl resin. Among these, transparency and affinity with (meth) acrylate are particularly preferable. Acrylic resin is preferable in that it is excellent in quality.

Further, as the resin used for the transfer type, particularly in the case of the transfer type using a cured film, it is preferable to have an active energy ray-curable functional group such as a carbon-carbon double bond in consideration of improvement in scratch resistance and hardness. Examples of the active energy ray-curable functional group include a (meth) acryloyl group and a vinyl ether compound. Among these, a (meth) acryloyl group, particularly an acryloyl group, is preferable in consideration of ease of introduction and reactivity.

In the course of further studies, when a resin having an active energy ray-curable functional group was used, not only the properties directly related to the active energy ray-curable functional group, such as scratch resistance and hardness, were improved. , It was found that the wrinkle-like uneven shape becomes smaller. That is, it was found that the Rsm of the transfer surface became smaller and the Sa also became smaller. In addition, there were cases where the haze was high and the gloss was low. These characteristics can exert a synergistic effect on the matte property, and are important characteristics particularly in applications where visibility is important such as display applications.

As an acrylic resin having an active energy ray-curable functional group such as a carbon-carbon double bond, for example, as a method for introducing the double bond, the acrylic resin having an epoxy group has a double bond and a carboxyl group. A method of reacting a compound (method 1), a method of reacting a compound having a double bond and an epoxy group with an acrylic resin having a carboxyl group (method 2), a compound having a double bond and a carboxyl group with an acrylic resin having a hydroxyl group. (Method 3), a method of reacting a compound having a double bond and a hydroxyl group with an acrylic resin having a carboxyl group (method 4), and reacting a compound having a double bond and a hydroxyl group with an acrylic resin having an isocyanate group. Examples thereof include a method of reacting the acrylic resin having a hydroxyl group with a compound having a double bond and an isocyanate group (method 6). Further, the above methods may be used in combination. In the following, a radically polymerizable monomer having a carbon-carbon double bond may be referred to as a vinyl monomer.

In the method 1, examples of the vinyl monomer having an epoxy group used for obtaining an acrylic resin having an epoxy group include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, and 3,4-epoxy. Cyclohexylmethyl (meth) acrylates can be mentioned. Among these, glycidyl (meth) acrylate is particularly preferable, and glycidyl methacrylate is particularly preferable, in consideration of good reactivity and ease of use of the material. Only one kind of these may be used, or two or more kinds may be combined.

Examples of the compound having a double bond and a carboxyl group in Method 1 include (meth) acrylic acid, carboxyethyl (meth) acrylate, an adduct of glycerindi (meth) acrylate and succinic anhydride, and pentaerythritol tri. Examples thereof include additions of (meth) acrylate and succinic anhydride, and additions of pentaerythritol tri (meth) acrylate and succinic anhydride. Among these, additions of (meth) acrylic acid, pentaerythritol tri (meth) acrylate and succinic anhydride are preferable, (meth) acrylic acid is more preferable, and acrylic acid is even more preferable. As the compound having a double bond and a carboxyl group, only one kind may be used, or two or more kinds may be combined.

In the method 2, examples of the vinyl monomer having a carboxyl group used for obtaining an acrylic resin having a carboxyl group include (meth) acrylic acid, carboxyethyl (meth) acrylate, and polybasic acid-modified (meth) acrylate. Can be mentioned. Among these, (meth) acrylic acid is preferable, and acrylic acid is more preferable. Only one kind of these may be used, or two or more kinds may be combined.

Further, in the method 2, examples of the compound having a double bond and an epoxy group include glycidyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate glycidyl ether. Of these, glycidyl (meth) acrylate is preferable. Only one kind of these may be used, or two or more kinds may be combined.

In the above method 3, examples of the vinyl monomer having a hydroxyl group used for obtaining an acrylic resin having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and hydroxypropyl (meth) acrylate. Can be mentioned. Only one kind of these may be used, or two or more kinds may be combined.

Further, in the method 3, as the compound having a double bond and a carboxyl group, the same compound as in the method 1 can be used.

In the method 4, the same acrylic resin as in the method 2 can be used as the acrylic resin having a carboxyl group.

Further, in the above method 4, examples of the compound having a double bond and a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and hydroxypropyl (meth) acrylate. Only one kind of these may be used, or two or more kinds may be combined.

Examples of the vinyl monomer having an isocyanate group used for obtaining an acrylic resin having an isocyanate group in the method 5 include isocyanate ethyl (meth) acrylate and the like.

Further, in the method 5, as the compound having a double bond and a hydroxyl group, for example, the same compound as the compound mentioned in the method 4 can be used.

In the method 6, as the acrylic resin having a hydroxyl group, the same one as the compound in the method 3 can be used.

Further, in the method 6, examples of the compound having a double bond and an isocyanate group include isocyanate ethyl (meth) acrylate. Only one kind of these may be used, or two or more kinds may be combined.

Among the above methods, method 1 is preferable because the reaction can be easily controlled. In Method 1, the double bond is introduced by a ring-opening / addition reaction between the epoxy group of the acrylic resin having the epoxy group and the carboxyl group in the compound having the double bond and the carboxyl group.

In the method 1, the monomer having an epoxy group in the acrylic resin having an epoxy group is preferably 5% by weight or more, more preferably 10% by weight or more, based on the total amount of the monomers constituting the acrylic resin having an epoxy group. More preferably, it is in the range of 15% by weight or more. The upper limit is not particularly limited, but is preferably 99.9% by weight or less, more preferably 80% by weight or less, still more preferably 70% by weight or less, particularly preferably 50% by weight or less, and most preferably 40% by weight or less. Is the range of. By using it in this range, not only the adhesion of the cured film to the substrate, the scratch resistance, and the hardness tend to be improved, but also the wrinkle-like uneven shape tends to be made finer, and the RSm is lowered, and Sa A reduction, and in some cases an increase in haze and, in some cases, a reduction in gloss can be achieved.

Further, in the above method 1, the compound having a double bond and a carboxyl group is preferably 10 to 150 mol% as the ratio of the compound having a double bond and a carboxyl group to the epoxy group in the acrylic resin having an epoxy group. It is more preferably 30 to 130 mol%, still more preferably 50 to 110 mol%. By using it in the above range, it is preferable from the viewpoint that the reaction proceeds without excess or deficiency and the residue of the raw material is reduced.

Further, the acrylic resin such as the above-mentioned acrylic resin having an epoxy group may be obtained by copolymerizing a (meth) acrylate or other vinyl monomer other than the above-mentioned. The polymerization reaction of these raw materials is usually radical polymerization, and can be polymerized under conventionally known conditions.

Examples of the monomer that can be used together as a raw material include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, and cyclohexyl. (Meta) acrylate, phenyl (meth) acrylate, methoxy (poly) ethylene glycol (meth) acrylate, methoxy (poly) propylene glycol (meth) acrylate, methoxy (poly) ethylene glycol (poly) propylene glycol (meth) acrylate, octoxy (Poly) ethylene glycol (meth) acrylate, octoxy (poly) propylene glycol (meth) acrylate, octoxytetramethylene glycol (meth) acrylate, lauroxy (poly) ethylene glycol (meth) acrylate, stearoxy (poly) ethylene glycol (meth) ) (Meta) acrylates such as acrylates; ethyl (meth) acrylamide, n-butyl (meth) acrylamide, i-butyl (meth) acrylamide, t-butyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N- Acrylamides such as hydroxypropyl (meth) acrylamide and N, N-dihydroxyethyl (meth) acrylamide; styrene-based monomers such as styrene, p-chlorostyrene and p-bromostyrene can be mentioned. Only one kind of these may be used, or two or more kinds may be combined.

The acrylic resin can be produced by a radical polymerization reaction using the above-mentioned raw material vinyl monomer. The radical polymerization reaction is preferably carried out in an organic solvent in the presence of a radical polymerization initiator.

Examples of the organic solvent used for radical polymerization include ketone solvents such as acetone and methyl ethyl ketone (MEK); alcohol solvents such as ethanol, methanol, isopropyl alcohol (IPA) and isobutanol; ethylene glycol dimethyl ether and propylene glycol monomethyl ether. Ether-based solvent; ester-based solvent such as ethyl acetate, propylene glycol monomethyl ether acetate, 2-ethoxyethyl acetate; aromatic hydrocarbon solvent 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 used for radical polymerization include organic peroxides such as benzoyl peroxide and di-t-butyl peroxide; 2,2'-azobisbutyronitrile, 2,2'-azobis (2). , 4-Dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) and other azo compounds. These radical polymerization initiators may be used alone or in combination of two or more. The radical polymerization initiator is preferably used in the range of 0.01 to 5 parts by weight with respect to a total of 100 parts by weight of the raw material vinyl monomer.

