JP2024015367A - Transfer mold, transferred object, and their manufacturing methods - Google Patents

Abstract

To provide a transfer mold with excellent matte finish, a transferred object, and their manufacturing methods.SOLUTION: There is provided a transfer mold that has a curing film of a curable composition in which a surface of the curing film forms a transfer surface, The transfer surface has a wrinkle-like uneven structure, wherein the wrinkle-like uneven shape can be formed by curing a surface side of a coating film of the curable composition by irradiating vacuum ultraviolet rays to form a cured film, and then the cured film on the surface side buckles by curing an inside of a coating film by irradiating active energy rays other than the vacuum ultraviolet rays. 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. There is also provided a transferred object, wherein a transfer surface has a wrinkle-like uneven structure that is obtained by transferring the wrinkle-like uneven structure of the transfer surface of the transfer mold.SELECTED DRAWING: None

Description

The present invention relates to a transfer mold, a transfer target, and a method for producing the same.

In order to impart matte properties to architectural materials such as wallpaper, display members, decorative films, etc., fine irregularities may be provided on the surface of the base material.
Patent Document 1 discloses that hairline processing is applied to a transfer foil film used in the production of 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, packaging containers, etc. , a method of providing fine irregularities by sandblasting, satin finishing, etc. 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 diffusion film used in a backlight unit of a liquid crystal display.
Patent Document 3 discloses a method of forming surface irregularities by phase separation to prevent anti-Newton rings.

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

However, the unevenness forming method described in Patent Document 1 does not provide a sufficient matting effect. Furthermore, during sandblasting, sand remaining in the film may cause quality problems.
In the method described in Patent Document 2, the acrylic particles fall off during use, which may impede visibility when used for displays and the like.
In the method described in Patent Document 3, the uneven structure is formed by using compounds that are incompatible with each other, so the components are not uniform in the layer forming the uneven structure. As a result, the hardness and scratch resistance become locally non-uniform, resulting in areas where these properties are inferior, and since the strength is non-uniform, there is also the drawback that parts are easily chipped during the transfer process. Another drawback is that the refractive index changes within 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 decreases, making it unsuitable for transfer applications.
In addition, in the case of a method based on phase separation, it is necessary to use materials with highly polar functional groups such as cellulose esters to make them incompatible with each other, and using such materials may deteriorate heat and humidity resistance. , resulting in poor dimensional stability, making it unsuitable for transfer applications.
Furthermore, due to the characteristic of phase separation, it is not possible to add a mold release agent because of leveling, and a mold release layer must be provided for transfer (resulting in a two-layer structure).

An object of the present invention is to provide a transfer mold and a transfer object with excellent matte properties, and a method for producing the same.

The present invention has the following aspects.
[1] The transfer surface has a wrinkle-like uneven structure, and the average length (RSm) of roughness curve elements of the transfer surface according to JIS B0601:2013 is 1 to 1000 μm, and is defined by ISO 25178. A transfer type with an arithmetic mean height (Sa) of 0.1 to 1000 μm.
[2] The transfer mold according to [1] above, wherein the average value (θa) of the local inclination angle of the transfer surface is 2° or more.
[3] The transfer mold according to [1] or [2], wherein the transfer surface has a 60° gloss of 50 or less.
[4] The transfer mold according to any one of [1] to [3] above, wherein the transfer surface is a cured film of a curable composition.
[5] The transfer mold according to [4] above, wherein the curable composition contains (meth)acrylate.
[6] The transfer mold according to [4] or [5], which has the cured film on a base material.
[7] The transfer mold according to [6] above, wherein the base material is a film.
[8] The method for producing a transfer mold according to the above [6] or [7], wherein the curable composition is laminated on the base material and cured by irradiation with vacuum ultraviolet rays.
[9] The surface to be transferred has a wrinkle-like uneven structure, and the average length (RSm) of roughness curve elements of the surface to be transferred according to JIS B0601:2013 is 1 to 1000 μm, and as defined in ISO 25178. A transferred object having an arithmetic mean height (Sa) of 0.1 to 1000 μm.
[10] The transferred object according to the above [9], wherein the average value (θa) of the local inclination angle of the transferred surface is 2° or more.
[11] The transferred object according to [9] or [10], wherein the 60° gloss of the transferred surface is 50 or less.
[12] The object to be transferred according to any one of [9] to [11] above, wherein the surface to be transferred is a cured film of a curable composition.
[13] The transferred material according to [12] above, wherein the curable composition contains (meth)acrylate.
[14] The transferred object according to [12] or [13], which has the cured film on a base material.
[15] The transferred object according to [14] above, wherein the base material is a film.
[16] The transfer target according to any one of [9] to [15] above, in which the wrinkle-like uneven structure of the transfer surface of the transfer mold according to any one of [1] to [7] is copied as a negative pattern. How things are manufactured.

The transfer mold and transferred material of the present invention have excellent matte properties. According to the method for producing a transfer mold and a transfer object of the present invention, a transfer mold and a transfer object with excellent matte properties can be obtained.

Embodiments of the present invention will be described in detail below.
In the present invention, "(meth)acrylate" is a general term for acrylate or methacrylate. "(Meth)acrylic" is a general term for acrylic and methacrylic.
"~" indicating a numerical range means that the numerical values written before and after it are included as the lower limit and upper limit.

[Transfer type]
In the transfer mold of the present invention, the transfer surface has a wrinkled uneven structure, and the average length (RSm) of the roughness curve element of the transfer surface according to JIS B0601:2013 is 1 to 1000 μm, and the transfer surface conforms to ISO25178. The arithmetic mean height (Sa) defined by is 0.1 to 1000 μm. As a result, the transfer mold has matte properties. The transfer mold of the present invention has excellent matte properties and is therefore suitable for producing an anti-glare film.

In consideration of durability and ease of manufacture, it is preferable for the transfer mold to have an uneven structure on the surface of the cured film.

(Thickness of transfer mold)
The thickness of the layer forming the uneven structure of the transfer mold (thickness of the cured film (uneven layer)) is preferably 0.1 to 100 μm, more preferably 0.2 to 20 μm, even more preferably 0.3 to 10 μm, especially Preferably it is in the range of 0.3 to 7 μm. If the thickness of the cured product is within the above range, desired matte properties can be easily achieved.
The thickness of the cured film indicates the maximum thickness of the uneven layer, and is determined by cross-sectional observation using an electron microscope.

(Average length of roughness curve element)
The average length of the roughness curve elements in the uneven structure of the cured film is the average length of the roughness curve elements (RSm, hereinafter also simply referred to as "RSm") according to JIS B0601:2013. The evaluation length when calculating RSm was 236.87 μm. The preferred range of RSm is 1 to 1000 μm, preferably 1.5 to 150 μm, more preferably 2 to 100 μm, even more preferably 3 to 60 μm, particularly preferably 4 to 50 μm, and most preferably 5 to 35 μm. be. Within the above range, the matte property is excellent, and when the transferred material is used for a display etc., the visibility and scratch resistance are also excellent, and the performance is well balanced.

(arithmetic mean height)
The arithmetic mean height of the uneven structure of the cured film is the arithmetic mean height (Sa, hereinafter also simply referred to as "Sa") defined in ISO25178. The evaluation area when 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, even 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 matting property is excellent, and when the transferred material is used for a display etc., the visibility and scratch resistance are also excellent, and the performance is well-balanced.

(Average value of inclination angle of uneven structure)
The average value of the local inclination angle (θa, hereinafter also simply referred to as “θa”) in the uneven structure of the cured film can be measured by the method described in the Examples below. The evaluation length when calculating θa was 236.87 μm. θa is preferably 2° or more, more preferably 4° or more, still more preferably 7° or more, particularly preferably 10° or more, most preferably 12° or more, and may have an upper limit of 90°. The higher θa is, the better the matting property is.

(Haze)
When the transfer mold has a cured film, the haze of the cured film measured by the method described in the Examples below is preferably 1% or more, more preferably 3% or more, even more preferably 5% or more, The range is particularly preferably 10% or more, most preferably 20% or more, and the upper limit is, for example, 99%. If the haze is greater than or equal to the above lower limit, it is easy to achieve good matting properties.
In addition, especially when used for anti-glare purposes in various displays, the range is preferably 40% or more, more preferably 50% or more, even more preferably 60% or more, and the upper limit is, for example, 99%. Furthermore, depending on the use, there are some uses where a higher value is more preferable. If it is more than the above lower limit, anti-glare properties are likely to be good.

(gross)
The 60° gloss (60° specular gloss) of the transfer surface measured by the method described in the Examples below is preferably 50 or less, more preferably 30 or less, even more preferably 20 or less, particularly preferably 15 or less, The most preferable range is 11 or less, and the lower the value, the more preferable it is. When it is below the above upper limit, the matte property is excellent.
Similarly, the 20° gloss is preferably 30 or less, more preferably 20 or less, even more preferably 10 or less, particularly preferably 5 or less, most preferably 2 or less, and the lower the value, the more preferable it is. When it is below the above upper limit, the matte property is excellent.

(Total light transmittance)
When searching for defects in the uneven structure of the transfer mold, it is preferable to have transparency. The total light transmittance measured by the method described in the Examples below is preferably 50% or more, more preferably 60% or more, even more preferably 70% or more, particularly preferably 80% or more, and most preferably 90%. It is within the above range, and the higher the value, 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 the Examples below is preferably F or higher, more preferably H or higher, and still more preferably 2H or higher. Within the above range, a transferred object can be obtained which has excellent scratch resistance, excellent scratch prevention properties in processes before and after transfer, and has few defects due to scratches on the transfer mold.

[Transfer mold manufacturing method]
An example of the transfer type of the present invention is one based on a cured film, and includes one made of a cured product of a curable composition containing an active energy ray-curable compound.
The transfer mold of the present invention can be produced, for example, by laminating a curable composition on a base material and curing it by irradiating it with vacuum ultraviolet rays. 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. Thereafter, when the inside of the coating film is cured, the cured coating film on the surface side buckles, thereby forming a cured film having wrinkle-like irregularities on the surface. The curable composition and the method for producing a cured film using the same will be explained in detail later.

(Transfer type curable composition)
The curable composition can 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. (Meth)acrylates are not particularly limited, and include mixtures of one or more types of monofunctional (meth)acrylates, bifunctional (meth)acrylates, and polyfunctional (meth)acrylates, and those commercially available as curable resin materials. Alternatively, in addition to these, other components may be added to the extent that the purpose of the present embodiment is not impaired. Among these, monofunctional or bifunctional (meth)acrylates are preferred from the viewpoint of easily forming a wrinkled uneven structure. Further, for applications requiring scratch resistance, difunctional (meth)acrylates are more preferred. Using polyfunctional (meth)acrylate is a preferable form in that it improves scratch resistance and hardness, but depending on the compound used, it may be difficult to form a wrinkle-like uneven structure. Care must be taken regarding the types of compounds used and their blending ratios.

Bifunctional polyfunctional (meth)acrylates are not particularly limited, but examples include 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, and 1,6-hexanediol. Di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, alkanediol di(meth)acrylate such as tricyclodecane dimethyloldi(meth)acrylate, bisphenol A ethylene oxide modified di(meth)acrylate, bisphenol Examples include bisphenol-modified di(meth)acrylates 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, in view of ease of forming a wrinkle-like uneven structure, a structure without branches is preferable, and alkyl diol di(meth)acrylates are more preferable, and alkyl diol di(meth)acrylates having 4 to 18 carbon atoms are preferable. More preferred are meth)acrylates.

Monofunctional (meth)acrylates are not particularly limited, but examples include methyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, and stearyl (meth)acrylate. Alkyl (meth)acrylates such as meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, hydroxyalkyl (meth)acrylates such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, etc. , alkoxyalkyl (meth)acrylates such as methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, methoxypropyl (meth)acrylate, ethoxypropyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, etc. Aromatic (meth)acrylate, diaminoethyl (meth)acrylate, amino group-containing (meth)acrylate such as diethylaminoethyl (meth)acrylate, methoxyethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, phenylphenol Examples include ethylene oxide-modified (meth)acrylate such as ethylene oxide-modified (meth)acrylate, glycidyl (meth)acrylate, and tetrahydrofurfuryl (meth)acrylate.