Further, in the case of radical polymerization, a chain transfer agent can be used for the purpose of controlling the weight average molecular weight of the acrylic resin. Examples of the chain transfer agent include butane thiol, octane thiol, decane thiol, dodecane thiol, hexadecane thiol, octadecane thiol, cyclohexyl mercaptan, thiophenol, octyl thioglycolate, octyl 2-mercaptopropionate, and octyl 3-mercaptopropionate. , Mercaptopropionic acid 2-ethylhexyl ester, thioglycolate 2-ethylhexyl, butyl-3-mercaptopropionate, mercaptopropyltrimethoxysilane, methyl-3-mercaptopropionate, 2,2- (ethylenedioxy) ) Dietanethiol, ethanethiol, 4-methylbenzenethiol, octanoic acid 2-mercaptoethyl ester, 1,8-dimercapto-3,6-dioxaoctane, decantrythiol, dodecyl mercaptan, diphenylsulfoxide, dibenzyl sulfide, 2,3-Dimethylcapto-1-propanol, mercaptoethanol, thiosalicylic acid, thioglycerol, thioglycolic acid, 3-mercaptopropionic acid, thioapple acid, mercaptoacetic acid, mercapto-amber acid, 2-mercaptoethanesulfonic acid, etc. Examples include thiol-based compounds. These may be used alone or in combination of two or more.

The amount of the chain transfer agent used is preferably 0.1 to 25 parts by weight, more preferably 0.5 to 20 parts by weight, and further preferably 1.0 to 15 parts by weight with respect to 100 parts by weight of the total vinyl monomer as a raw material. preferable.

The reaction time of radical polymerization is preferably 1 to 20 hours, more preferably 3 to 12 hours. The reaction temperature is preferably 40 to 120 ° C, more preferably 50 to 100 ° C.

In order to react the acrylic resin with a compound having a double bond and a carboxyl group, a compound having a double bond and a carboxyl group is added to the acrylic resin obtained as described above to obtain triphenylphosphine. If the reaction is usually carried out at a temperature of 90 to 140 ° C., preferably 100 to 120 ° C. for about 3 to 9 hours in the presence of one or more catalysts such as tetrabutylammonium bromide, tetramethylammonium chloride and triethylamine. good. Here, the catalyst is used at a ratio of about 0.5 to 3 parts by weight with respect to a total of 100 parts by weight of the raw material (meth) acrylic acid ester-based polymer and a compound such as a compound having a double bond and a carboxyl group. It is preferable to use it. This reaction may be continued after the acrylic resin is produced by the polymerization reaction. After the acrylic resin is once separated from the reaction system, a compound such as a compound having a double bond and a carboxyl group is added. You may.

The amount of the double bond in the acrylic resin is preferably 0.1 to 10 mmol / g, more preferably 0.2 to 7.0 mmol / g, still more preferably 0.5 to 5.0 mmol / g, and particularly preferably 0. It is in the range of 8 to 4.0 mmol / g, most preferably 1.0 to 3.0 mmol / g. By using it in this range, not only the adhesion of the cured film to the substrate, the scratch resistance, and the hardness tend to be improved, but also the wrinkle-like uneven shape tends to be made finer, and the Rsm is lowered, and Sa A reduction, and in some cases an increase in haze and, in some cases, a reduction in gloss can be achieved. The double bond amount means the concentration of (meth) acryloyl group in the acrylic resin, that is, the amount of (meth) acryloyl group introduced.

The weight average molecular weight (Mw) of the resin should be appropriately selected depending on the use of the curable composition, but is usually 5000 or more, preferably 7000 or more, and more preferably 9000 or more. It is usually 200,000 or less, preferably 100,000 or less, more preferably 70,000 or less, and further preferably 50,000 or less. Within the above range, surface irregularities are likely to be formed. The weight average molecular weight (Mw) of the resin can be determined as a conversion value according to the polystyrene standard by using gel permeation chromatography (GPC). Specific measurement conditions are shown in the examples below.

When the resin is contained in the transfer mold, the content thereof is preferably in the range of 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, from the viewpoint of the appearance and adhesion of the cured film. Is. If the resin content is too high, there is a concern that the hardness of the cured film will decrease.

(particle)
It is also possible to use particles in order to further improve the matting property due to the transfer type wrinkle-like uneven structure. The particles are not particularly limited, and conventionally known particles can be used. Specific examples include inorganic particles such as silica, hollow silica, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, calcium phosphate, magnesium phosphate, kaolin, aluminum oxide, zirconium oxide, and titanium oxide, acrylic resin, styrene resin, and urea. Examples thereof include organic particles such as a resin, a phenol resin, an epoxy resin, and a 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 contained in the transfer mold, the content thereof is preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably 10% by mass, based on the non-volatile content, from the viewpoint of improving the matting property. % Or less, particularly preferably 8% by mass or less. There is no particular lower limit, but it is preferably in the range of 0.1% by mass or more, more preferably 1% by mass or more. Note that if the amount of particles is too large, they will easily fall off.

(Antistatic agent)
It is also possible to use an antistatic agent for the transfer type. By containing an antistatic agent, it is possible to impart antistatic properties to the transfer type, for example, it is possible to contribute to the prevention of adhesion of foreign substances such as dust due to peeling charge, etc., and the defects due to transfer are reduced, as designed. The transferred material can be obtained.

The antistatic agent is not particularly limited, and conventionally known antistatic agents can be used. Examples thereof include organic compounds such as polymer type and surfactant type, and inorganic compounds such as metal oxides. Among these, an antistatic agent which is an organic compound is preferable because of the ease of forming an uneven structure. Further, since heat resistance, moisture heat resistance, and durability are good, a polymer type antistatic agent is more preferable. Examples of the polymer type antistatic agent include a compound having an ammonium group, a polyether compound, a compound having a sulfonic acid group, a betaine compound, a conductive polymer and the like. Among these, a compound having an ammonium group is more preferable in consideration of the coating appearance.

Further, the antistatic agent can be a compound having an active energy ray-curable functional group. Examples of the active energy ray-curable functional group include (meth) acryloyl groups. By containing the functional group, it is possible to contribute to the formation of an uneven structure and to improve the characteristics such as scratch resistance.

The compound having an ammonium group is a compound having an ammonium group in the molecule, and examples thereof include an aliphatic amine, an alicyclic amine, and an ammonium compound of an aromatic amine. The compound having an ammonium group is preferably a compound having a polymer type ammonium group, and the ammonium group has a structure incorporated in the main chain or side chain of the polymer, not as a counter ion. Is preferable. Further, among the polymers, those capable of increasing the concentration of ammonium groups in order to effectively impart antistatic properties are preferable, and for that reason, (meth) acrylic polymers are preferable. For example, a polymer compound obtained by polymerizing a monomer containing an addition-polymerizable ammonium group or a precursor of an ammonium group such as an amine to a polymer compound having an ammonium group can be mentioned and is preferably used. As the polymer, a monomer containing an addition-polymerizable ammonium group or a precursor of an ammonium group such as an amine may be polymerized alone, or a monomer containing these and another monomer may be polymerized. It may be a copolymer of.

Examples of the precursor monomer of an ammonium group such as an ammonium group or an amine include a (meth) acrylic acid ester of an amino alcohol, specifically, N, N-dimethylaminoethyl (meth) acrylate, N, N-. Diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, N, N-dimethylaminobutyl (meth) acrylate, N, N-diethylaminobutyl (meth) acrylate ) Acrylate, N, N-dihydroxyethylaminoethyl (meth) acrylate and the like can be mentioned, and N, N-dimethylaminoethyl (meth) acrylate is particularly preferably used. The two alkyl groups of the N, N-dialkylamino group may be different.

Examples of the ammonium group of the N, N-dialkylamino group-containing monomer include a quaternized product of commercially available N, N-dimethylaminoethyl methacrylate by methyl chloride [for example, trade name “Light Ester (registered trademark) DQ-”. 100 ”, manufactured by Kyoeisha Chemical Co., Ltd.] and the like. The ammonium group of the N, N-dialkylamino group-containing monomer can also be produced, for example, by a quaternization reaction of a (meth) acrylic acid ester of an amino alcohol.

In the case of a (meth) acrylic polymer, a polymerizable monomer unit other than the precursor monomer of an ammonium group such as an ammonium group or an amine may be contained, and such a polymerizable monomer may contain. For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth). ) Alkyl (meth) acrylates such as acrylates; (meth) acrylic acid esters of the above amino alcohols; hydroxyalkyls such as 2-hydroxyethyl (meth) acrylates, 2-hydroxypropyl (meth) acrylates and hydroxybutyl (meth) acrylates. (Meta) acrylate; benzyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, ethylcarbi Examples thereof include various (meth) acrylates such as toll (meth) acrylate, butoxyethyl (meth) acrylate, cyanoethyl (meth) acrylate, and glycidyl (meth) acrylate, styrene, and methylstyrene. Only one kind of these may be used, or two or more kinds may be combined. Among these, when a polymerizable monomer having a highly hydrophobic long-chain alkyl group is contained, it can be segregated at the air interface of the cured film to enhance the antistatic property of the cured film, which is a preferable form. Is. The polymerizable monomer having such a long-chain alkyl group is preferably an alkyl (meth) acrylate having 8 to 30 carbon atoms, and more preferably an alkyl (meth) acrylate having 12 to 22 carbon atoms. For example, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate and the like can be mentioned.