Trifunctional or higher polyfunctional (meth)acrylates are not particularly limited, but include, for example, dipentaerythritol hexa(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, Ethylene oxide modified (meth)acrylates such as pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethylene oxide modified dipentaerythritol hexa(meth)acrylate, ethylene oxide modified pentaerythritol tetra(meth)acrylate, isocyanuric Isocyanuric acid modified tri(meth)acrylate such as acid ethylene oxide modified tri(meth)acrylate, ε-caprolactone modified tris(acryloxyethyl) isocyanurate, pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer, pentaerythritol triacrylate toluene diisocyanate Examples include urethane acrylates such as urethane prepolymers, dipentaerythritol pentaacrylate hexamethylene diisocyanate urethane prepolymers. Among these, ethylene oxide modified types and trifunctional (meth)acrylates are preferred in view of ease of forming a wrinkled uneven structure.

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

When using an active energy ray-curable compound in forming the transfer mold, the content of the compound derived from the active energy ray-curable compound in the transfer mold is preferably 5% by mass or more, more preferably 30% by mass. The content is more preferably 40% by mass or more, particularly preferably 50% by mass or more, and most preferably 60% by mass or more. There is no particular upper limit, and it may be 100% by mass, but it is preferably 99% by mass or less, more preferably 98% by mass or less. In the case of the above range, a wrinkle-like uneven structure can be easily formed, a cured film having excellent hardness and scratch resistance can be formed, and an appropriate transfer mold can be obtained.

(resin)
It is also possible to use various resins as the transfer mold for the purpose of improving adhesion to the base material. As the resin, various conventionally known resins can be used, such as acrylic resins, polyester resins, polyurethane resins, polyvinyl resins, etc. Among these, those with particularly high transparency and affinity with (meth)acrylates can be used. Acrylic resin is preferred in terms of its excellent properties.

Further, as the resin used for the transfer mold, especially in the case of a transfer mold 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 improving scratch resistance and hardness. Examples of active energy ray-curable functional groups include (meth)acryloyl groups and vinyl ether compounds. Among these, a (meth)acryloyl group, particularly an acryloyl group, is preferred in consideration of ease of introduction and reactivity.

In the course of further investigation, we used a resin with active energy ray-curable functional groups, which not only improved properties that are directly related to active energy ray-curable functional groups, such as improved scratch resistance and hardness. It was found that the wrinkle-like uneven shape becomes smaller. That is, it was found that Rsm and Sa of the transfer surface became smaller. In addition, there were cases where the haze increased and cases where the gloss decreased. These properties can have a synergistic effect on matte properties, and are particularly important properties 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, an acrylic resin having a double bond and a carboxyl group has an epoxy 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 an acrylic resin having a carboxyl group with a compound having a double bond and a hydroxyl group (method 4), a method of reacting an acrylic resin having an isocyanate group with a compound having a double bond and a hydroxyl group (method 5), and a method (method 6) in which an acrylic resin having a hydroxyl group is reacted with a compound having a double bond and an isocyanate group. Moreover, the above methods may be used in combination. Note that hereinafter, a radically polymerizable monomer having a carbon-carbon double bond may be referred to as a vinyl monomer.

In method 1, the vinyl monomer having an epoxy group used to obtain the acrylic resin having an epoxy group includes, for example, glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxy Examples include cyclohexylmethyl (meth)acrylate. Among these, glycidyl (meth)acrylate is preferred, particularly glycidyl methacrylate, considering good reactivity and ease of use of the material. These may be used alone or in combination of two or more.

Further, as the compound having a double bond and a carboxyl group in the method 1, for example, (meth)acrylic acid, carboxyethyl (meth)acrylate, an adduct of glycerin di(meth)acrylate and succinic anhydride, pentaerythritol tri Examples include adducts of (meth)acrylate and succinic anhydride, and adducts of pentaerythritol tri(meth)acrylate and phthalic anhydride. Among these, (meth)acrylic acid, an adduct of pentaerythritol tri(meth)acrylate and succinic anhydride are preferred, (meth)acrylic acid is more preferred, and acrylic acid is even more preferred. In addition, only one type of compound having a double bond and a carboxyl group may be used, or two or more types may be used in combination.

In method 2, the vinyl monomer having a carboxyl group used to obtain the acrylic resin having a carboxyl group includes, for example, (meth)acrylic acid, carboxyethyl (meth)acrylate, and polybasic acid-modified (meth)acrylate. Can be mentioned. Among these, (meth)acrylic acid is preferred, and acrylic acid is more preferred. These may be used alone or in combination of two or more.

In 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. Among these, glycidyl (meth)acrylate is preferred. These may be used alone or in combination of two or more.

In method 3, the vinyl monomer having a hydroxyl group used to obtain the acrylic resin having a hydroxyl group includes, for example, 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and hydroxypropyl (meth)acrylate. can be mentioned. These may be used alone or in combination of two or more.

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

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

Further, in the 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. These may be used alone or in combination of two or more.

In Method 5, examples of the vinyl monomer having an isocyanate group used to obtain the acrylic resin having an isocyanate group include isocyanate ethyl (meth)acrylate.

Further, in the method 5, as the compound having a double bond and a hydroxyl group, for example, compounds similar to those listed in the method 4 can be used.

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

Further, in the method 6, examples of the compound having a double bond and an isocyanate group include isocyanate ethyl (meth)acrylate. These may be used alone or in combination of two or more.

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

In method 1, the epoxy group-containing monomer in the epoxy group-containing acrylic resin is preferably 5% by weight or more, more preferably 10% by weight or more of the total amount of monomers constituting the epoxy group-containing acrylic resin, More preferably, it is in a 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, even more preferably 70% by weight or less, particularly preferably 50% by weight or less, and most preferably 40% by weight or less. is within the range of By using within this range, it tends to not only improve the adhesion of the cured film to the substrate, scratch resistance, and hardness, but also to make the wrinkle-like uneven shape finer, resulting in a decrease in RSm and a decrease in Sa. A reduction and possibly an increase in haze and a reduction in gloss can be achieved.

Further, in method 1, the compound having a double bond and a carboxyl group is preferably 10 to 150 mol% as a proportion of the compound having a double bond and a carboxyl group to the epoxy group in the acrylic resin having an epoxy group. and more preferably 30 to 130 mol%, still more preferably 50 to 110 mol%. Use within this range is preferable from the viewpoint of allowing the reaction to proceed in just the right amount and reducing the amount of raw material residue.

Furthermore, the acrylic resin, such as the acrylic resin having an epoxy group mentioned above, may be one obtained by copolymerizing (meth)acrylates other than those mentioned above or other vinyl monomers. The polymerization reaction of these raw materials is usually radical polymerization, and the polymerization can be carried out under conventionally known conditions.

Examples of monomers that can be used in combination as raw materials include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, and cyclohexyl. (meth)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)acrylate ) Acrylate and other (meth)acrylates; ethyl (meth)acrylamide, n-butyl (meth)acrylamide, i-butyl (meth)acrylamide, t-butyl (meth)acrylamide, N-hydroxyethyl (meth)acrylamide, N- Examples include acrylamide such as hydroxypropyl (meth)acrylamide and N,N-dihydroxyethyl (meth)acrylamide; and styrenic monomers such as styrene, p-chlorostyrene, and p-bromostyrene. These may be used alone or in combination of two or more.

Acrylic resins can be produced by radical polymerization using the above raw material vinyl monomers. The radical polymerization reaction is preferably carried out in an organic solvent in the presence of a radical polymerization initiator.

Examples of organic solvents used in 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, propylene glycol monomethyl ether, etc. ether solvents; ester solvents such as ethyl acetate, propylene glycol monomethyl ether acetate, and 2-ethoxyethyl acetate; and aromatic hydrocarbon solvents such as toluene. These organic solvents may be used alone or in combination of two or more.

Examples of radical polymerization initiators used in radical polymerization include organic peroxides such as benzoyl peroxide and di-t-butyl peroxide; 2,2'-azobisbutyronitrile, 2,2'-azobis(2 , 4-dimethylvaleronitrile) and 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile). These radical polymerization initiators may be used alone or in combination of two or more. The radical polymerization initiator is preferably used in an amount of 0.01 to 5 parts by weight based on a total of 100 parts by weight of the raw vinyl monomer.

Furthermore, during radical polymerization, a chain transfer agent can be used for purposes such as controlling the weight average molecular weight of the acrylic resin. Examples of chain transfer agents include butanethiol, octanethiol, decanethiol, dodecanethiol, hexadecanethiol, octadecanethiol, cyclohexylmercaptan, thiophenol, octyl thioglycolate, octyl 2-mercaptopropionate, octyl 3-mercaptopropionate. , mercaptopropionate 2-ethylhexyl ester, 2-ethylhexyl thioglycolate, butyl-3-mercaptopropionate, mercaptopropyltrimethoxysilane, methyl-3-mercaptopropionate, 2,2-(ethylenedioxy) ) diethanethiol, ethanethiol, 4-methylbenzenethiol, 2-mercaptoethyl octanoate, 1,8-dimercapto-3,6-dioxaoctane, decanetrithiol, dodecylmercaptan, diphenyl sulfoxide, dibenzyl sulfide, 2,3-dimethylcapto-1-propanol, mercaptoethanol, thiosalicylic acid, thioglycerol, thioglycolic acid, 3-mercaptopropionic acid, thiomalic acid, mercaptoacetic acid, mercaptosuccinic acid, 2-mercaptoethanesulfonic acid, etc. Examples include thiol 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 still more preferably 1.0 to 15 parts by weight, based on a total of 100 parts by weight of the raw material vinyl monomer. preferable.

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

In order to react an acrylic resin with a compound having a double bond and a carboxyl group, the compound having a double bond and a carboxyl group is added to the acrylic resin obtained as described above, and triphenylphosphine, triphenylphosphine, The reaction is carried out in the presence of one or more catalysts such as tetrabutylammonium bromide, tetramethylammonium chloride, triethylamine, etc. at a temperature of usually 90 to 140°C, preferably 100 to 120°C, for usually about 3 to 9 hours. good. Here, the catalyst is used in a proportion of about 0.5 to 3 parts by weight based on the total of 100 parts by weight of the raw material (meth)acrylic acid ester polymer and compounds such as compounds having double bonds and carboxyl groups. It is preferable to use This reaction may be performed continuously after the acrylic resin is produced by a polymerization reaction, or it can be performed by once separating the acrylic resin from the reaction system and then adding a compound such as a compound having a double bond and a carboxyl group. It's okay.

The amount of double bonds 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, particularly preferably 0. It ranges from 8 to 4.0 mmol/g, most preferably from 1.0 to 3.0 mmol/g. By using it within this range, it tends to not only improve the adhesion of the cured film to the base material, scratch resistance, and hardness, but also to make the wrinkle-like uneven shape finer, resulting in a decrease in Rsm and a decrease in Sa. A reduction and possibly an increase in haze and a reduction in gloss can be achieved. Note that the double bond amount means the concentration of (meth)acryloyl groups in the acrylic resin, that is, the amount of (meth)acryloyl groups 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, more preferably 9000 or more, It is usually 200,000 or less, preferably 100,000 or less, more preferably 70,000 or less, and still more preferably 50,000 or less. Within the above range, it becomes easy to form surface irregularities. Note that the weight average molecular weight (Mw) of the resin can be determined as a converted value using a polystyrene standard using gel permeation chromatography (GPC). Specific measurement conditions are shown in Examples below.

When the transfer mold contains a resin, its content is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less, from the viewpoint of the appearance and adhesion of the cured film. It is. If the resin content is too large, there is a concern that the hardness of the cured film will decrease.

(particle)
It is also possible to use particles to further improve the matting properties due to the wrinkled uneven structure of the transfer mold. 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 include organic particles such as resin, phenol resin, epoxy resin, and benzoguanamine resin. The inorganic particles may be particles surface-modified with a silane coupling agent having a reactive group such as a (meth)acryloyl group. The organic particles are preferably crosslinked to maintain their shape, and crosslinked acrylic resin particles and crosslinked styrene resin particles are more preferable. Two or more types 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, even more preferably 0.1 to 5 μm, particularly preferably 0.5 to 3 μm. In the case of this range, the matte property is excellently improved.

When particles are contained in the transfer mold, their content is preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 10% by mass based on the nonvolatile content, from the viewpoint of improving matting properties. % or less, particularly preferably 8% by mass or less. Although there is no particular lower limit, it is preferably 0.1% by mass or more, more preferably 1% by mass or more. If the amount of particles is too large, they will easily fall off, so care must be taken.