When the compound having an ammonium group is realized by a (meth) acrylic polymer (polymer), the ratio of the ammonium group-containing monomer unit in the polymer is preferably 5 to 95% by mass, more preferably 10. It is in the range of about 90% by mass, more preferably 20 to 80% by mass, and particularly preferably 30 to 70% by mass. The larger the ratio, the higher the antistatic property, and the smaller the ratio, the better the appearance of the cured product layer after coating, and the balance can be obtained by using the cured product layer in the above range.
When a long-chain alkyl group is used in combination, the proportion of the long-chain alkyl group-containing monomer unit in the polymer is preferably 80% by mass or less, more preferably 50% by mass or less, still more preferably 40% by mass. The range is as follows. By using it in the above range, it becomes easy to develop antistatic properties.

When the compound having an ammonium group is realized by a (meth) acrylic polymer (polymer), the weight average molecular weight of the polymer is preferably 800 to 120,000, more preferably 2,000 to 60,000.

When the compound having an ammonium group is realized by a (meth) acrylic polymer (polymer), the polymer can be produced by a radical polymerization reaction using the above-mentioned raw material monomer. The radical polymerization reaction is preferably carried out in an organic solvent in the presence of a radical polymerization initiator.

Examples of the organic solvent used for the radical polymerization reaction include ketone solvents such as acetone and methyl ethyl ketone (MEK); alcohol solvents such as ethanol, methanol, isopropyl alcohol (IPA) and isobutanol; ethylene glycol dimethyl ether and propylene glycol monomethyl ether. Ether-based solvents such as ethyl acetate, propylene glycol monomethyl ether acetate, 2-ethoxyethyl acetate and the like; aromatic hydrocarbon solvents such as toluene and the like can be mentioned. These organic solvents may be used alone or in combination of two or more.

Examples of the radical polymerization initiator used in the radical polymerization reaction include organic peroxides such as benzoyl peroxide and di-t-butyl peroxide; 2,2'-azobisbutyronitrile, 2,2'-azobis ( Examples thereof include azo compounds such as 2,4-dimethylvaleronitrile) and 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile). These radical polymerization initiators may be used alone or in combination of two or more. The radical polymerization initiator is preferably used in the range of 0.01 to 5 parts by mass with respect to 100 parts by mass of the total of the raw material monomers.

Further, in the radical polymerization reaction, a chain transfer agent can be used for the purpose of controlling the weight average molecular weight of the polymer. Examples of the chain transfer agent include butane thiol, octane thiol, decane thiol, dodecane thiol, hexadecane thiol, octadecane thiol, cyclohexyl mercaptan, thiophenol, octyl thioglycolate, octyl 2-mercaptopropionate, and octyl 3-mercaptopropionate. , Mercaptopropionic acid 2-ethylhexyl ester, thioglycolate 2-ethylhexyl, butyl-3-mercaptopropionate, mercaptopropyltrimethoxysilane, methyl-3-mercaptopropionate, 2,2- (ethylenedioxy) ) Dietanethiol, ethanethiol, 4-methylbenzenethiol, octanoic acid 2-mercaptoethyl ester, 1,8-dimercapto-3,6-dioxaoctane, decantrythiol, dodecyl mercaptan, diphenylsulfoxide, dibenzyl sulfide, 2,3-Dimethylcapto-1-propanol, mercaptoethanol, thiosalicylic acid, thioglycerol, thioglycolic acid, 3-mercaptopropionic acid, thioapple acid, mercaptoacetic acid, mercapto-amber acid, 2-mercaptoethanesulfonic acid, etc. Examples include thiol-based compounds. These may be used alone or in combination of two or more.

The amount of the chain transfer agent used is preferably 0.1 to 25 parts by weight, more preferably 0.5 to 20 parts by weight, and further preferably 1.0 to 15 parts by weight with respect to 100 parts by weight of the total raw material monomers. preferable.

The reaction time of the radical polymerization reaction is preferably 1 to 20 hours, more preferably 3 to 12 hours. The reaction temperature is preferably 40 to 120 ° C, more preferably 50 to 100 ° C.

Examples of the antistatic agent include polyethylene oxide, a polyether ester amide, and an acrylic resin having polyethylene glycol in the side chain.

The compound having a sulfonic acid group as an antistatic agent is a compound containing a sulfonic acid or a sulfonate in the molecule, and is a compound in which a large amount of the sulfonic acid or the sulfonate is present, for example, polystyrene sulfonic acid. Is preferably used.

Examples of the conductive polymer as the antistatic agent include polythiophene-based, polyaniline-based, polypyrrole-based, polyacetylene-based, and among them, for example, poly (3,4-ethylenedioxythiophene) may be used in combination with polystyrene sulfonic acid. The polythiophene system is preferably used. Conductive polymers are more suitable than the other antistatic agents described above in that they have a lower resistance value. However, on the other hand, in applications where coloring and cost are a concern, it is necessary to take measures such as reducing the amount used.

Examples of the antistatic agent include anionic surfactants, cationic surfactants, amphoteric ionic surfactants, and nonionic surfactants. Among these, anionic surfactants and nonionic surfactants are preferable, and anionic surfactants are particularly preferable, from the viewpoint of improving antistatic property and compatibility with various resins.

Examples of the anionic surfactant include sulfonic acid types such as alkyl sulfonates, alkylaryl sulfonates and ester sulfonates, alkyl phosphate esters or salts thereof, polyoxyalkylene alkyl ether phosphate esters or salts thereof. Examples thereof include a phosphate type such as, an alkyl sulfate ester salt, a sulfate ester type such as an alkyl ether sulfate ester salt, and a carboxylate type such as an alkyl fatty acid salt. Among these, the sulfonic acid type is preferable from the viewpoint of excellent antistatic property.

Examples of the sulfonic acid type anionic surfactant include alkyl sulfonates such as decyl sulfonate, dodecyl sulfonate, tetradecyl sulfonate, hexadecyl sulfonate, and octadecyl sulfonate, and butylbenzene sulfonic acid. Salt, hexylbenzene sulfonate, octylbenzene sulfonate, decylbenzene sulfonate, dodecylbenzene sulfonate, tetradecylbenzene sulfonate, hexadecylbenzene sulfonate, octadecylbenzene sulfonate, dibutylnaphthalene sulfonic acid Alkylaryl sulfonates such as salt and triisopropylnaphthalene sulfonate, ester sulfonates such as dibutyl sulfosuccinic acid SL salt, dioctyl sulfosuccinic acid ester salt, dodecyl sulfoacetate ester salt, and nonylphenoxy polyethylene glycol sulfoacetate ester salt can be mentioned. Be done. Among these, from the viewpoint of excellent antistatic property, the alkyl group has 8 or more carbon atoms, preferably 10 to 22 carbon atoms, and more preferably 12 to 18 carbon atoms. Further, as the salt, a metal salt is preferable, an alkali metal salt such as lithium, sodium and potassium is more preferable, and a sodium salt is further preferable. As the type, an alkyl sulfonate is preferable from the viewpoint of antistatic property.

Examples of the phosphoric acid type anionic surfactant include butyl phosphate, butyl phosphate, hexyl phosphate, hexyl phosphate, octyl phosphate, octyl phosphate, decyl phosphate, and decyl phosphate. , Lauryl phosphate, lauryl phosphate, tetradecyl phosphate, tetradecyl phosphate, hexadecyl phosphate, hexadecyl phosphate, stearyl phosphate, stearyl phosphate, etc. Alkyl phosphate ester or its salt, polyoxyethylene butyl ether phosphate ester, polyoxyethylene butyl ether phosphate ester salt, polyoxyethylene hexyl ether phosphate ester, polyoxyethylene hexyl ether phosphate ester salt, polyoxyethylene octyl ether phosphorus Acid ester, polyoxyethylene octyl ether phosphoric acid ester salt, polyoxyethylene decyl ether phosphoric acid ester, polyoxyethylene decyl ether phosphoric acid ester salt, polyoxyethylene lauryl ether phosphoric acid ester, polyoxyethylene lauryl ether phosphoric acid ester salt , Polyoxyethylene tetradecyl ether phosphate, polyoxyethylene tetradecyl ether phosphate, polyoxyethylene hexadecyl ether phosphate, polyoxyethylene hexadecyl ether phosphate, polyoxyethylene stearyl ether phosphate Esters, polyoxyethylene stearyl ether phosphates, polyoxypropylene octyl ether phosphates, polyoxypropylene octyl ether phosphates, polyoxypropylene decyl ether phosphates, polyoxypropylene decyl ether phosphates, Examples thereof include polyoxyalkylene alkyl ether phosphoric acid esters such as polyoxypropylene lauryl ether phosphoric acid ester and polyoxypropylene lauryl ether phosphoric acid ester salts, or salts thereof.

Among these, an alkyl phosphate ester salt, a polyoxyalkylene alkyl ether phosphate ester or a salt thereof is preferable from the viewpoint of performance as a surfactant and antistatic performance.

Regarding the alkyl phosphate ester salt, the alkyl group has 4 or more carbon atoms, preferably 4 to 22 carbon atoms, more preferably 6 to 12 carbon atoms, and the polyoxyalkylene alkyl ether phosphate ester or its salt thereof. The alkyl group has 4 or more carbon atoms, preferably 6 to 22, and more preferably 8 to 18. The salt is preferably a metal salt or an amine salt, more preferably an alkali metal salt such as lithium, sodium or potassium, an alkylamine salt or an alcoholamine salt, and even more preferably a sodium salt or a monoethanolamine salt.

When an antistatic agent is used to impart antistatic properties to the transfer mold, the content of the antistatic agent in the transfer mold is preferably 0.01% by mass or more, more preferably 0.1% by mass or more. It is more preferably 0.5% by mass or more, particularly preferably 1.0% by mass or more, and most preferably 2.0% by mass or more. The upper limit is not particularly limited and may be 100% by mass, but when the hardness of the cured film is taken into consideration, it is preferably 50% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less, and particularly preferably 10. It is in the range of mass% or less, most preferably 8 mass% or less. When it is at least the above lower limit value, the antistatic property is excellent.

(Release agent)
The transfer type may contain a mold release agent, for example, a compound having a fluorine atom or a silicone compound in order to improve antifouling property and transferability. By including the compound in the transfer form, transfer abnormalities due to contamination can be reduced. In addition, it also leads to easy peeling of the transfer material from the transfer mold during transfer, for example, improvement of productivity by eliminating the need to provide a release layer (two-layer structure) in the transfer mold, and transfer. This is a preferable form because it can contribute to the production of a transferred material with few foreign matter defects generated by the transfer material remaining in the mold.

The compound having a fluorine atom is a compound containing a fluorine atom in the compound. As the compound having a fluorine atom, an organic fluorine compound is preferably used, for example, a perfluoroalkyl group-containing compound, a perfluoropolyether compound, a polymer of an olefin compound containing a fluorine atom, and aromatics such as fluorobenzene. Examples include fluorine compounds. From the viewpoint of antifouling property, a compound having a perfluoroalkyl group or a perfluoropolyether compound is preferable. Further, as the fluorine compound, a silicone compound or a compound containing a long-chain alkyl compound 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. And so on. 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 silicone compound or a long-chain alkyl compound.

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.

Further, it is also preferable that the compound having a fluorine atom or the silicone compound described above is a compound having an active energy ray-curable functional group. Examples of the active energy ray-curable functional group include a (meth) acryloyl group and a vinyl ether compound. Among these, a (meth) acryloyl group, particularly an acryloyl group, is preferable in consideration of ease of introduction and reactivity. By containing the functional group, it is possible to contribute to the formation of an uneven structure and to improve the characteristics such as scratch resistance.

The content of the compound having a fluorine atom or the silicone compound in the transfer type is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, still more preferably 0.3% by mass or more, and particularly preferably 0. It is in the range of 5.5% by mass or more, most preferably 0.7% by mass or more. The upper limit is not particularly limited and may be 100% by mass, but when the hardness of the cured film is taken into consideration, it is preferably 50% by mass or less, more preferably 20% by mass or less, still more preferably 10% by mass or less, and particularly preferably 5. It is in the range of mass% or less, most preferably 3 mass% or less. When it is at least the above lower limit, transferability and antifouling property are excellent.

(Photopolymerization initiator)
When the transfer type is formed of a cured film (active energy ray-curable compound), a photopolymerization initiator may be used to promote the curability of the cured film. 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 a photopolymerization initiator is used in the transfer type, the content of the compound derived from the photopolymerization initiator is preferably 20% by mass or less, more preferably 10% by mass or less, and further, from the viewpoint of promoting curability and hardness of the cured film. The range is preferably 8% by mass or less, and particularly preferably 6% by mass or less.

(Leveling agent)
Leveling agents can be used to improve the appearance of the transfer type.
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 the leveling agent is contained in the transfer type membrane, the content thereof is preferably 10% by mass or less, more preferably 8% by mass or less, still more preferably 8% by mass, based on the non-volatile content, from the viewpoint of improving the appearance of the cured membrane. It is in the range of 5% by mass or less.

(Various additives)
As the transfer type, a polymerization accelerator such as a compound containing a thiol group, a plasticizer, a surfactant, an antioxidant, an ultraviolet absorber and the like may be used as long as the effects of the present invention are not impaired.

(Organic solvent)
Further, when the transfer type is formed of a cured film, an organic solvent can be used as necessary for the purpose of improving workability when the transfer type is applied onto the substrate in the curable composition.
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, ethylene glycol diethyl ether and 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-methylpyrrolidone and the like. Amid-based solvents; 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.

The ratio of the organic solvent to 100 parts by mass of the non-volatile content of the curable composition is preferably 10 parts by mass or more and 1900 parts by mass or less, and more preferably 40 parts by mass or more and 400 parts by mass or less, from the viewpoint of improving operability in the coating operation. ..
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.

(Formation of coating film)
As a transfer type forming method, in the case of transfer type forming by a cured film, a curable composition is applied on the surface of a substrate or an article to form a coating film, and if necessary, it is dried and then applied to the coating film. It can be formed by irradiating with active energy rays.
The method of applying the curable composition is not particularly limited. For example, it can be applied by a known method 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.

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)
As the active energy ray, vacuum ultraviolet rays (ultraviolet rays having a wavelength of 200 nm or less) are preferable because it is important that the energy is high in order to effectively cure the surface of the film. Among them, excimer light having a half width of 50 nm or less is most suitable, and examples thereof include argon (126 nm), krypton (146 nm), xenon (172 nm), and argon / fluorine (193 nm). Among these, xenon excimer light is suitable in consideration of ease of use, effective unevenness formation, curability of the cured film, and the like.

When vacuum ultraviolet rays are used, the integrated light intensity for irradiation 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. It is in the range of ² . The illuminance is preferably in the range of 1 to 500 mW / cm ² , more preferably 2 to 300 mW / cm ² , and even more preferably 3 to 100 mW / cm ² .

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 is preferably in the range of 10% or less, more preferably 5% or less, still more preferably 3% or less, and particularly preferably 1% or less.

After the above-mentioned irradiation with vacuum ultraviolet rays, it is preferable to irradiate with active energy rays other than vacuum ultraviolet rays in order to cure the cured film to a deep part. Examples of active energy rays other than vacuum ultraviolet rays include ultraviolet rays and electron beams, and among these, ultraviolet rays are more preferable in consideration of the curability of the cured film.
The integrated amount of ultraviolet rays to be irradiated is preferably in the range of 1 to 5000 mJ / cm ² , more preferably 50 to 3000 mJ / cm ² , still more preferably 100 to 1000 mJ / cm ² , and particularly preferably 200 to 700 mJ / cm ² . .. The illuminance is preferably in the range of 1 to 1000 mW / cm ² , more preferably 50 to 500 mW / cm ² , and even more preferably 80 to 300 mW / cm ² .

[Transcribed material]
The transferred product of the present invention is produced by transferring the shape of the transfer type using the above-mentioned transfer type as a negative pattern. The transferred material has a wrinkled uneven structure on the transferred surface, and the average length (RSm) of the roughness curve elements according to JIS B0601: 2013 of the transferred surface is 1 to 1000 μm, and ISO25178. The arithmetic mean height (Sa) defined in is 0.1 to 1000 μm. As a result, the transferred material has a matte property and can be suitably used for optical applications such as display members.

(Thickness of transfer material)
The thickness of the transfer material (the layer forming the uneven structure of the transfer material) is preferably 0.1 to 1000 μm, more preferably 0.2 to 200 μm, still more preferably 0.3 to 100 μm, and particularly preferably 0. It is in the range of .5 to 30 μm. When the thickness of the transferred material is within the above range, it is easy to realize the desired matting property and it is easy to adjust the hardness.
The thickness of the object to be transferred indicates the maximum thickness of the uneven layer, and is determined by observing the cross section with an electron microscope.

(RSm, Sa, θa of the transferred material)
The RSm, Sa, and θa of the transfer surface of the transfer material are preferably in the same range as the transfer type described above. A major feature of the object to be transferred of the present invention is that it has a structure similar to that of the transfer type. That is, the structure of the transfer type has a shape close to the top and bottom about the zero plane in the height direction, and the transferred object by the transfer type also has a shape similar to that of the transfer type. As a result, once the shape of the transfer type is determined, the shape of the transferred object is assumed to be the same as it is, and the design of the transferred object becomes easy. In addition, normally, in order to create the same shape as the transfer type, the transfer must be repeated twice (that is, a transferred material obtained by transferring the transfer type is created, and the transferred material is used as the transfer type this time. Unless a further transfer material is prepared, the shape will not be the same as that of the first transfer type). According to the transfer type of the present invention, a transfer type having the same shape as the transfer type can be manufactured by one transfer, which is cost effective. In addition, it is superior in terms of the probability of defect occurrence.

The RSm, Sa, and θa of the transferred product of the present invention are preferably in the range of −50 to 50%, more preferably in the range of −30 to 30%, and further preferably in the range of −50 to 50% of the same characteristic value of the transfer type. It is in the range of 20 to 20%, particularly preferably in the range of -10 to 10%. Within the range, the design of the object to be transferred described above becomes easy, and a desired shape can be obtained without performing two transfers.