(Antistatic agent)
It is also possible to use an antistatic agent in the transfer mold. By containing an antistatic agent, it is possible to impart antistatic properties to the transfer mold, and for example, it can contribute to preventing the adhesion of foreign substances such as dust due to peeling electrification, etc., reducing defects caused by transfer, and ensuring that the transfer mold does not perform as designed. A transfer target can be obtained.

The antistatic agent is not particularly limited, and conventionally known antistatic agents can be used. Examples include organic compounds such as polymer type and surfactant type, and inorganic compounds such as metal oxides. Among these, antistatic agents that are organic compounds are preferred because they facilitate the formation of an uneven structure. Moreover, a polymer type antistatic agent is more preferable because it has good heat resistance, moist heat resistance, and durability. Examples of the polymer type antistatic agent include compounds having an ammonium group, polyether compounds, compounds having a sulfonic acid group, betaine compounds, and conductive polymers. Among these, compounds having an ammonium group are more preferable in consideration of coating appearance.

Further, the antistatic agent can also be a compound having an active energy ray-curable functional group. Examples of the active energy ray-curable functional group include (meth)acryloyl group. Containing the functional group can contribute to the formation of an uneven structure and can also contribute to improving properties such as scratch resistance.

The compound having an ammonium group is a compound having an ammonium group in the molecule, and includes ammonium compounds of aliphatic amines, alicyclic amines, and aromatic amines. The compound having an ammonium group is preferably a polymer-type compound having an ammonium group, and the ammonium group has a structure in which it is incorporated into the main chain or side chain of the polymer, rather than as a counter ion. It is preferable. Furthermore, among polymers, in order to effectively impart antistatic properties, it is preferable to use a polymer that can have a high concentration of ammonium groups, and for this purpose, a (meth)acrylic polymer is preferable. For example, a polymer compound having an ammonium group made from a polymer obtained by polymerizing a monomer containing an addition-polymerizable ammonium group or a precursor of an ammonium group such as an amine can be mentioned and preferably used. As a polymer, a monomer containing an addition-polymerizable ammonium group or an ammonium group precursor such as an amine may be polymerized alone, or a monomer containing these and other monomers may be polymerized. It may be a copolymer of

Examples of ammonium groups or precursor monomers for ammonium groups such as amines include (meth)acrylic acid esters of amino alcohols, 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, etc., and N,N-dimethylaminoethyl (meth)acrylate is particularly preferably used. The two alkyl groups of the N,N-dialkylamino group may be different.

The ammonium group of the N,N-dialkylamino group-containing monomer includes, for example, a quaternized product of commercially available N,N-dimethylaminoethyl methacrylate with methyl chloride [for example, the product name "Light Ester (registered trademark) DQ- 100'', manufactured by Kyoeisha Kagaku Co., Ltd.). The ammonium group of the N,N-dialkylamino group-containing monomer can also be produced, for example, by quaternization reaction of (meth)acrylic acid ester of amino alcohol.

In the case of a (meth)acrylic polymer, it may contain polymerizable monomer units other than ammonium groups or ammonium group precursor monomers such as amines, and such polymerizable monomers include , 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)acrylate, ) acrylate; (meth)acrylic esters of the above amino alcohols; hydroxyalkyl such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, etc. (meth)acrylate; benzyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, ethylcarbyl Examples include various (meth)acrylates such as tall (meth)acrylate, butoxyethyl (meth)acrylate, cyanoethyl (meth)acrylate, and glycidyl (meth)acrylate, styrene, methylstyrene, and the like. These may be used alone or in combination of two or more. Among these, when containing a polymerizable monomer having a highly hydrophobic long-chain alkyl group, it is preferable because it can be segregated at the air interface of the cured film and improve the antistatic properties of the cured film. It is. The polymerizable monomer having such a long-chain alkyl group is preferably an alkyl (meth)acrylate having 8 to 30 carbon atoms, more preferably an alkyl (meth)acrylate having 12 to 22 carbon atoms, Examples include lauryl (meth)acrylate, tridecyl (meth)acrylate, and stearyl (meth)acrylate.

When a compound having ammonium groups is realized using a (meth)acrylic polymer, the proportion of ammonium group-containing monomer units in the polymer is preferably 5 to 95% by mass, more preferably 10% by mass. The range is from 90% by weight, more preferably from 20 to 80% by weight, particularly preferably from 30 to 70% by weight. The higher the ratio, the higher the antistatic property, and the lower the ratio, the better the appearance of the cured product layer after coating.If used within the above range, a good balance can be obtained.
In addition, when a long-chain alkyl group is used in combination, the proportion of long-chain alkyl group-containing monomer units in the polymer is preferably 80% by mass or less, more preferably 50% by mass or less, and even more preferably 40% by mass. The range is as follows. When used within the above range, antistatic properties can be easily exhibited.

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

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

Examples of organic solvents used in radical polymerization reactions 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. Ester solvents such as ethyl acetate, propylene glycol monomethyl ether acetate and 2-ethoxyethyl acetate; aromatic hydrocarbon solvents such as toluene. 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 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 an amount of 0.01 to 5 parts by weight based on a total of 100 parts by weight of the raw material monomers.

Furthermore, during 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 chain transfer agents include butanethiol, octanethiol, decanethiol, dodecanethiol, hexadecanethiol, octadecanethiol, cyclohexylmercaptan, thiophenol, octyl thioglycolate, octyl 2-mercaptopropionate, octyl 3-mercaptopropionate. , mercaptopropionate 2-ethylhexyl ester, 2-ethylhexyl thioglycolate, butyl-3-mercaptopropionate, mercaptopropyltrimethoxysilane, methyl-3-mercaptopropionate, 2,2-(ethylenedioxy) ) diethanethiol, ethanethiol, 4-methylbenzenethiol, 2-mercaptoethyl octanoate, 1,8-dimercapto-3,6-dioxaoctane, decanetrithiol, dodecylmercaptan, diphenyl sulfoxide, dibenzyl sulfide, 2,3-dimethylcapto-1-propanol, mercaptoethanol, thiosalicylic acid, thioglycerol, thioglycolic acid, 3-mercaptopropionic acid, thiomalic acid, mercaptoacetic acid, mercaptosuccinic acid, 2-mercaptoethanesulfonic acid, etc. Examples include thiol 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 even more preferably 1.0 to 15 parts by weight, based on 100 parts by weight of the raw material monomers. preferable.

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

Examples of polyether compounds used as antistatic agents include polyethylene oxide, polyether ester amide, and acrylic resins having polyethylene glycol in their side chains.

A compound having a sulfonic acid group as an antistatic agent is a compound containing a sulfonic acid or sulfonate in the molecule. For example, a compound in which a large amount of sulfonic acid or sulfonate exists, such as polystyrene sulfonic acid. is preferably used.

Examples of conductive polymers used as antistatic agents include polythiophene-based, polyaniline-based, polypyrrole-based, polyacetylene-based, etc. Among them, for example, poly(3,4-ethylenedioxythiophene) is used in combination with polystyrene sulfonic acid. Polythiophene-based materials are preferably used. The conductive polymer is more suitable than the other antistatic agents mentioned above in that it has 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 surfactants used as antistatic agents include anionic surfactants, cationic surfactants, amphoteric surfactants, and nonionic surfactants. Among these, anionic surfactants and nonionic surfactants are preferred, and anionic surfactants are particularly preferred, from the viewpoint of good antistatic properties and compatibility with various resins.

Examples of anionic surfactants include sulfonic acid types such as alkyl sulfonates, alkylaryl sulfonates, and ester sulfonates, alkyl phosphate esters or salts thereof, and polyoxyalkylene alkyl ether phosphates or salts thereof. Examples include phosphoric acid type, such as alkyl sulfate ester salt, sulfuric acid ester type, such as alkyl ether sulfate ester salt, and carboxylate type, such as alkyl fatty acid salt. Among these, the sulfonic acid type is preferred from the viewpoint of excellent antistatic properties.

Examples of sulfonic acid type anionic surfactants include alkyl sulfonates such as decyl sulfonate, dodecyl sulfonate, tetradecyl sulfonate, hexadecyl sulfonate, and octadecyl sulfonate, and butylbenzenesulfonic acid. salt, hexylbenzene sulfonate, octylbenzene sulfonate, decylbenzene sulfonate, dodecylbenzene sulfonate, tetradecylbenzene sulfonate, hexadecylbenzene sulfonate, octadecylbenzene sulfonate, dibutylnaphthalene sulfonate salts, alkylaryl sulfonates such as triisopropylnaphthalene sulfonate, ester sulfonates such as dibutyl sulfosuccinate ester salt, dioctyl sulfosuccinate ester salt, dodecyl sulfoacetate ester salt, and nonylphenoxypolyethylene glycol sulfoacetate ester salt. It will be done. Among these, from the viewpoint of excellent antistatic properties, the alkyl group has 8 or more carbon atoms, preferably 10 to 22 carbon atoms, and more preferably 12 to 18 carbon atoms. Furthermore, as the salt, metal salts are preferred, particularly alkali metal salts such as lithium, sodium, potassium, etc. are more preferred, and sodium salts are even more preferred. From the viewpoint of antistatic properties, alkyl sulfonates are preferred.

Examples of phosphate-type anionic surfactants include butyl phosphate, butyl phosphate salt, hexyl phosphate, hexyl phosphate salt, octyl phosphate, octyl phosphate salt, decyl phosphate, and decyl phosphate salt. , lauryl phosphate, lauryl phosphate, tetradecyl phosphate, tetradecyl phosphate, hexadecyl phosphate, hexadecyl phosphate, stearyl phosphate, stearyl phosphate, etc. Alkyl phosphate or its salt, polyoxyethylene butyl ether phosphate, polyoxyethylene butyl ether phosphate salt, polyoxyethylene hexyl ether phosphate salt, polyoxyethylene hexyl ether phosphate salt, polyoxyethylene octyl ether phosphate Acid ester, polyoxyethylene octyl ether phosphate ester salt, polyoxyethylene decyl ether phosphate ester, polyoxyethylene decyl ether phosphate ester salt, polyoxyethylene lauryl ether phosphate ester, polyoxyethylene lauryl ether phosphate ester salt , polyoxyethylene tetradecyl ether phosphate, polyoxyethylene tetradecyl ether phosphate salt, polyoxyethylene hexadecyl ether phosphate salt, polyoxyethylene hexadecyl ether phosphate salt, polyoxyethylene stearyl ether phosphate ester, polyoxyethylene stearyl ether phosphate ester salt, polyoxypropylene octyl ether phosphate ester, polyoxypropylene octyl ether phosphate ester salt, polyoxypropylene decyl ether phosphate ester, polyoxypropylene decyl ether phosphate ester salt, Examples include polyoxyalkylene alkyl ether phosphates or salts thereof, such as polyoxypropylene lauryl ether phosphate and polyoxypropylene lauryl ether phosphate salts.

Among these, alkyl phosphate ester salts, polyoxyalkylene alkyl ether phosphate esters, or salts thereof are preferred from the viewpoint of surfactant performance and antistatic performance.

Regarding the alkyl phosphate ester salt, the number of carbon atoms in the alkyl group is 4 or more, preferably from 4 to 22, more preferably from 6 to 12, and regarding the polyoxyalkylene alkyl ether phosphate or its salt, The alkyl group has 4 or more carbon atoms, preferably 6 to 22 carbon atoms, and more preferably 8 to 18 carbon atoms. Further, as the salt, metal salts and amine salts are preferable, particularly alkali metal salts such as lithium, sodium, and potassium, alkyl amine salts, and alcohol amine salts are more preferable, and sodium salts and monoethanolamine salts are even more preferable.

When using an antistatic agent 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. , more preferably 0.5% by mass or more, particularly preferably 1.0% by mass or more, most preferably 2.0% by mass or more. The upper limit is not particularly limited and may be 100% by mass, but in consideration of the hardness of the cured film, it is preferably 50% by mass or less, more preferably 30% by mass or less, even more preferably 20% by mass or less, particularly preferably 10% by mass or less. The range is 8% by weight or less, most preferably 8% by weight or less. When it is at least the above lower limit, antistatic properties are excellent.

(Release agent)
The transfer mold can also contain a release agent, such as a compound having a fluorine atom or a silicone compound, in order to improve stain resistance and transferability. By including the compound in the transfer mold, abnormal transcription due to contamination can be reduced. It also leads to the transfer material being easily peeled off from the transfer mold during transfer, which improves productivity by eliminating the need to provide a release layer on the transfer mold (two-layer structure), and This is a preferred form because it can contribute to the production of transferred objects with fewer foreign object defects caused by the transfer material remaining on 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, such as a perfluoroalkyl group-containing compound, a perfluoropolyether compound, a polymer of an olefin compound containing a fluorine atom, an aromatic compound such as fluorobenzene, etc. Examples include fluorine compounds. From the viewpoint of antifouling properties, a compound having a perfluoroalkyl group or a perfluoropolyether compound is preferable. Furthermore, silicone compounds and compounds containing long-chain alkyl compounds can also be used as the fluorine compound.

Compounds having a perfluoroalkyl group include, for example, perfluoroalkyl (meth)acrylate, perfluoroalkylmethyl (meth)acrylate, 2-perfluoroalkylethyl (meth)acrylate, 3-perfluoroalkylpropyl (meth)acrylate. , 3-perfluoroalkyl-1-methylpropyl (meth)acrylate, 3-perfluoroalkyl-2-propenyl (meth)acrylate and other perfluoroalkyl group-containing (meth)acrylates and their polymers, perfluoroalkylmethyl vinyl 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. etc. In consideration of heat resistance and stain resistance, polymers are preferred. The polymer may be a single compound or a polymer of multiple compounds. Further, from the viewpoint of antifouling properties, the perfluoroalkyl group preferably has 3 to 11 carbon atoms. Furthermore, it may be a polymer with a compound containing a silicone compound or a long-chain alkyl compound.

The silicone compound refers to a compound having a silicone structure in the molecule, and includes, for example, alkyl silicones such as dimethyl silicone and diethyl silicone, phenyl silicone having a phenyl group, and methyl phenyl silicone. Silicones having various functional groups can also be used, such as ether groups, hydroxyl groups, amino groups, epoxy groups, carboxylic acid groups, halogen groups such as fluorine, perfluoroalkyl groups, various alkyl groups, and various silicones. Examples include hydrocarbon groups such as aromatic groups. As other functional groups, silicone with a vinyl group and hydrogen silicone in which a hydrogen atom is directly bonded to a silicon atom are also common, and by using both together, an addition type silicone (a type formed by an addition reaction between a vinyl group and a hydrogen silane) is produced. It is also possible to use it as Also preferred is a method of introducing a double bond such as an acryloyl group and reacting at the double bond.

Further, as the silicone compound, it is also possible to use modified silicones such as acrylic grafted silicone, silicone grafted acrylic, amino-modified silicone, and perfluoroalkyl-modified silicone. Considering heat resistance and stain resistance, it is preferable to use a curable silicone resin, and any curing reaction type such as a condensation type, addition type, or active energy ray curing type can be used.

Further, it is also preferable that the above-mentioned compound having a fluorine atom or silicone compound 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 preferred in consideration of ease of introduction and reactivity. Containing the functional group can contribute to the formation of an uneven structure and can also contribute to improving properties such as scratch resistance.

The content of the compound having a fluorine atom or the silicone compound in the transfer mold 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, particularly preferably 0. The range is .5% by weight or more, most preferably 0.7% by weight or more. The upper limit is not particularly limited and may be 100% by mass, but in consideration of the hardness of the cured film, it is preferably 50% by mass or less, more preferably 20% by mass or less, even more preferably 10% by mass or less, particularly preferably 5% by mass. The range is 3% by weight or less, most preferably 3% by weight or less. When it is at least the above lower limit, transferability and antifouling properties are excellent.

(Photopolymerization initiator)
When the transfer mold is formed of a cured film (active energy ray-curable compound), a photopolymerization initiator may be used to accelerate the curing 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, pivaloin ethyl ether, benzyl dimethyl ketal, 1,1-dichloroacetophenone, pt-butyl Dichloroacetophenone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-diethylthioxanthone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-dichloro-4-phenoxyacetophenone, Phenylglyoxylate, α-hydroxyisobutylphenone, dibenzosparone, 1-(4-isopropylphenyl)-2-hydroxy-2-methyl-1-propanone, 2-methyl-[4-(methylthio)phenyl]-2- Examples include morpholino-1-propanone, tribromophenyl sulfone, tribromomethyl phenyl sulfone, and the like. These photopolymerization initiators may be used alone or in combination of two or more.

When using a photopolymerization initiator in the transfer mold, the content of the compound derived therefrom is preferably 20% by mass or less, more preferably 10% by mass or less, and The content is preferably 8% by mass or less, particularly preferably 6% by mass or less.

(Leveling agent)
Leveling agents can be used to improve the appearance of the transfer mold.
Examples of the leveling agent include acrylic leveling agents, silicone leveling agents, and fluorine leveling agents. These leveling agents may be used alone or in combination of two or more.

When a leveling agent is contained in the transfer type film, the content thereof is preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably The content is in the range of 5% by mass or less.

(Various additives)
In the transfer type, polymerization accelerators such as compounds containing thiol groups, plasticizers, surfactants, antioxidants, ultraviolet absorbers, etc. may be used within the range that does not impair the effects of the present invention.

(Organic solvent)
Furthermore, when the transfer mold is formed of a cured film, an organic solvent may be used as necessary in the curable composition for the purpose of improving workability when coating the composition on the base material.
Organic solvents include aromatic solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone, acetone, methyl isobutyl ketone, and cyclohexanone; diethyl ether, isopropyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and diethylene glycol dimethyl ether. , diethylene glycol diethyl ether, propylene glycol monomethyl ether, anisole, phenetol, etc.; ester solvents such as ethyl acetate, butyl acetate, isopropyl acetate, ethylene glycol diacetate; dimethylformamide, diethylformamide, N-methylpyrrolidone, etc. Amide solvents; cellosolve solvents such as methyl cellosolve, ethyl cellosolve and butyl cellosolve; alcohol solvents such as methanol, ethanol, propanol, isopropanol and butanol; halogen solvents such as dichloromethane and chloroform; and the like. These organic solvents may be used alone or in combination of two or more. Among these organic solvents, ester solvents, ether solvents, alcohol solvents, and ketone solvents are preferred since they tend to improve workability during coating.

The ratio of the organic solvent to 100 parts by mass of the nonvolatile content of the curable composition is preferably 10 parts by mass or more and 1900 parts by mass or less, 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. .
Note that the nonvolatile content of the curable composition is the total mass of components other than solvents such as organic solvents. The nonvolatile content of a curable composition can be measured by a conventionally known method. For example, the weight of 1 g of the composition is measured by spreading it and heating it at 100°C for 1 hour to evaporate the organic solvent. Measured by change.

(Formation of coating film)
In the case of forming a transfer mold using a cured film, a curable composition is applied onto the surface of the base material or article to form a coating film, and if necessary, after drying, the coating film is formed using a cured film. It can be formed by irradiating active energy rays.
The method of applying the curable composition is not particularly limited. For example, the coating can be performed by a known method such as dip coating, air knife coating, curtain coating, spin coating, roller coating, bar coating, wire bar coating, gravure coating, or spray coating.

When the curable composition contains an organic solvent, it is preferably heat-dried in advance before irradiation 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, 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, 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 with 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 optimal, and examples include argon (126 nm), krypton (146 nm), xenon (172 nm), and argon/fluorine (193 nm). Among these, xenon excimer light is preferred in consideration of ease of use, effective unevenness formation, curability of the cured film, and the like.

When using vacuum ultraviolet rays, the cumulative amount of light for irradiation is preferably 1 to 3000 mJ/cm ² , more preferably 3 to 1000 mJ/cm ² , even more preferably 5 to 500 mJ/cm ² , particularly preferably 10 to 100 mJ/cm 2 The range is ² . Further, the illuminance is preferably in the range of 1 to 500 mW/cm ² , more preferably 2 to 300 mW/cm ² , and still more preferably 3 to 100 mW/cm ² .

Further, as the atmosphere during vacuum ultraviolet irradiation, it is preferable to perform the irradiation in an environment with little oxygen, such as a nitrogen atmosphere. The oxygen concentration is preferably 10% or less, more preferably 5% or less, still more preferably 3% or less, particularly preferably 1% or less.

After the above vacuum ultraviolet ray irradiation, it is preferable to irradiate active energy rays other than vacuum ultraviolet rays in order to deeply cure the cured film. 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 cumulative 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 , even more preferably 100 to 1000 mJ/cm ² , particularly preferably 200 to 700 mJ/cm ² . Further, the illumination intensity is preferably in the range of 1 to 1000 mW/cm ² , more preferably 50 to 500 mW/cm ² , and still more preferably 80 to 300 mW/cm ² .

[Transferred material]
The object to be transferred of the present invention is manufactured by using the above-mentioned transfer mold as a negative pattern and transferring the shape of the transfer mold. The transferred object has a wrinkle-like uneven structure on the transferred surface, and the average length (RSm) of the roughness curve element of the transferred surface according to JIS B0601:2013 is 1 to 1000 μm, and conforms to ISO 25178. The arithmetic mean height (Sa) defined by is 0.1 to 1000 μm. As a result, the transferred material has matte properties and can be suitably used for optical applications such as display members.

(Thickness of transferred object)
The thickness of the transferred object (the layer forming the uneven structure of the transferred object) is preferably 0.1 to 1000 μm, more preferably 0.2 to 200 μm, even more preferably 0.3 to 100 μm, particularly preferably 0. It is in the range of .5 to 30 μm. If the thickness of the transferred material is within the above range, desired matteness can be easily achieved and hardness can be easily adjusted.
Note that the thickness of the transferred object indicates the maximum thickness of the uneven layer, and is determined by cross-sectional observation using an electron microscope.

(RSm, Sa, θa of the transferred object)
The preferred ranges for RSm, Sa, and θa of the transfer surface of the transfer object are the same ranges as those of the transfer type described above. Another major feature of the transfer target of the present invention is that it has a structure similar to that of the transfer mold. That is, the structure of the transfer mold has a similar shape vertically centering on the zero plane in the height direction, and the object to be transferred by the transfer mold also has a similar shape to the transfer mold. Thereby, once the shape of the transfer mold is determined, the shape as it is is the expected shape of the object to be transferred, and the design of the object to be transferred becomes easy. Also, normally, in order to create the same shape as the transfer mold, it is necessary to repeat the transfer twice (in other words, create a transferred object with the transfer mold transferred, then use that transferred object as the transfer mold, According to the transfer mold of the present invention, an object having the same shape as the transfer mold can be manufactured with one transfer, which is cost-effective. It is also advantageous in terms of the probability of defects and failures occurring.

The above-mentioned RSm, Sa, and θa of the transfer material of the present invention are preferably in the range of -50 to 50%, more preferably -30 to 30%, and even more preferably - The range is from 20 to 20%, particularly preferably from -10 to 10%. Within this range, the above-mentioned design of the transferred object becomes easy, and a desired shape can be obtained without performing two transfers.

In addition, if there is a difference between the transferred material and the transfer type in 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. Below, the most preferred range is 5 μm or less, and in the case of Sa, the range is preferably 5 μm or less, more preferably 3 μm or less, even more 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, particularly preferably 1° or less. Within this range, the above-mentioned design of the transferred object becomes easy, and a desired shape can be obtained without performing two transfers.

(Haze of transferred material, 60° gloss, 20° gloss)
Regarding the haze of the transferred object (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 also preferable.
For 60° gloss, it is preferably in the range of -50 to 50% of the same characteristics of the transfer mold, more preferably in the range of -30 to 30%, still more preferably in the range of -20 to 20%, particularly preferably In the range -10% to 10%, most preferably in the range -5% to 5%. Within this range, the design of the above-mentioned transfer target becomes easy.

In addition, if there is a difference between the transferred material and the transfer type in 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 in the range of 4 or less, most preferably 1 or less, and in the case of 20° gloss, is preferably 10 or less, more preferably 5 or less, still more preferably 3 or less, particularly preferably 1 or less. Within this range, the design of the above-mentioned transfer target becomes easy.

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

(Pencil hardness of transferred material)
There are no particular limitations on the hardness of the object to be transferred. For example, in the case of an adhesive, it is preferable to use one that does not reduce the performance of the adhesive. On the other hand, when used for optical purposes such as displays, such as anti-glare and anti-blocking purposes, higher hardness may be preferable. When used in applications where higher hardness is preferred, the pencil hardness is F or higher, more preferably H or higher, still more preferably 2H or higher, particularly preferably 3H or higher. Within the above range, it is possible to have excellent scratch resistance, excellent scratch prevention properties of the transferred object, and less defects.