Further, in the case of the difference between the transferred material and the transfer type having each characteristic, the absolute value of the difference is preferably 25 μm or less, more preferably 20 μm or less, still more preferably 15 μm or less, and particularly preferably 10 μm in the case of RSm. Hereinafter, it is most preferably in the range of 5 μm or less, and in the case of Sa, it is preferably in the range of 5 μm or less, more preferably 3 μm or less, further preferably 2 μm or less, particularly preferably 1 μm or less, and most preferably 0.5 μm or less. In the case of θa, the range is preferably 5 ° or less, more preferably 3 ° or less, still more preferably 2 ° or less, and particularly preferably 1 ° or less. Within the range, the design of the object to be transferred described above becomes easy, and a desired shape can be obtained without performing two transfers.

(Haze of transferred material, 60 ° gloss, 20 ° gloss)
As for the haze of the transferred material (for example, the haze of the cured film when it is formed by a cured film), 60 ° gloss, and 20 ° gloss, the same range as that of the transfer type is a preferable range.
At 60 ° gloss, it is preferably in the range of -50 to 50% of the same characteristics of the transfer type, more preferably in the range of -30 to 30%, still more preferably in the range of -20 to 20%, and particularly preferably in the range of -20 to 20%. It is in the range of -10% to 10%, most preferably in the range of -5% to 5%. Within this range, the design of the transferred material described above becomes easy.

Further, in the case of the difference between the transferred material and the transfer type having each characteristic, the absolute value of the difference is preferably 20 or less, more preferably 10 or less, still more preferably 5 or less, particularly preferably 5 or less in the case of 60 ° gloss. Is 4 or less, most preferably 1 or less, and in the case of 20 ° gloss, it is preferably 10 or less, more preferably 5 or less, still more preferably 3 or less, and particularly preferably 1 or less. Within this range, the design of the transferred material described above becomes easy.

(Total light transmittance of the transferred material)
The total light transmittance of the transferred material is not particularly limited, but it is preferable to have high transmittance when used for an optical film such as an anti-glare film. The total light transmittance including the base material is preferably in the range of 50% or more, more preferably 60% or more, further preferably 70% or more, particularly preferably 80% or more, and most preferably 90% or more, which is high. It is more preferable (the upper limit is 100%).

(Pencil hardness of transfer material)
The hardness of the transferred material is not particularly limited. For example, in the case of a pressure-sensitive adhesive, it is preferable that the performance of the pressure-sensitive adhesive is not deteriorated. On the other hand, when used for optics such as for displays such as anti-glare and blocking prevention, it may be preferable that the hardness is high. When the pencil is used for a purpose in which a higher hardness is preferable, the pencil hardness is F or more, more preferably H or more, still more preferably 2H or more, and particularly preferably 3H or more. Within the above range, it is possible to have excellent scratch resistance, excellent scratch prevention property of the transferred material, and few defects.

In particular, in the material to be transferred, there are few restrictions on the transfer material because it is created by transferring the shape from the transfer mold. Therefore, it is possible to design the hardness to be higher than that of the transfer type, and when a higher hardness is required for optical applications or the like, the transferred material according to the method of the present invention is suitable.

(Curable composition of transferred product)
An example of the transferred product of the present invention is a cured film, and examples thereof include a cured product of a curable composition containing an active energy ray-curable compound.

The transferred product of the present invention is suitable for an antiglare film because it has excellent matting properties.

As long as the transferred material has the above structure, there are no particular restrictions on the material of the transferred material. A method of making a transferred product by contacting the cured product with the transfer mold in an uncured state (in a fluid state) and then curing the cured product, or pressing the transfer mold against a material to be transferred (for example, an adhesive). A method of creating a transferred material and the like can be mentioned. Among these methods, it is preferable that the transferred product is formed from a curable compound (that is, it is a cured film) in consideration of durability and stability of the transferred product, ease of production, and the like. Specific examples thereof include a method of forming a coating film of a curable composition and curing the coating film.

As the curable compound, conventionally known compounds such as active energy ray curing and thermosetting can be used. Among these, an active energy ray-curable compound is preferable, and an ultraviolet-curable compound is more preferable, in consideration of ease of production, repeated use of the transfer type, durability of the transferred material, and the like.

As the active energy ray-curable compound, (meth) acrylate that can be used in the transfer type is also a suitable material for the transferred material. Among the (meth) acrylates, it is preferable to use a trifunctional or higher polyfunctional (meth) acrylate, and a hexafunctional or higher (meth) acrylate is more preferable for applications where it is desired to increase the hardness. For example, dipentaerythritol hexa (meth) acrylate, pentaerythritol tetra (meth) acrylate and trifunctional or higher urethane (meth) acrylate are preferable, and dipentaerythritol hexa (meth) acrylate and hexafunctional or higher urethane (meth) acrylate are preferable. Especially preferable.

Further, it is also possible to use an active energy ray-curable compound other than the (meth) acrylate in the curable composition. For example, vinyl compounds such as styrene, vinyl halide and vinyl acetate, diene compounds such as vinylidene halide, 1,3-butadiene, isoprene and chloroprene can be mentioned.

When an active energy ray-curable compound is used in the formation of the transferred material, the content of the compound derived from the active energy ray-curable compound in the layer forming the uneven structure of the transferred material is preferably 5% by mass. % Or more, more preferably 30% by mass or more, still more preferably 40% by mass or more, particularly preferably 50% by mass or more, and most preferably 60% by mass or more. The upper limit is not particularly limited and may be 100% by mass, but is preferably 99% by mass or less, more preferably 98% by mass or less. In the above range, a transferred material (cured film) having excellent hardness can be formed.
In particular, in applications where it is necessary to improve the hardness and scratch resistance of the transferred material, it is preferable that the content of the trifunctional or higher polyfunctional (meth) acrylate is high, and the trifunctional or higher polyfunctional (meth) acrylate is used. The content of the derived compound is preferably 5% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass or more, particularly preferably 40% by mass or more, and the upper limit is in the range of 100% by mass. ..
Further, in applications where hardness is more important, it is preferable to use a hexafunctional or higher polyfunctional (meth) acrylate, and in that case, the content of the compound derived from the hexafunctional or higher polyfunctional (meth) acrylate is preferable. Is 5% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass or more, particularly preferably 40% by mass or more, and the upper limit is in the range of 100% by mass.

Further, in the formation of the transfer material, it is also possible to use various resins, particles, antistatic agents, antifouling agents, photopolymerization initiators, leveling agents, organic solvents and the like in the formation of the transfer type. ..

(Manufacturing method of transferred material)

As a method for forming a transferable substance, in the case of forming a transferable substance by a cured film, a curable composition is applied on the surface of a substrate or an article to form a coating film, and if necessary, it is dried and then coated. It can be formed by curing the film. The coating method is not particularly limited, and 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. It can be applied by the method.

When the curable composition contains an organic solvent, it is preferably heat-dried in advance. 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.

In the formation of a transferred material by an active energy ray-curable compound, the transferred material is cured by irradiation with active energy rays to form a transferred material by a cured film. The active energy rays are preferably active energy rays other than vacuum ultraviolet rays in order to cure to a deep part, and ultraviolet rays, electron beams and the like are mentioned. Among these, ultraviolet rays are more preferable in consideration of the curability of the cured film.

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

[Layer other than transfer type uneven layer]
The transfer type of the present invention may have a base material layer in addition to a layer having an uneven structure (concave and convex layer) forming a transfer surface. The transfer type is selected from a group consisting of a primer layer provided between the uneven layer and the base material layer, and a back surface functional layer provided on the surface of the base material layer opposite to the uneven layer side. It may have one or more layers. Further, as long as the effect of the present invention is not impaired, the surface functional layer may be provided on the surface of the uneven layer opposite to the base material layer side.

(Transfer type base material layer)
As the base material layer, 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, etc. Polyvinyl alcohol film, nylon film and the like can be mentioned.
When developing this laminate for display applications, polyester films, poly (meth) acrylate films, polyolefin films, polycarbonate films, polyimide films, and triacetyl cellulose films 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 the base material layer 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, 1,4-cyclohexanedimethanol and the like. 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, neopentyl glycol and the like. 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. Considering the above, a film formed from polyethylene terephthalate is more preferable.

As the poly (meth) acrylate constituting the poly (meth) acrylate film that can be used as the base material layer, any acrylic resin may be used as long as it has a unit based on the (meth) acrylate. Examples of the (meth) acrylate include alkyl (meth) acrylates 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. Examples thereof include alkyl (meth) acrylates having an alkyl group having a large number of carbon atoms.
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 layer can 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, if necessary.

The average 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 particle size is 10 μm or less, problems due to a decrease in transparency of the base material layer are unlikely to occur.
The average particle size of the particles is a value of 50% integrated (mass basis) in the equivalent spherical distribution measured by the centrifugal sedimentation type particle size distribution measuring device.

When the base material layer contains particles, the content of the particles in the base material layer cannot be unequivocally determined because it has a balance with the average particle size of the particles, but it is the total number of layers containing the particles in the base material layer. 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 mass. 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 layer are unlikely to occur.

The base material layer can 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.

The thickness of the base material layer is not particularly limited as long as it can form 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.

(Transfer type primer layer)
The primer layer is provided to impart various functions between the base material layer and the uneven layer.
Examples of the primer layer include an adhesion improving layer and an antistatic layer.
The primer layer may have a plurality of functions.

In a preferred embodiment, the primer layer is an adhesion improving layer. If the adhesion between the base material layer 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 layer and the uneven layer is improved, and the uneven layer is less likely to be peeled off from the base material layer during the transfer step.
When the primer layer is an adhesion improving layer, the primer layer preferably contains one or both of a resin and a compound derived from a cross-linking agent from the viewpoint of improving the adhesion between the base material layer and the uneven layer.

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 layer. This makes it possible to reduce defects due to foreign matter contamination during the transfer process.
To make the primer layer an antistatic layer, for example, the primer layer may contain an antistatic agent.

As the resin, 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 layer is a resin film, the resin of the base material layer is preferably a resin of the same type as the resin of the resin film from the viewpoint of the affinity between the primer layer and the base material layer. For example, when the base material layer is a polyester film, the primer layer preferably contains a polyester resin. When the base material layer 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. 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 trimellitic acid, trimesic acid, pyromellitic acid, trimellitic anhydride, phthalic anhydride, trimellitic acid monopotassium salt 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, Polyethylene glycol, Polytetramethylene glycol, Poly Examples thereof include tetramethylene oxide glycol, dimethylolpropionic acid, glycerin, trimethylolpropane, sodium dimethylolethylsulfonate, potassium dimethylolpropionate and the like.
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 polyhydric alcohols include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, and 1,5-pentanediol. , 1,6-Hexanediol, 1,4-Cyclohexanediol, 1,4-Cyclohexanedimethanol, 1,7-Heptanediol, 1,8-octanediol, 1,9-Nonandiol, 1,10-decanediol , Neopentyl glycol, 3-methyl-1,5-pentanediol, 3,3-dimethylol heptane and the like. Examples of the carbonate compound include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate and the like.
Specific examples of the polycarbonate polyol include poly (1,6-hexylene) carbonate, poly (3-methyl-1,5-pentylene) carbonate and the like.

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

Examples of the polyester polyol include those obtained by reacting a polyvalent carboxylic acid or an acid anhydride thereof with a polyhydric alcohol, those having a derivative unit of a lactone compound such as polycaprolactone, and the like.
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, isophthalic acid and the like.
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-butanediol. 2-Methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol , 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', α'. -Adicyclic diisocyanate having an aromatic ring such as tetramethylxylylene diisocyanate; aliphatic diisocyanate such as methylene diisocyanate, propylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene diisocyanate; cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, dicyclohexyl Examples thereof include alicyclic diisocyanates such as methane diisocyanate and isopropyridene dicyclohexyl diisocyanate. 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, and 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 further 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, there are 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. 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 neutralized with a neutralizing agent. Examples include salt that has been neutralized.

The primer layer preferably contains a compound derived from a cross-linking agent in order to strengthen the primer layer and improve performance such as adhesion.
As the cross-linking agent, known materials can be used, and examples thereof include melamine compounds, oxazoline compounds, isocyanate 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. By using two or more types together, the adhesion and durability may be further improved and improved.

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, isobutanol and the like. 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 in which urea or the like is co-condensed 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 naphthalenedi isocyanate; aromatic rings such as α, α, α', α'-tetramethylxylylene diisocyanate. Lipid isocyanate compounds such as methylene diisocyanate, propylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene diisocyanate; cyclohexanediisocyanate, methylcyclohexanediisocyanate, isophorone diisocyanate, methylenebis (4-cyclohexylisocyanate), isopropi. Examples thereof include alicyclic isocyanate compounds such as redendicyclohexyldiisocyanate. Further, polymers and derivatives such as burettes, isocyanurates, uretdiones, and carbodiimide-modified compounds of these isocyanate compounds can also be mentioned. These may be used alone or in combination of two or more. Among the above isocyanate compounds, an aliphatic isocyanate compound or an alicyclic isocyanate compound is more preferable than 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-based compound is blocked by 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. Active methylene compounds such as methyl isobutanoyl acetate, methyl acetoacetate, ethyl acetoacetate, and acetylacetone, mercaptan compounds such as butyl mercaptan and dodecyl mercaptan, lactam compounds such as ε-caprolactam and δ-valerolactam, diphenylaniline, aniline, Examples thereof include amine compounds such as ethyleneimine, acid amide compounds such as acetoanilide and acetate amide, and oxime compounds such as formaldehyde, acetoaldoxime, acetone oxime, methyl ethyl ketone oxime and cyclohexanone oxime. These may be used alone or in combination of two or more.
As the blocked isocyanate compound, an isocyanate compound blocked with an active methylene compound is preferable from the viewpoint that the primer layer is not easily destroyed.

The isocyanate compound may be used alone, or may be used as a mixture or a bond with various polymers. In the sense of improving the dispersibility and crosslinkability of the isocyanate compound, it is preferable to use a mixture or a bond with a polyester resin or a urethane resin.

The oxazoline compound is a compound having an oxazoline group in the molecule.
As the oxazoline compound, a polymer containing an oxazoline group is preferable. The polymer containing an oxazoline group can be obtained by polymerization of an addition-polymerizable oxazoline group-containing monomer alone or with another monomer.
Examples of the additive-polymerizable oxazoline group-containing monomer include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, and 2-isopropenyl-2-oxazoline. , 2-Isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline and the like. These may be used alone or in combination of two or more. Among these, 2-isopropenyl-2-oxazoline is suitable because it is easily available industrially.
The other monomer is not particularly limited as long as it is a monomer copolymerizable with the addition-polymerizable oxazoline group-containing monomer, and is, for example, an alkyl (meth) acrylate (as the alkyl group, a methyl group, an ethyl group, an n-propyl group, etc.). (Meta) acrylates such as isopropyl group, n-butyl group, isobutyl group, t-butyl group, 2-ethylhexyl group, cyclohexyl group); acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, styrene Unsaturated carboxylic acids such as 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 (meth) ) 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 group. , Cyclohexyl group, 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, vinyl fluoride and the like. Halogen-containing α, β-unsaturated monomers; 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 because of better primer layer strength and the like.

The carbodiimide-based compound can be synthesized by a known technique, 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. Specifically, tolylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, phenylenedi isocyanate, naphthalenedi isocyanate, hexa. Examples thereof include methylene diisocyanate, trimethylhexamethylene diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, dicyclohexyldiisocyanate, dicyclohexylmethane diisocyanate and the like.

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 and the like.

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 more 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 thereof 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.

(Transfer type surface functional layer)
The transfer type surface functional layer can be provided to impart various functions to the transfer type surface (on the surface of the uneven layer opposite to the base material layer side).
Examples of the transfer type surface functional layer include a mold release layer and an antistatic layer.

The release layer is provided to improve the transferability. As the material used for the release 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 release performance, and a fluorine compound or a long-chain alkyl group-containing compound is preferable from the viewpoint of not contaminating the transferred material.

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 in the compound. 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. And so on. 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 group-containing compound is a compound having a linear or branched alkyl group having usually 6 or more carbon atoms, preferably 8 or more carbon atoms, and more preferably 12 or more carbon atoms. 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, an acid anhydride and the like. Examples of the compound having these reactive groups include polyvinyl alcohol, polyethyleneimine, polyethyleneamine, a reactive group-containing polyester resin, a reactive group-containing poly (meth) acrylic resin, and the like. 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. Be done.

The content of the mold release agent in the surface functional layer for exhibiting the above-mentioned mold release performance 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 is possible to have effective mold release performance.

As the antistatic agent used when forming the antistatic layer for preventing dust adhesion as the surface functional layer, various conventionally known antistatic agents can be used.

The thickness of the transfer type surface functional layer is preferably 5 times or less the height from the concave portion to the convex portion formed by the uneven layer. This is because the matting performance due to the unevenness is reduced when the height of the unevenness is 5 times or more. The thickness of the surface functional layer cannot be unequivocally determined because it depends on the height of the unevenness, but it is usually 0.001 to 3 μm, preferably 0.005 to 2 μm, more preferably 0.01 to 1 μm, and further preferably 0.02. It is in the range of ~ 0.5 μm, 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 by the unevenness of the uneven layer.
The surface functional layer can be formed by a known method.

(Transfer type back surface functional layer)
The transfer type back surface functional layer can be provided to impart various functions to the surface of the transfer type opposite to the transfer side (the surface of the base material layer opposite to the uneven layer side).
Examples of the back surface functional layer include an adhesive layer, an antistatic layer, an anti-blocking layer and the like.

The thickness of the transfer type 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.

[Layer other than the uneven layer of the transferred material]
The transfer material of the present invention may have a base material layer in addition to the layer having the uneven structure of the transfer material (concave and convex layer). Further, the transfer material is composed of a group consisting of a primer layer provided between the uneven layer and the base material layer, and a back surface functional layer provided on a surface of the base material layer opposite to the uneven layer side. It may have one or more layers of choice. Further, as long as the effect of the present invention is not impaired, the surface functional layer may be provided on the surface of the uneven layer opposite to the base material layer side.

(Base layer of transfer material)
As the base material layer of the transferred material, the same base material layer as the transfer type base material layer can be used.

(Primer layer of transfer material)
As the primer layer of the transfer material, the same primer layer as that of the transfer type primer layer can be used. For example, in the case of an adhesion improving layer, the adhesion between the base material layer and the transferred material can be made sufficient to prevent peeling when the transferred material is used, and in the case of an antistatic layer, the surface of the transferred material can be prevented from peeling off. It is possible to reduce the dust adhering to the dust.