In particular, the transferred object is created by transferring the shape from a transfer mold, so there are fewer restrictions on the transfer material. Therefore, it is possible to design the material to have a higher hardness than that of the transfer mold, and in cases where higher hardness is required, such as in optical applications, the material to be transferred by the method of the present invention is suitable.

(Curable composition for transferred material)
An example of the transfer target of the present invention includes a cured film, and includes a cured product of a curable composition containing an active energy ray-curable compound.

The transfer material of the present invention has excellent matte properties and is therefore suitable for use as an anti-glare film.

There are no particular restrictions on the material of the transfer object, as long as the transfer object has the above structure. A method of creating a transferred object by bringing the cured material into contact with the transfer mold in an uncured state (in a fluid state) and then curing it, or pressing the transfer mold onto the transfer material (e.g. adhesive) Examples include a method of creating a transfer target using a method. Among these methods, in consideration of the durability, stability, and ease of production of the transferred object, it is preferable that the transferred object be formed from a curable compound (that is, a cured film). Specifically, a method may be mentioned in which a coating film of a curable composition is formed and the coating film is cured.

As the curable compound, conventionally known compounds such as active energy ray curing, thermosetting, etc. can be used. Among these, in consideration of ease of manufacture, repeated use of the transfer mold, durability of the transferred object, etc., active energy ray-curable compounds are preferred, and ultraviolet ray-curable compounds are particularly preferred.

As the active energy ray-curable compound, (meth)acrylate, which can be used in a transfer mold, is also a suitable material for the transferred object. For applications where high hardness is desired, it is preferable to use trifunctional or higher functional (meth)acrylates among (meth)acrylates, and hexafunctional or higher functional (meth)acrylates are more preferred. For example, dipentaerythritol hexa(meth)acrylate, pentaerythritol tetra(meth)acrylate, and trifunctional or higher functional urethane (meth)acrylate are preferable, and dipentaerythritol hexa(meth)acrylate and hexafunctional or higher functional urethane (meth)acrylate are preferable. Particularly preferred.

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

When an active energy ray-curable compound is used in forming the transferred object, the content of the compound derived from the active energy ray-curable compound in the layer forming the uneven structure of the transferred object is preferably 5 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, most preferably 60% by mass or more. There is no particular upper limit, and it may be 100% by mass, but it is preferably 99% by mass or less, more preferably 98% by mass or less. In the case of the above range, a transferred object (cured film) with 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 to have a high content of trifunctional or higher polyfunctional (meth)acrylate; The content of the derived compound is preferably 5% by mass or more, more preferably 20% by mass or more, even more 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. .
In addition, in applications where hardness is more important, it is preferable to use polyfunctional (meth)acrylates having hexafunctionality or more, and in that case, the content of compounds derived from polyfunctional (meth)acrylates having hexafunctionality or more is preferably is 5% by mass or more, more preferably 20% by mass or more, even more 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.

In addition, in forming the transferred object, it is also possible to use various resins, particles, antistatic agents, antifouling agents, photopolymerization initiators, leveling agents, organic solvents, etc., as in the case of forming the transfer mold. .

(Method for manufacturing transferred material)
In the case of forming a transfer target using a cured film, the method for forming the transfer target is to apply a curable composition onto the surface of the base material or article to form a coating film, dry as necessary, and then apply the coating. It can be formed by curing the film. The coating method is not particularly limited, and examples include known methods such as dip coating, air knife coating, curtain coating, spin coating, roller coating, bar coating, wire bar coating, gravure coating, and spray coating. It can be applied by any method.

When the curable composition contains an organic solvent, it is preferable to heat and dry it 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, 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, more preferably 0.1 minutes or more and 10 minutes or less.

In forming a transfer target using an active energy ray-curable compound, the transfer target is formed by curing by irradiating active energy rays to form a cured film. The active energy rays are preferably active energy rays other than vacuum ultraviolet rays in order to cure deeply, and include ultraviolet rays, electron beams, etc. Among these, ultraviolet rays are more preferable in consideration of the curability of the cured film.

The cumulative 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 , even more preferably 100 to 1000 mJ/cm ² , particularly preferably 200 to 700 mJ/cm ² . Further, the illumination intensity is preferably in the range of 1 to 1000 mW/cm ² , more preferably 50 to 500 mW/cm ² , and still more preferably 80 to 300 mW/cm ² .

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

(Transfer type base material layer)
As the base material layer, known materials can be used, such as resin base materials, metal base materials, and paper base materials. Among these, resin base materials are preferred from the viewpoint of processability.
The resin base material may have a single layer structure or a multilayer structure of two or more layers, and is not particularly limited. It is preferable that the resin base material has a multilayer structure of two or more layers, each layer having its own characteristics, and multifunctionality.

Various resin films (sheets) can be used as the resin base material, such as polyester film, poly(meth)acrylate film, polyolefin film, polycarbonate film, polyimide film, triacetyl cellulose film, polystyrene film, polyvinyl chloride film, Examples include polyvinyl alcohol film and nylon film.
When this laminate is used for display purposes, polyester films, poly(meth)acrylate films, polyolefin films, polycarbonate films, polyimide films, and triacetyl cellulose films are preferred. Among these, polyester films, poly(meth)acrylate films, and polyolefin films are preferred for anti-glare applications, and polyester films are more preferred in consideration of transparency, moldability, and versatility.
The polyester film may be a non-stretched film or a stretched film, and a stretched film is preferred. Among these, a uniaxially stretched film stretched in a uniaxial direction or a biaxially stretched film stretched in a biaxial direction is preferred, and a biaxially stretched film is more preferred from the viewpoint of excellent balance of mechanical properties and flatness.

The polyester constituting the polyester film that can be used as the base layer may be a homopolyester or a copolyester.
As the homopolyester, one obtained by polycondensing an aromatic dicarboxylic acid and an aliphatic glycol is preferable. Examples of aromatic dicarboxylic acids include terephthalic acid and 2,6-naphthalene dicarboxylic acid. Examples of aliphatic glycols include ethylene glycol, diethylene glycol, and 1,4-cyclohexanedimethanol. The aromatic dicarboxylic acids and aliphatic glycols 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-naphthalene dicarboxylic 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.
Typical polyesters include polyethylene terephthalate and polyethylene naphthalate.

Among the polyester films mentioned above, films formed from polyethylene terephthalate and polyethylene naphthalate are more preferable in consideration of mechanical strength and heat resistance, and are easy to manufacture and easy to handle for applications such as surface protection films. Considering this, a film formed from polyethylene terephthalate is more preferable.

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

The base material layer can contain particles for the purpose of imparting slipperiness, preventing scratches in each step, and improving anti-blocking properties.
The type of particles can be appropriately selected depending on 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 include organic particles such as resin, epoxy resin, and benzoguanamine resin. Furthermore, when the base material layer includes a polyester film, precipitated particles in which a part of a metal compound such as a catalyst is precipitated in the polyester manufacturing process can also be used. Among these, silica particles and calcium carbonate particles are particularly preferred because they are effective even in small amounts.
The shape of the particles is not particularly limited, and may be spherical, lumpy, rod-like, flat, or the like. Further, there are no particular limitations on its hardness, specific gravity, color, etc.
Two or more types of these particles may be used in combination as necessary.

The average particle size of the particles is preferably 10 μm or less, more preferably 0.01 to 5 μm, and even more preferably 0.01 to 3 μm. If the average particle size is 10 μm or less, problems due to a decrease in transparency of the base layer are unlikely to occur.
The average particle diameter of the particles is the value of 50% of the integrated value (based on mass) in the equivalent spherical distribution measured by a centrifugal sedimentation type particle size distribution analyzer.

When the base material layer contains particles, the content of particles in the base material layer cannot be determined unconditionally because it also has to do with the average particle size of the particles, but the total content of the particles in the base material layer The amount is preferably 5% by mass or less, more preferably 0.0003 to 3% by mass, and even more preferably 0.0005 to 1% by mass. When the content of particles is 5% by mass or less, problems such as falling off of particles and reduction in transparency of the base layer are less likely to occur.

The base layer can contain additives other than the above-mentioned particles, if necessary. As additives, known additives such as ultraviolet absorbers, antioxidants, antistatic agents, heat stabilizers, lubricants, dyes, and pigments can be used.

The thickness of the base material layer is not particularly limited as long as it can be formed into a film, but is preferably in the range of 2 to 350 μm, more preferably 5 to 250 μm, and still more preferably 10 to 100 μm.

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

In one preferred embodiment, the primer layer is an adhesion-enhancing layer. If the adhesion between the base 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 becomes difficult to peel off from the base material layer during the transfer process.
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 crosslinking agent from the viewpoint of improving the adhesion between the base 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 electrification and frictional electrification to the outermost surface of the laminate, particularly to the outermost surface on the side where the uneven layer is present with respect to the base material layer. Thereby, defects caused by foreign matter contamination during the transfer process can be reduced.
In order to make the primer layer an antistatic layer, for example, an antistatic agent may be contained in the primer layer.

As the resin, conventionally known resins 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 these, polyester resins, acrylic resins, and urethane resins are preferred in consideration of adhesion performance and coating properties.
When the base material layer is a resin film, the resin of the base material layer is preferably the same type of resin as the resin of the resin film from the viewpoint of affinity between the primer layer and the base material layer. For example, when the base layer is a polyester film, the primer layer preferably contains a polyester resin. When the base layer is a poly(meth)acrylate film, the primer layer preferably contains an acrylic resin.

Examples of polyester resins include those whose main constituent components are polyhydric carboxylic acids and polyhydric hydroxy compounds.
Examples of polyhydric carboxylic acids include terephthalic acid, isophthalic acid, orthophthalic acid, 4,4'-diphenyldicarboxylic acid, 2,5-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, and 2,6-naphthalene dicarboxylic acid. 2,7-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2-potassium sulfoterephthalic acid, 5-sodium sulfoisophthalic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, glutaric acid, succinic acid, Examples thereof include trimellitic acid, trimesic acid, pyromellitic acid, trimellitic anhydride, phthalic anhydride, trimellitic acid monopotassium salt, and ester-forming derivatives thereof.
Examples of polyhydric hydroxy compounds include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 2-methyl-1 , 5-pentanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, p-xylylene glycol, bisphenol A-ethylene glycol adduct, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, poly Examples include tetramethylene oxide glycol, dimethylolpropionic acid, glycerin, trimethylolpropane, sodium dimethylolethylsulfonate, potassium dimethylolpropionate, and the like.
One or more of these compounds may be selected as appropriate, and a polyester resin may be synthesized by a conventional polycondensation reaction.

Acrylic resin is a polymer of polymerizable monomers including (meth)acrylic monomers.
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 other polymers (eg, polyester, polyurethane, etc.). Such copolymers are, for example, block copolymers and graft copolymers. Alternatively, it also includes a polymer (in some cases, a mixture of polymers) obtained by polymerizing a polymerizable monomer in a polyester solution or dispersion. Similarly, polymers (or mixtures of polymers in some cases) obtained by polymerizing polymerizable monomers in polyurethane solutions or dispersions are also included. Similarly, polymers obtained by polymerizing polymerizable monomers in solutions or dispersions of other polymers (in some cases, polymer mixtures) are also included.

The polymerizable monomer is not particularly limited, but typical examples include carboxyl group-containing monomers such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, and citraconic acid; salts; hydroxyl group-containing monomers such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, monobutyl hydroxyl fumarate, monobutyl hydroxy itaconate; 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-methylolacrylamide, (meth)acrylonitrile; styrene compounds such as styrene, α-methylstyrene, divinylbenzene, and vinyltoluene; vinyl esters such as vinyl propionate and vinyl acetate; γ- Examples include silicon-containing monomers such as methacryloxypropyltrimethoxysilane and vinyltrimethoxysilane; phosphorus-containing vinyl monomers; vinyl halides such as vinyl chloride and polypylidene chloride; and conjugated dienes such as butadiene.

A urethane resin is a polymer compound having a urethane bond in its 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.
Polyols 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.

A polycarbonate polyol is obtained by a reaction (dealcoholization 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-nonanediol, 1,10-decanediol , neopentyl glycol, 3-methyl-1,5-pentanediol, 3,3-dimethylolheptane and the like. Examples of the carbonate compound include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, and ethylene carbonate.
Specific examples of polycarbonate polyols include poly(1,6-hexylene) carbonate, poly(3-methyl-1,5-pentylene) carbonate, and the like.