(Surface functional layer of transfer material)
The surface functional layer of the transfer material can be provided to impart various functions to the surface of the transfer material (on the surface of the uneven layer opposite to the base material layer side).
Examples of the surface functional layer of the transferred material 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, a color correction layer, and the like.

The antifouling layer is provided to improve the antifouling performance by imparting water repellency and oil repellency to the uneven layer. 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. Specific examples of the compound include the same materials as those used for the release layer as the transfer type surface functional layer.

As the antistatic agent used when forming the antistatic layer as the surface functional layer of the transferred material, various conventionally known antistatic agents can be used.

Examples of the refractive index adjusting layer include a high refractive index layer, a low refractive index layer, and a laminate thereof.
As a material used when forming a refractive index adjusting layer as a surface functional layer of a transfer material, for the purpose of increasing the refractive index, for example, a benzene structure, a bisphenol A structure, a melamine structure, a fluorene structure, etc. Like naphthalene, anthracene, phenanthrene, naphthalcene, benzo [a] anthracene, benzo [a] phenanthrene, pyrene, benzo [c] phenanthrene, and perylene structures, which are considered to be aromatic-containing compounds and high refractive index compounds among aromatics. Condensed polycyclic aromatic compounds, zirconium oxide, titanium oxide, zinc oxide, tin oxide, antimony oxide, yttrium oxide, indium oxide, cerium oxide, ATO (antimony tin oxide), ITO (indium tin oxide) Examples thereof include metal oxides such as, metal-containing compounds such as 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 particle size thereof is preferably 100 nm or less, more preferably, from the viewpoint of the appearance of coating and the like. Is in the range of 50 nm or less, more preferably 25 nm or less.

As a material used when forming the refractive index adjusting layer as the surface functional layer of the transferred material, a conventionally known material can be used for the purpose of lowering the refractive index, for example, acrylic resin or urethane. Resins are generally possible because of their 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 of the transferred material is preferably 5 times or less the height from the concave portion to the convex portion formed by the uneven layer. This is because the matting performance due to the unevenness is reduced when the height of the unevenness is 5 times or more. The thickness of the surface functional layer cannot be unequivocally determined because it depends on the height of the unevenness, but it is usually 0.001 to 3 μm, preferably 0.005 to 2 μm, more preferably 0.01 to 1 μm, and further preferably 0.02. It is in the range of ~ 0.5 μm, 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 by the unevenness of the uneven layer.
The surface functional layer can be formed by a known method.

(Functional layer on the back surface of the transfer material)
The back surface functional layer of the transfer material can be provided to impart various functions to the surface of the base material layer opposite to the uneven layer side (transfer material side).
Examples of the back surface functional layer of the transferred material include an adhesive layer, an antistatic layer, a refractive index adjusting layer, an anti-blocking layer and the like.
The adhesive layer is provided to join the laminated body to various adherends. The antistatic layer is used to prevent the adhesion of surrounding dust and the like due to peeling and triboelectric charging to the outermost surface of the laminate, especially the outermost surface on the side opposite to the uneven layer side of the base material layer, and defects due to it. It will be provided. 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.

As the pressure-sensitive adhesive for forming the pressure-sensitive adhesive layer, known ones can be used, and examples thereof include acrylic type, polyester type, urethane type, and rubber type. Among them, acrylic is preferable in consideration of versatility.
The antistatic layer and the refractive index adjusting layer are the same as the antistatic layer and the refractive index adjusting layer as the surface functional layer, respectively.

The thickness of the back surface functional layer of the transferred material depends on the material used for the back surface functional layer and the performance to be developed, and therefore cannot be unequivocally determined, 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)
Regarding the formation of the front surface functional layer and the back surface functional layer in both the transfer type and the transfer material, the above-mentioned series of compounds are used as a solution or a dispersion of a solvent, and the solid content concentration is about 0.1 to 80% by mass as a guide. It is preferable to produce the laminate by coating the prepared liquid on the substrate.

As a method for forming the front surface functional layer and the back surface functional layer in both the transfer type and the transfer material, for example, a gravure coat, a reverse roll coat, a die coat, an air doctor coat, a blade coat, a rod coat, a bar coat, and a curtain coat. , Knife coat, transfer roll coat, squeeze coat, impregnation coat, kiss coat, spray coat, calendar coat, extrusion coat and the like, conventionally known coating methods can be used.

The drying and curing conditions for forming the front surface functional layer and the back surface functional layer on the base film in both the transfer type and the transfer material are not particularly limited, but in the case of the coating method, the coating liquid is used. Regarding the drying of the solvent such as water used in the above, the temperature is usually in the range of 50 to 150 ° C, preferably 80 to 130 ° C, and more preferably 90 to 120 ° C. The drying time is, as a guide, 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, when performed in the film manufacturing process, a heat treatment step in the range of usually 150 to 270 ° C., preferably 170 to 230 ° C., more preferably 180 to 210 ° C. is performed. It goes through. The time of the heat treatment step is, as a guide, in the range of 3 to 200 seconds, preferably 5 to 120 seconds.

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 resin
The weight average molecular weight (Mw) of the resin 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) RSm, Sa and θa
Using a surface shape measurement system (Hitachi High-Tech Science Co., Ltd. scanning white interference microscope "VS1330"), the surface shape of the 236.9 μm × 177.6 μm region of the surface of the cured film is measured by the optical interferometry method and complemented. And baseline correction was performed and the data was read. 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.
Regarding the comparison of the physical characteristics of the transfer type and the transfer type, in the percentage comparison, the value obtained by subtracting the transfer type physical property value from the transfer type physical property value is divided by the transfer type physical property value. Calculated. For the difference in each physical property, the absolute value of the value obtained by subtracting the physical property value of the transfer type from the physical property value of the transferred object was calculated.

(5) 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).
Regarding the haze, the haze of only the base material was measured, and the haze of only the concavo-convex structure layer (cured film) due to the transfer type or the transferred material was evaluated by subtracting from the haze measurement value of the laminated body.

(6) 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.

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

(8) Measuring method of surface resistance value High resistivity meter manufactured by Mitsubishi Chemical Analytech Co., Ltd .: After adjusting the humidity of the sample for 30 minutes in the measurement atmosphere of overvoltage 100V, 23 ° C, 50% RH using High Resta MCP-HP450. The surface resistivity of was measured. When the surface resistance value is OVER, it means that the surface resistance value is too high to be measured.

(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.

(10) Magic antifouling property (oil repellent / antifouling property)
After writing on the uneven layer with the oil-based black magic "McKee Fine" manufactured by Zebra Co., Ltd., it was visually observed and evaluated. Repelling the ink is the result of superior oil repellency (stain resistance), and evaluations A and B are judgments that the stain resistance can be confirmed.
A: The ink is repelled.
B: Only the edge where the ink is written is slightly repelled.
C: The ink is not repelled.

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.

(Manufacture of acrylic resin (b1) having an active energy ray-curable functional group)
An acrylic resin (b1) having an active energy ray-curable functional group was produced by the following method.
In a flask equipped with a thermometer, a stirrer and a reflux condenser, propylene glycol monomethyl ether (178 parts by mass), glycidyl methacrylate (20 parts by mass), methyl methacrylate (79 parts by mass), ethyl acrylate (1.0 part by mass), And 2,2'-azobis (2,4-dimethylvaleronitrile) (0.6 parts by mass) were added, and the mixture was reacted at 65 ° C. for 3 hours. Then, 2,2'-azobis (2,4-dimethylvaleronitrile) (0.3 parts by mass) was further added and reacted for 3 hours, and then propylene glycol monomethyl ether (48 parts by mass) and p-methoxyphenol (48 parts by mass) were added. 0.5 part by mass) was added and heated to 100 ° C. Next, acrylic acid (10 parts by mass) and triphenylphosphine (1.6 parts by mass) were added and reacted at 110 ° C. for 6 hours to cause a double bond amount (acryloyl group concentration (introduction of acryloyl group)). Amount)) An acrylic resin (b1) having a radically polymerizable double bond on a 1.2 mmol / g side chain was obtained. The weight average molecular weight (Mw) was 48,800.

(Manufacture of acrylic resin (b2) having an active energy ray-curable functional group)
An acrylic resin (b2) having an active energy ray-curable functional group was produced by the following method.
In a flask equipped with a thermometer, a stirrer and a reflux cooling tube, propylene glycol monomethyl ether (157 parts by mass), glycidyl methacrylate (98 parts by mass), methyl methacrylate (1.0 part by mass), ethyl acrylate (1.0 part by mass). ), Mercaptopropyltrimethoxysilane (1.9 parts by mass), and 2,2'-azobis (2,4-dimethylvaleronitrile) (1.0 part by mass), γ-trimethoxysilylpropanethiol (Shinetsu Chemical Industry Co., Ltd.) KBM-803) manufactured by KBM Co., Ltd. was added in an amount of 1.9 parts by mass, 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 a double bond amount (acryloyl equivalent (acryloyl radical introduction amount)). )) An acrylic resin (b2) having a radically polymerizable double bond on a side chain of 4.6 mmol / g was obtained. The weight average molecular weight (Mw) was 17,700.