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

Examples of polyester polyols include those obtained by reacting a polyvalent carboxylic acid or its acid anhydride with a polyhydric alcohol, and those having a derivative unit of a lactone compound such as polycaprolactone.
Examples of polyhydric carboxylic acids include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, fumaric acid, maleic acid, terephthalic acid, and isophthalic acid.
Examples of polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2-Methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol , 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, alkyl dialkanolamine, lactone diol and the like.

As the polyol, in consideration of adhesion performance, polyester polyols and polycarbonate polyols are preferred, and polyester polyols are particularly preferred.

The polyisocyanate compounds used to obtain the urethane resin include aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, methylene diphenyl diisocyanate, phenylene diisocyanate, naphthalene diisocyanate, and toridine diisocyanate; α, α, α', α' -Aliphatic diisocyanates with aromatic rings such as tetramethylxylylene diisocyanate; Aliphatic diisocyanates such as methylene diisocyanate, propylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene diisocyanate; cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, dicyclohexyl Examples include alicyclic diisocyanates such as methane diisocyanate and isopropylidene 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 isocyanate groups, and in general, chain extenders 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, butanediol, aromatic glycols such as xylylene glycol and bishydroxyethoxybenzene, and esters such as neopentyl glycol hydroxypivalate. Examples include glycol compounds such as glycol.
Examples of the chain extender having two amino groups include aromatic diamines such as tolylene diamine, xylylene diamine, and diphenylmethane diamine, ethylene diamine, propylene diamine, hexane diamine, and 2,2-dimethyl-1,3-propane diamine. , 2-methyl-1,5-pentanediamine, trimethylhexanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine Aliphatic diamines such as 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, dicyclohexylmethanediamine, isoprobilitine cyclohexyl-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. The medium for the dispersion or solution may be a solvent, but preferably water.
Examples of the aqueous dispersion or solution of urethane resin include a forced emulsification type using an emulsifier, a self-emulsification type in which a hydrophilic group is introduced into the structure of the urethane resin, and a water-soluble type. In particular, a 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 has excellent liquid storage stability and the resulting primer layer has excellent water resistance and transparency.

Ionic groups introduced into the structure of the urethane resin include various groups such as carboxyl groups, sulfonic acid groups, phosphoric acid groups, phosphonic acid groups, and quaternary ammonium bases, but carboxyl groups are preferred.
The carboxyl group is preferably in the form of a salt that is neutralized with a neutralizing agent such as ammonia, amine, alkali metals, and inorganic alkalis. Particularly preferred neutralizing agents are ammonia, trimethylamine, and triethylamine. In a urethane resin having carboxyl groups neutralized with a neutralizing agent, the carboxyl groups from which the neutralizing agent has been removed during the drying process after coating can be used as crosslinking reaction points with a crosslinking agent. This not only provides excellent stability in the liquid state before coating, but also makes it possible to further improve the durability, solvent resistance, water resistance, blocking resistance, etc. of the resulting primer layer.

Various methods can be used to introduce carboxyl groups into the urethane resin at each stage of the polymerization reaction. For example, there is a method in which a resin having a carboxyl group is used as a copolymerization component during prepolymer synthesis, and a method in which a component having a carboxyl group is used as a component such as a polyol, a polyisocyanate compound, or a chain extender. Particularly preferred is a method in which a carboxyl group-containing diol is used and a desired amount of carboxyl groups is introduced depending on the amount of this component. For example, a carboxyl group-containing diol can be copolymerized with a diol used in the synthesis of a urethane resin.
Examples of carboxyl group-containing diols include dimethylolpropionic acid, dimethylolbutanoic acid, bis-(2-hydroxyethyl)propionic acid, and bis-(2-hydroxyethyl)butanoic acid, whose carboxyl groups are neutralized with a neutralizing agent. Examples include salts such as salts.

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

A melamine compound is a compound that has a melamine skeleton in the compound, and includes, for example, an alkylolated melamine derivative, a compound that is partially or completely etherified by reacting an alkylolated melamine derivative with alcohol, and these compounds. Mixtures may be mentioned. Examples of the alcohol used for etherification include methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butanol, and isobutanol. The melamine compound may be a monomer, a dimer or more, or a mixture thereof. Furthermore, melamine co-condensed with urea or the like can also be used, and a catalyst can also be used to increase the reactivity of the melamine compound.
As the melamine compound, one having a hydroxyl group is preferable in consideration of reactivity with various compounds.

The isocyanate compound refers to an isocyanate compound or a compound having an isocyanate derivative structure typified by a blocked isocyanate compound.
Examples of the isocyanate compound include aromatic isocyanate compounds such as tolylene diisocyanate, xylylene diisocyanate, methylene diphenyl diisocyanate, phenylene diisocyanate, and naphthalene diisocyanate; aromatic rings such as α, α, α', α'-tetramethylxylylene diisocyanate; aliphatic isocyanate compounds such as methylene diisocyanate, propylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene diisocyanate; cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, methylene bis(4-cyclohexyl isocyanate), isopropylene diisocyanate; Examples include alicyclic isocyanate compounds such as lidene dicyclohexyl diisocyanate. Also included are polymers and derivatives of these isocyanate compounds, such as burettes, isocyanurates, uretdionates, and carbodiimide-modified products. These may be used alone or in combination of two or more. Among the above-mentioned isocyanate compounds, aliphatic isocyanate compounds or alicyclic isocyanate compounds are more preferable than aromatic isocyanate compounds from the viewpoint of avoiding yellowing due to ultraviolet rays.

Examples of the blocked isocyanate compound include those in which the isocyanate groups of the above-mentioned isocyanate compounds are blocked with a blocking agent. Examples of blocking agents include bisulfites, phenol compounds such as phenol, cresol, and ethylphenol, alcohol compounds such as propylene glycol monomethyl ether, ethylene glycol, benzyl alcohol, methanol, and ethanol, dimethyl malonate, 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 include amine compounds such as ethyleneimine, acid amide compounds such as acetanilide and acetate amide, and oxime compounds such as formaldehyde, acetaldoxime, acetone oxime, methyl ethyl ketone oxime, and cyclohexanone oxime. These may be used alone or in combination of two or more.
As the blocked isocyanate compound, an isocyanate compound blocked with an active methylene compound is preferable from the viewpoint that the primer layer is not easily destroyed.

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

An oxazoline compound is a compound having an oxazoline group in its molecule.
As the oxazoline compound, a polymer containing an oxazoline group is preferred. The oxazoline group-containing polymer can be obtained by polymerizing an addition-polymerizable oxazoline group-containing monomer alone or with other monomers.
Examples of addition-polymerizable oxazoline group-containing monomers 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 industrially easily available.
Other monomers are not particularly limited as long as they are copolymerizable with the addition-polymerizable oxazoline group-containing monomer, such as alkyl (meth)acrylate (alkyl groups include methyl, ethyl, n-propyl, (Meth)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 acids and their salts (sodium salts, potassium salts, ammonium salts, tertiary amine salts, 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) unsaturated amides 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, etc. halogen-containing α,β-unsaturated monomers; α,β-unsaturated aromatic monomers such as styrene, α-methylstyrene, and the like. These may be used alone or in combination of two or more.

The amount of oxazoline groups per 1 g of oxazoline compound is preferably in the range of 0.5 to 10 mmol/g, more preferably 1 to 9 mmol/g, even more preferably 3 to 8 mmol/g, particularly preferably 4 to 6 mmol/g. . If the amount of oxazoline groups is within the above range, the durability of the coating film will be improved and the adhesion will be easier to adjust.

An epoxy compound is a compound having an epoxy group in its molecule.
Examples of epoxy compounds include condensates of epichlorohydrin and compounds having a hydroxyl group or amino group (ethylene glycol, polyethylene glycol, glycerin, polyglycerin, bisphenol A, etc.), polyepoxy compounds, diepoxy compounds, Examples include monoepoxy compounds and glycidylamine compounds. Examples of the polyepoxy compound include sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, triglycidyl tris(2-hydroxyethyl) isocyanate, glycerol polyglycidyl ether, and trimethylolpropane. Examples include polyglycidyl ethers. Examples of diepoxy compounds 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, polypropylene glycol diglycidyl ether, Examples 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.

A carbodiimide compound is a compound having one or more carbodiimide structures or carbodiimide derivative structures in its molecule.
As the carbodiimide compound, a polycarbodiimide compound having two or more carbodiimide structures or carbodiimide derivative structures in the molecule is more preferable for better strength of the primer layer.

Carbodiimide compounds can be synthesized by known techniques, and generally a condensation reaction of diisocyanate compounds is used. The diisocyanate compound is not particularly limited, and both aromatic and aliphatic types can be used. Specifically, tolylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, phenylene diisocyanate, naphthalene diisocyanate, hexane diisocyanate, etc. Examples include methylene diisocyanate, trimethylhexamethylene diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, dicyclohexyl diisocyanate, dicyclohexylmethane diisocyanate, and the like.

In order to improve the water solubility and water dispersibility of polycarbodiimide compounds, surfactants may be added to the extent that the effects of the present invention are not lost, or quaternary ammonium salts of polyalkylene oxides and dialkylamino alcohols may be added. Hydrophilic monomers such as hydroxyalkyl sulfonate and the like may be added.

A silane coupling compound is an organosilicon compound having an organic functional group and a hydrolyzable group such as an alkoxy group in one molecule.
Examples of the silane coupling compound include 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, Epoxy group-containing compounds such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, vinyl group-containing compounds such as vinyltrimethoxysilane, vinyltriethoxysilane, p-styryltrimethoxysilane, p-styryltriethoxysilane Styryl group-containing compounds such as 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth)acryloxy (Meth)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-mercaptopropylmethyldiethoxysilane and other mercapto group-containing compounds.

Among the above compounds, from the viewpoint of the strength of the primer layer, silane coupling compounds containing epoxy groups, silane coupling compounds containing double bonds such as vinyl groups and (meth)acrylic groups, and silane coupling compounds containing amino groups are recommended. More preferred are silane coupling compounds.

Note that these crosslinking agents react during the drying process and film forming process to improve the performance of the primer layer. It can be assumed that unreacted products of the crosslinking agent, compounds after the reaction, or a mixture thereof exist as compounds derived from the crosslinking agent in the formed primer layer.

The antistatic agent to be included in the primer layer is not particularly limited, and any known antistatic agent may be used, such as a compound having an ammonium group, a polyether compound, a compound having a sulfonic acid group, betaine, etc. Examples include compounds, conductive organic polymers, and the like.

The primer layer may contain particles for blocking and improving slipperiness.
The primer layer may contain an antifoaming agent, a coating improver, a thickener, an organic lubricant, an ultraviolet absorber, an antioxidant, a foaming agent, a dye, as necessary, within a range that does not impair the gist of the present invention. It may contain additives such as pigments.

The proportion of the resin in 100% by mass of the primer layer is, for example, 5% by mass or more, preferably 10 to 99% by mass, more preferably 20 to 95% by mass, and even more preferably 30 to 90% by mass. If the proportion of the resin is within the above range, the adhesion performance and the appearance of the primer layer will be better.

The proportion of the compound derived from the crosslinking agent in 100% by mass of the primer layer is, for example, 80% by mass or less, preferably 0.5 to 65% by mass, more preferably 3 to 50% by mass, and still more preferably 5 to 40% by mass. range. If the proportion of the compound derived from the crosslinking agent is within the above range, the adhesion performance and the strength of the primer layer will be better.

The thickness of the primer layer cannot be determined unconditionally because it depends on the material used for the primer layer and the performance to be developed, but it is preferably 0.001 to 10 μm, more preferably 0.01 to 4 μm, and still more preferably 0.001 to 10 μm. It is in the range of 0.02 to 1 μm.
The primer layer can be formed by a known method.

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

The release layer is provided to improve transferability. As the material used for the release layer, conventionally known materials such as silicone compounds, fluorine compounds, and long-chain alkyl group-containing compounds can be used. Among these, silicone compounds and fluorine compounds are preferred in order to exhibit stronger mold release performance, and fluorine compounds and long-chain alkyl group-containing compounds are preferred from the viewpoint of not contaminating the transferred material.

The silicone compound refers to a compound having a silicone structure in the molecule, and includes, for example, alkyl silicones such as dimethyl silicone and diethyl silicone, phenyl silicone having a phenyl group, and methyl phenyl silicone. Silicones having various functional groups can also be used, such as ether groups, hydroxyl groups, amino groups, epoxy groups, carboxylic acid groups, halogen groups such as fluorine, perfluoroalkyl groups, various alkyl groups, and various silicones. Examples include hydrocarbon groups such as aromatic groups. As other functional groups, silicone with a vinyl group and hydrogen silicone in which a hydrogen atom is directly bonded to a silicon atom are also common, and by using both together, an addition type silicone (a type formed by an addition reaction between a vinyl group and a hydrogen silane) is produced. It is also possible to use it as Also preferred is a method of introducing a double bond such as an acryloyl group and reacting at the double bond.

Further, as the silicone compound, it is also possible to use modified silicones such as acrylic grafted silicone, silicone grafted acrylic, amino-modified silicone, and perfluoroalkyl-modified silicone. Considering heat resistance and stain resistance, it is preferable to use a curable silicone resin, and any curing reaction type such as a condensation type, addition type, or active energy ray curing type can be used.

The fluorine compound is a compound containing a fluorine atom in the compound. As the fluorine compound, organic fluorine compounds are suitably used, and examples thereof include perfluoroalkyl group-containing compounds, polymers of olefin compounds containing fluorine atoms, and aromatic fluorine compounds such as fluorobenzene. From the viewpoint of mold releasability, a compound having a perfluoroalkyl group is preferable. Further, as the fluorine compound, a compound containing a long-chain alkyl compound as described below can also be used.

Compounds having a perfluoroalkyl group include, for example, perfluoroalkyl (meth)acrylate, perfluoroalkylmethyl (meth)acrylate, 2-perfluoroalkylethyl (meth)acrylate, 3-perfluoroalkylpropyl (meth)acrylate. , 3-perfluoroalkyl-1-methylpropyl (meth)acrylate, 3-perfluoroalkyl-2-propenyl (meth)acrylate and other perfluoroalkyl group-containing (meth)acrylates and their polymers, perfluoroalkylmethyl vinyl 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. etc. In consideration of heat resistance and stain resistance, polymers are preferred. The polymer may be a single compound or a polymer of multiple compounds. Further, from the viewpoint of antifouling properties, the perfluoroalkyl group preferably has 3 to 11 carbon atoms. Furthermore, it may be a polymer with a compound containing a long-chain alkyl compound as described 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 hexyl group, octyl group, decyl group, lauryl group, octadecyl group, and behenyl group. Examples of the compound having an alkyl group include various long-chain alkyl group-containing polymer compounds, long-chain alkyl group-containing amine compounds, long-chain alkyl group-containing ether compounds, and long-chain alkyl group-containing quaternary ammonium salts. . In consideration of heat resistance and stain resistance, a polymer compound is preferable. Further, from the viewpoint of effectively obtaining antifouling properties, it is more preferable to use a polymer compound having a long-chain alkyl group in its side chain.

A polymer compound having a long-chain alkyl group in its 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 above-mentioned reactive group include a hydroxyl group, an amino group, a carboxyl group, an acid anhydride, and the like. Examples of compounds having these reactive groups include polyvinyl alcohol, polyethyleneimine, polyethyleneamine, reactive group-containing polyester resin, reactive group-containing poly(meth)acrylic resin, and the like. Among these, polyvinyl alcohol is preferred in consideration of stain resistance and ease of handling.

The compound having an alkyl group that can react with the above-mentioned reactive group includes, for example, isocyanate containing a long chain alkyl group such as hexyl isocyanate, octyl isocyanate, decyl isocyanate, lauryl isocyanate, octadecyl isocyanate, and behenyl isocyanate, hexyl chloride, and octyl chloride. , long-chain alkyl group-containing acid chlorides such as decyl chloride, lauryl chloride, octadecyl chloride, and behenyl chloride, long-chain alkyl group-containing amines, and long-chain alkyl group-containing alcohols. Among these, long-chain alkyl group-containing isocyanates are preferred in consideration of mold releasability and ease of handling, and octadecyl isocyanate is particularly preferred.

Additionally, polymer compounds having long-chain alkyl groups in their side chains can also be obtained by polymerizing long-chain alkyl (meth)acrylates or copolymerizing long-chain alkyl (meth)acrylates with other vinyl group-containing monomers. . Examples of long-chain alkyl (meth)acrylates include hexyl (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, octadecyl (meth)acrylate, and behenyl (meth)acrylate. It will be done.

The content of the mold release agent in the surface functional layer to exhibit the above-mentioned mold release performance depends on the materials used, so it cannot be determined unconditionally, but in the case of silicone compounds and fluorine compounds, it is usually 0.01. The content is in the range of at least 0.1% by mass, more preferably at least 0.2% by mass, and the upper limit may be 100% by mass. In addition, when using a long-chain alkyl group-containing compound, the content is usually 0.1% by mass or more, preferably 1% by mass or more, more preferably 3% by mass or more, and even if the upper limit is 100% by mass. I don't mind. By using it within the above range, effective mold release performance can be achieved.

As the antistatic agent used when forming the antistatic layer as a surface functional layer to prevent dust adhesion, etc., various conventionally known antistatic agents can be used.

The thickness of the surface functional layer of the transfer mold is preferably 5 times or less the height from the concave portions to the convex portions formed by the uneven layer. This is because when the height of the unevenness is 5 times or more, the matting performance due to the unevenness is reduced. The thickness of the surface functional layer depends on the height of the unevenness, so it cannot be determined unconditionally, but it is usually 0.001 to 3 μm, preferably 0.005 to 2 μm, more preferably 0.01 to 1 μm, and even more preferably 0.02 μm. ~0.5 μm, particularly preferably from 0.03 to 0.2 μm. By using it within the above range, it becomes possible to achieve both the expression of function by the surface functional layer and the matte property due to the unevenness of the uneven layer.
The surface functional layer can be formed by a known method.

(Back functional layer of transfer mold)
The back functional layer of the transfer mold can be provided to impart various functions to the surface of the transfer mold opposite to the transfer side (the surface of the base material layer opposite to the uneven layer side).
Examples of the back functional layer include an adhesive layer, an antistatic layer, an antiblocking layer, and the like.

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

[Layer other than the uneven layer of the transferred object]
The object to be transferred of the present invention may have a base material layer in addition to the layer having an uneven structure (uneven layer) of the object to be transferred. Further, the transferred object is selected from the group consisting of a primer layer provided between the uneven layer and the base layer, and a back functional layer provided on the surface of the base layer opposite to the uneven layer side. It may have one or more layers selected. Furthermore, a surface functional layer may be provided on the surface of the uneven layer opposite to the base layer side, as long as it does not impair the effects of the present invention.

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

(Primer layer of transferred object)
As the primer layer of the transferred object, the same material as the transfer type primer layer can be used. For example, an adhesion-improving layer can ensure sufficient adhesion between the base layer and the transferred object to prevent it from peeling off when the transferred object is used, and an antistatic layer can provide sufficient adhesion between the substrate layer and the transferred object, and an antistatic layer can ensure sufficient adhesion between the substrate layer and the transferred object, and an antistatic layer can provide sufficient adhesion between the substrate layer and the transferred object to prevent it from peeling off when the transferred object is used. can reduce dust adhering to

(Surface functional layer of transferred object)
The surface functional layer of the transfer object can be provided to impart various functions to the surface of the transfer object (on the surface of the uneven layer opposite to the base layer side).
Examples of the surface functional layer of the transferred object include an antifouling layer, an antistatic layer, a refractive index adjustment layer (an antireflection layer, a 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 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 silicone compounds, fluorine compounds, and long-chain alkyl group-containing compounds can be used. Among these, silicone compounds and fluorine compounds are preferred in order to exhibit stronger antifouling performance, and fluorine compounds and long-chain alkyl group-containing compounds are preferred from the viewpoint of not contaminating those with which the antifouling layer comes into contact. As for specific compounds, the same materials as those used for the release layer as the surface functional layer of the transfer mold can be mentioned.

As the antistatic agent used when forming the antistatic layer as the surface functional layer of the transfer object, 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 to be used when forming a refractive index adjustment layer as a surface functional layer of the transferred object, when the purpose is to increase the refractive index, materials such as benzene structure, bisphenol A structure, melamine structure, and fluorene structure are used. Aromatic-containing compounds, such as naphthalene, anthracene, phenanthrene, naphthacene, benzo[a]anthracene, benzo[a]phenanthrene, pyrene, benzo[c]phenanthrene, and perylene structures, which are considered to be high refractive index compounds among aromatics. fused 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 include metal oxides such as, metal-containing compounds such as metal chelate compounds such as titanium chelate and zirconium chelate, compounds containing a sulfur element, and compounds containing a halogen element.

Metal oxides are preferably used in the form of particles, as there is a concern that adhesion may deteriorate depending on the form in which they are used, and the average particle size is preferably 100 nm or less, more preferably 100 nm or less, from the viewpoint of coating appearance, etc. is in the range of 50 nm or less, more preferably 25 nm or less.

When the purpose is to lower the refractive index, conventionally known materials can be used as the material used when forming the refractive index adjustment layer as the surface functional layer of the transferred object, such as acrylic resin and urethane. This is possible because resins generally have a low refractive index. Further, in particular, compounds in which fluorine atoms are incorporated into the resin, such as fluororesins, compounds containing a fluororesin in the main skeleton, and compounds containing perfluoroalkyl groups in the side chains, are mentioned. Examples of inorganic materials 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 object is preferably 5 times or less the height from the concave portions to the convex portions formed by the uneven layer. This is because when the height of the unevenness is 5 times or more, the matting performance due to the unevenness is reduced. The thickness of the surface functional layer depends on the height of the unevenness, so it cannot be determined unconditionally, but it is usually 0.001 to 3 μm, preferably 0.005 to 2 μm, more preferably 0.01 to 1 μm, and even more preferably 0.02 μm. ~0.5 μm, particularly preferably from 0.03 to 0.2 μm. By using it within the above range, it becomes possible to achieve both the expression of function by the surface functional layer and the matte property due to the unevenness of the uneven layer.
The surface functional layer can be formed by a known method.

(Functional layer on the back side of the transferred object)
The back surface functional layer of the transfer object can be provided in order to impart various functions to the surface of the base material layer on the side opposite to the uneven layer side (transfer object side).
Examples of the functional layer on the back surface of the transferred object include an adhesive layer, an antistatic layer, a refractive index adjusting layer, and an anti-blocking layer.
The adhesive layer is provided to bond the laminate to various adherends. The antistatic layer is used to prevent the adhesion of surrounding dust, etc. due to peel-off charging and frictional charging, and the resulting defects on the outermost surface of the laminate, especially on the outermost surface of the base material layer on the side opposite to the uneven layer side. provided. The refractive index adjustment layer is provided, for example, in order to improve the total light transmittance of the laminate. The anti-blocking layer is provided to reduce blocking of the laminate.

As the adhesive for forming the adhesive layer, known adhesives can be used, including acrylic, polyester, urethane, rubber, and the like. Among them, acrylic is preferred 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, respectively, as surface functional layers.

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

(Formation of surface functional layer and back functional layer)
Regarding the formation of the front functional layer and the back functional layer in both the transfer mold and the transferred object, use the above-mentioned series of compounds as a solution or dispersion in a solvent, with a solid content concentration of about 0.1 to 80% by mass as a guide. It is preferable to manufacture a laminate by coating a substrate with the prepared liquid.

Examples of methods for forming the front functional layer and the back functional layer in both the transfer mold and the transferred object include gravure coating, reverse roll coating, die coating, air doctor coating, blade coating, rod coating, bar coating, and curtain coating. Conventionally known coating methods such as , knife coat, transfer roll coat, squeeze coat, impregnation coat, kiss coat, spray coat, calendar coat, and extrusion coat can be used.

There are no particular limitations regarding the drying and curing conditions when forming the front functional layer and back functional layer on the base film for both the transfer mold and the transferred material, but in the case of a coating method, the coating liquid Regarding drying of the solvent such as water used in the drying process, the temperature is usually 50 to 150°C, preferably 80 to 130°C, and more preferably 90 to 120°C. As a guideline, the drying time is in the range of 3 to 200 seconds, preferably 5 to 120 seconds. In addition, in order to improve the strength of the front functional layer and the back functional layer, 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 carried out in the film manufacturing process. It's something you have to go through. As a guide, the time for the heat treatment step is in the range of 3 to 200 seconds, preferably 5 to 120 seconds.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof.
The measurement method and evaluation method used in the present invention are as follows.