(Manufacturing of transferable curable composition)
Each of the materials shown below was mixed in an amount (part by mass, converted to non-volatile content) shown in Table 1. Then, a mixed solvent of propylene glycol monomethyl ether (hereinafter, PGM) and methyl ethyl ketone (hereinafter, MEK) (PGM: MEK (mass ratio) 7: 3) was added so that the solid content concentration was 30% by mass, and the mixture was uniform. A coating liquid (transfer-type curable composition) was obtained by stirring until
-(Meta) acrylate (a1): Urethane acrylate (Shikou UV-1700B manufactured by Mitsubishi Chemical Corporation) (trifunctional or higher)
(Meta) acrylate (a2): Modified epoxy acrylate (EBECRYL 3708 manufactured by Dycel Ornex Co., Ltd.) (bifunctional)
(Meta) acrylate (a3): 1,6-hexanediol diacrylate (bifunctional)
(Meta) acrylate (a4): Dimethylol tricyclodecane diacrylate (light acrylate DCP-A manufactured by Kyoeisha Chemical Co., Ltd.) (bifunctional)
(Meta) acrylate (a5): Dipentaerythritol hexaacrylate (six-functional)
(Meta) acrylate (a6): Mixture of pentaerythritol triacrylate (trifunctional) and pentaerythritol tetraacrylate (tetrafunctional) (Viscoat # 300 manufactured by Osaka Organic Chemical Industry Co., Ltd.)
(Meta) acrylate (a7): Polyester urethane (meth) acrylate (Mitsubishi Chemical Corporation Shikou UT-6042 (bifunctional)
(Meta) acrylate (a8): Methoxyethyl acrylate (2-MTA manufactured by Osaka Organic Chemical Industry Co., Ltd.) (monofunctional)
Acrylic resin (b1): Acrylic resin (b1) having an active energy ray-curable functional group produced by the above method.
Acrylic resin (b2): Acrylic resin (b2) having an active energy ray-curable functional group produced by the above method.
-Acrylic resin (b3): BR-80 (acrylic copolymer) manufactured by Mitsubishi Chemical Corporation
-Release agent (compound having a fluorine atom) (c1): Perfluoropolyether compound having an active energy ray-curable functional group (KY-1203 manufactured by Shin-Etsu Chemical Co., Ltd.)
-Release release agent (silicone compound) (c2): Silicone-containing polymer (GL-04R manufactured by Kyoeisha Chemical Co., Ltd.)
-Release release agent (silicone compound) (c3): Silicone hexaacrylate (EBECRYL 1360 manufactured by Dycel Ornex)
-Particle (d): Cross-linked acrylic particles with an average particle diameter of 1.8 μm (MX-180TA manufactured by Soken Chemical Co., Ltd.)
-Photopolymerization initiator (e): IGM Resins B. V. Omnirad 184 manufactured by the company
-Antistatic agent (f): quaternary ammonium base-containing (meth) acrylic polymer (Nikka Whiskey Distillery, manufactured by Mitsubishi Chemical Corporation, number average molecular weight: 28,000)

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

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

[Examples 1 to 6]
The coating liquid (transfer-type curable composition) shown in Table 1 is applied onto the primer layer of the polyester film, dried at 70 ° C. for 1 minute, and irradiated with excimer light (half-value width 14 nm) by xenone (wavelength 172 nm). 15mJ / cm ² , illuminance 5mW / cm ² (Xenon excimer 172nm light irradiator manufactured by Usio Electric Co., Ltd., lamp unit model: SUS05 (lamp house model: H0011, lighting power supply model: B0005), nitrogen flow (oxygen concentration 1% or less) ) Is applied to the coating film consisting of the coating liquid shown in Table 1, 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. -X1802-X1202) UV conveyor) was irradiated with ultraviolet rays to obtain a cured film (transfer type) having a wrinkle-like uneven structure having a thickness (after drying) of 5 μm shown in Table 3. The obtained transfer type had a wrinkle-like uneven structure and had good matting property. The characteristics of this transfer type are shown in Table 3.

[Comparative Example 1]
A cured film (transfer type (T-7)) was obtained in the same manner as in Example 1 except that the film was cured only by irradiation with ultraviolet rays from a high-pressure mercury lamp without using excimer light in Example 1. When the obtained cured film was evaluated, as shown in Table 3, no wrinkle-like uneven structure was formed, the surface was smooth, and no matting property was observed.

[Comparative Example 2]
In Example 1, a cured film (transfer type (T-8)) was obtained by producing in the same manner as in Example 1 except that the composition of the transfer type curable composition was changed to the composition shown in Table 1. When the obtained cured film was evaluated, as shown in Table 3, a wrinkle-like uneven structure was not formed and a convex surface shape was obtained.

[Example 7]
On the transfer mold (T-1) obtained in Example 1, the solution B-1 shown in Table 1 was applied to impart releasability from the transferred material, dried at 70 ° C. for 1 minute, and aired. In the atmosphere, a high-pressure mercury lamp is used to irradiate ultraviolet rays with an integrated light intensity of 400 mJ / cm ² , an illuminance of 200 mW / cm ² (UV conveyor of a high-power UV device manufactured by Eye Graphics (model: US5-X1802-X1202)), and the thickness is increased. A release layer (after drying) of 0.1 μm was formed.
The solvent-free coating liquid (transfer-curable composition C-1) shown in Table 2 was applied onto the release layer, and the polyester film before transfer mold formation obtained in Example 1 was used as a primer for the polyester film. Arranged so that the layer and the curable composition to be transferred are in contact with each other, and in an air atmosphere, the integrated light amount is 400 mJ / cm ² and the illuminance is 200 mW / cm ² with a high-pressure mercury lamp (high-power UV device manufactured by Eye Graphics (model: US5). -X1802-X1202) UV conveyor) was irradiated with ultraviolet rays to form a cured film having a thickness (after drying) of 9 μm. The obtained cured film was peeled off from the transfer type (T-1) to obtain a laminate in which a transfer material was formed on the primer layer of the polyester film.
The obtained transferred material had a wrinkle-like uneven structure and had good matting property. The characteristics of this transferred material are shown in Tables 4 to 6.

[Examples 8 to 13]
In Example 7, the composition was produced in the same manner as in Example 7 except that the composition of the cured composition to be transferred was changed to the composition shown in Table 2, and a transferred film with a cured film was obtained. The characteristics of the obtained transfer material are shown in Tables 4 to 6.

[Example 14]
In Example 7, the product to be transferred was produced in the same manner as in Example 7 except that the release layer was not provided and the curable composition to be transferred shown in Table 2 was directly applied onto the transfer mold. Got The characteristics of the obtained transfer material are shown in Tables 4 to 6.

[Examples 15 to 19]
In Example 14, the composition was produced in the same manner as in Example 14 except that the composition of the transferred product curable composition was changed to the composition shown in Table 2, and a transferred product with a cured film was obtained. The characteristics of the obtained transfer material are shown in Tables 4 to 6.

[Comparative Example 3]
In Example 7, the composition was produced in the same manner as in Example 7 except that the composition of the cured composition to be transferred was changed to the composition shown in Table 2, and a transferred film with a cured film was obtained. The obtained transfer material was concave and had a shape different from that of the transfer type. Other characteristics are shown in Tables 4-6.

Claims (16)

The transfer surface has a wrinkled uneven structure, the average length (RSm) of the roughness curve element according to JIS B0601: 2013 of the transfer surface is 1 to 1000 μm, and the arithmetic mean height defined by ISO25178. Transfer type having a Sa (Sa) of 0.1 to 1000 μm. The transfer type according to claim 1, wherein the average value (θa) of the local inclination angles of the transfer surface is 2 ° or more. The transfer type according to claim 1 or 2, wherein the 60 ° gloss of the transfer surface is 50 or less. The transfer type according to any one of claims 1 to 3, wherein the transfer surface is a cured film of a curable composition. The transfer type according to claim 4, wherein the curable composition contains (meth) acrylate. The transfer type according to claim 4 or 5, which has the cured film on a substrate. The transfer type according to claim 6, wherein the substrate is a film. The transfer type manufacturing method according to claim 6 or 7, wherein the curable composition is laminated on a substrate and cured by irradiating with vacuum ultraviolet rays. The surface to be transferred has a wrinkled uneven structure, the average length (RSm) of the roughness curve elements according to JIS B0601: 2013 of the surface to be transferred is 1 to 1000 μm, and the arithmetic defined by ISO25178. An object to be transferred having an average height (Sa) of 0.1 to 1000 μm. The object to be transferred according to claim 9, wherein the average value (θa) of the local inclination angles of the surface to be transferred is 2 ° or more. The transferred product according to claim 9 or 10, wherein the 60 ° gloss of the transferred surface is 50 or less. The transferred product according to any one of claims 9 to 11, wherein the transferred surface is a cured film of a curable composition. The transferred product according to claim 12, wherein the curable composition contains (meth) acrylate. The transfer product according to claim 12 or 13, which has the cured film on a substrate. The transfer product according to claim 14, wherein the substrate is a film. The method for producing a transferred material according to any one of claims 9 to 15, wherein the wrinkled uneven structure of the transfer surface of the transfer type according to any one of claims 1 to 7 is copied as a negative pattern.