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

(2) Average primary particle diameter (d50: μm)
The average primary particle diameter was defined as the 50% cumulative (weight basis) value in the equivalent spherical distribution measured using a centrifugal sedimentation type particle size distribution analyzer Model SA-CP3 manufactured by Shimadzu Corporation.

(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. In addition, a calibration curve was created using F288/F80/F40/F10/F4/F1/A5000/A1000/A500 (manufactured by Tosoh Corporation) and styrene as standard polystyrene. The measurement was carried out at a column oven temperature of 40° C. using 100 μl of a solution in which the polymer was dissolved in tetrahydrofuran to a concentration of 0.4%. The weight average molecular weight (Mw) was calculated in terms of standard polystyrene.

(4) RSm, Sa and θa
Using a surface shape measurement system (scanning white interference microscope "VS1330" manufactured by Hitachi High-Tech Science Co., Ltd.), the surface shape of a 236.9 μm x 177.6 μm area on the surface of the cured film was measured using optical interferometry and complemented. and baseline correction and read the data. The magnification of the objective lens at the time of measurement was set to 20 times. In addition, in this evaluation, the presence or absence of a wrinkle-like uneven structure was also confirmed.
In addition, when comparing the physical properties of the transfer mold and the transferred material, when comparing percentages, the value obtained by subtracting the physical property value of the transfer mold from the physical property value of the transferred material is divided by the physical property value of the transfer mold. Calculated. Regarding the difference in each physical property, the absolute value of the value obtained by subtracting the physical property value of the transfer mold from the physical property value of the transferred object was calculated.

(5) Total light transmittance/haze A laminate in which a cured film was formed on a base material was measured. Total light transmittance and haze are determined according to JIS Z8722:2009 (Geometric conditions for irradiation and light reception of transparent objects) and JIS K7361-1:1997 (Plastic - Test method for total light transmittance of transparent materials) JIS K7136:2000 (Plastic -Measurement was made using a haze meter "SH7000" manufactured by Nippon Denshoku Kogyo Co., Ltd. in accordance with ``How to Determine Haze of Transparent Materials''.
Regarding haze, the haze of only the uneven structure layer (cured film) caused by the transfer mold or the transferred object was evaluated by measuring the haze of only the base material and subtracting it from the measured haze value of the laminate.

(6) 20° and 60° gloss/matte properties A laminate in which a cured film was formed on a base material was measured. 20° and 60° gloss (20° and 60° specular gloss) were measured in accordance with JIS Z 8741-1997 using a gloss meter "VG2000" manufactured by Nippon Denshoku Industries. The lower the gloss value, the better the matte property.

(7) Pencil hardness The pencil hardness of the cured film was measured according to JIS K5600-5-4:1999 Paint General Test Methods - Part 5: Mechanical Properties of Coating Films - Section 4: Scratch Hardness (Pencil Method).

(8) Method of measuring surface resistance value Using a high resistivity meter: Hiresta MCP-HP450 manufactured by Mitsubishi Chemical Analytech Co., Ltd., the sample was conditioned for 30 minutes in a measurement atmosphere with an applied voltage of 100 V, 23°C, and 50% RH. The surface resistivity was measured. If the surface resistance value is OVER, this indicates that the surface resistance value is too high to be measured.

(9) Matting property The laminate was installed in a room lit with a white linear fluorescent light, and the distance between the fluorescent light and the laminate was set to 2.5 m, and the uneven layer side was visually observed to be matte. The quality (reflection of fluorescent lights) was evaluated using the following evaluation criteria A to D. Evaluations A to C are judgments in which matte properties can be confirmed.
A: The reflected image of the fluorescent light is strongly blurred, and the outline of the fluorescent light cannot be confirmed.
B: The image reflected from the fluorescent light is blurred, but the outline can be seen faintly.
C: The image reflected from the fluorescent light is a little blurry, and although the outline can be seen, it is observed as a wavy shape and appears dark white.
D: The reflected image of the fluorescent light is clear, the outline can be clearly seen, and the image appears straight and white.

(10) Magic stain resistance (oil repellency/stain resistance)
After writing was written on the uneven layer with an oil-based black marker "Macky Fine" manufactured by Zebra Co., Ltd., it was visually observed and evaluated. The result shows that the ink repelling property is superior in oil repellency (stain resistance), and the evaluations A and B are judgments that confirm the dirt resistance.
A: Ink is repelled.
B: Only the edge where the ink was written was slightly repelled.
C: Ink is not repelled.

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

(Production of acrylic resin (b1) having 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 parts 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. Thereafter, 2,2'-azobis(2,4-dimethylvaleronitrile) (0.3 parts by mass) was further added and reacted for 3 hours, followed by propylene glycol monomethyl ether (48 parts by mass) and p-methoxyphenol ( 0.5 parts 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. Amount)) An acrylic resin (b1) having 1.2 mmol/g of radically polymerizable double bonds in the side chain was obtained. The weight average molecular weight (Mw) was 48,800.

(Production of acrylic resin (b2) having 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, stirrer, and reflux condenser, propylene glycol monomethyl ether (157 parts by mass), glycidyl methacrylate (98 parts by mass), methyl methacrylate (1.0 parts by mass), and ethyl acrylate (1.0 parts by mass). ), mercaptopropyltrimethoxysilane (1.9 parts by mass), and 2,2'-azobis(2,4-dimethylvaleronitrile) (1.0 parts by mass), γ-trimethoxysilylpropanethol (Shin-Etsu Chemical Co., Ltd.) 1.9 parts by mass of KBM-803) (manufactured by Co., Ltd.) was added, and the mixture was reacted at 65° C. for 3 hours. Thereafter, 2,2'-azobis(2,4-dimethylvaleronitrile) (0.5 parts by mass) was further added and reacted for 3 hours, and propylene glycol monomethyl ether (138 parts by mass) and p-methoxyphenol ( 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. )) An acrylic resin (b2) having 4.6 mmol/g of radically polymerizable double bonds in the side chain was obtained. The weight average molecular weight (Mw) was 17,700.

(Manufacture of transfer-type curable composition)
Each material shown below was mixed in the amount shown in Table 1 (parts by mass, converted to non-volatile content). Thereafter, a mixed solvent of propylene glycol monomethyl ether (hereinafter referred to as PGM) and methyl ethyl ketone (hereinafter referred to as MEK) (PGM:MEK (mass ratio) of 7:3) was added so that the solid content concentration was 30% by mass, and a uniform A coating liquid (transfer type curable composition) was obtained by stirring until the mixture was mixed.
・(Meth)acrylate (a1): Urethane acrylate (Mitsubishi Chemical Shikou UV-1700B) (trifunctional or higher)
・(Meth)acrylate (a2): Modified epoxy acrylate (EBECRYL 3708 manufactured by Daicel Allnex) (bifunctional)
・(Meth)acrylate (a3): 1,6-hexanediol diacrylate (bifunctional)
・(Meth)acrylate (a4): Dimethylol tricyclodecane diacrylate (light acrylate DCP-A manufactured by Kyoeisha Chemical Co., Ltd.) (bifunctional)
・(Meth)acrylate (a5): Dipentaerythritol hexaacrylate (6 functional)
・(Meth)acrylate (a6): Mixture of pentaerythritol triacrylate (trifunctional) and pentaerythritol tetraacrylate (tetrafunctional) (Viscoat #300, manufactured by Osaka Organic Chemical Industry Co., Ltd.)
・(Meth)acrylate (a7): Polyester urethane (meth)acrylate (manufactured by Mitsubishi Chemical Corporation Shiko UT-6042 (bifunctional)
・(Meth)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): Mitsubishi Chemical Corporation BR-80 (acrylic copolymer)
・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 agent (silicone compound) (c2): Silicone-containing polymer (GL-04R manufactured by Kyoeisha Chemical Co., Ltd.)
・Mold release agent (silicone compound) (c3): Silicone hexaacrylate (EBECRYL 1360 manufactured by Daicel Allnex)
・Particles (d): Crosslinked acrylic particles with an average particle diameter of 1.8 μm (MX-180TA manufactured by Soken Kagaku Co., Ltd.)
- Photopolymerization initiator (e): IGM Resins B. V. Manufactured by Omnirad 184
・Antistatic agent (f): (meth)acrylic polymer containing quaternary ammonium base (Mitsubishi Chemical Corporation Nikka Taibo number average molecular weight: 28,000)

(Composition for forming primer layer)
The following polyester resin (P1), urethane resin (P2), melamine compound (P3), and particles (P4) were mixed into polyester resin (P1)/urethane resin (P2)/melamine compound (P3)/particles (P4) (solid A composition for forming a primer layer was obtained by mixing the components at a weight ratio of 60/25/10/5.
・Polyester resin (P1): Aqueous dispersion of polyester resin with the following composition Monomer composition: (Acid component) Terephthalic acid / Isophthalic acid / 5-Sodium sulfoisophthalic acid // (Diol component) Ethylene glycol / 1,4- Butanediol/diethylene glycol = 56/40/4//70/20/10 (mol%)
・Urethane resin (P2): Water dispersion of polyester urethane resin consisting of the following composition: Isophorone diisocyanate: Terephthalic acid: Isophthalic acid: Ethylene glycol: Diethylene glycol: Dimethylolpropanoic acid = 12:19:18:21:25:5 ( mol%)
・Melamine compound (P3): Hexamethoxymethylolmelamine ・Particles: (P4): Silica particles with an average primary particle diameter of 0.07 μm

(Polyester film base material)
A raw material obtained by mixing polyester (S1), (S2), and (S3) in proportions of 91% by mass, 3% by mass, and 6% by mass, respectively, was used as the raw material for the outermost layer (surface layer). 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 coextrusion with a layer configuration of 2 types and 3 layers (surface layer/intermediate layer/surface layer = 1:8:1 discharge rate), cooling and solidifying.
Next, the longitudinally stretched film was stretched 3.1 times in the longitudinal direction at a film temperature of 85°C using the difference in peripheral speed of the rolls, and then a composition for forming a primer layer was applied to one side of the longitudinally stretched film, introduced into a tenter, and stretched at 95°C. After drying for 10 seconds at A polyester film base material 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 was applied onto the primer layer of the polyester film, dried at 70°C for 1 minute, and exposed to excimer light (half width 14 nm) using xenon (wavelength 172 nm). 15 mJ/cm ² , illuminance 5 mW/cm ² (Ushio Inc. xenon excimer 172 nm light irradiator, lamp unit model: SUS05 (lamp house model: H0011, lighting power supply model: B0005), nitrogen flow (oxygen concentration 1% or less) ) to a coating film made of the coating solution shown in Table 1, and then in an air atmosphere with a high-pressure mercury lamp at a cumulative light intensity of 400 mJ/cm ² and an illumination intensity of 200 mW/cm ² (high output UV device manufactured by Eye Graphics (model: US5). -X1802-X1202) UV conveyor) to obtain a cured film (transfer type) having a wrinkle-like uneven structure and having a thickness (after drying) of 5 μm as shown in Table 3. The resulting transfer mold had a wrinkled uneven structure and had good matting properties. Table 3 shows the characteristics of this transcription type.

[Comparative example 1]
A cured film (transfer type (T-7)) was obtained in the same manner as in Example 1, except that in Example 1, the excimer light was not used and the curing was performed only by ultraviolet irradiation from a high-pressure mercury lamp. 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 matte property was observed.

[Comparative example 2]
In Example 1, a cured film (transfer type (T-8)) was obtained by manufacturing 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, no wrinkled uneven structure was formed, but it had a convex surface shape.

[Example 7]
On the transfer mold (T-1) obtained in Example 1, in order to impart releasability from the transferred material, liquid B-1 in Table 1 was applied, dried at 70°C for 1 minute, and then exposed to air. In an atmosphere, ultraviolet light was irradiated with a high-pressure mercury lamp at a cumulative light intensity of 400 mJ/cm ² and an illuminance of 200 mW/cm ² (UV conveyor of a high-output UV device (model: US5-X1802-X1202) manufactured by Eye Graphics). A release layer having a thickness of 0.1 μm (after drying) was formed.
A solvent-free coating solution shown in Table 2 (transfer material curable composition C-1) was applied onto the release layer, and the polyester film obtained in Example 1 before the formation of the transfer mold was coated with a primer for the polyester film. Place the layer so that it is in contact with the transfer material curable composition, and apply a high-pressure mercury lamp in an air atmosphere with an integrated light amount of 400 mJ/cm ² and an illuminance of 200 mW/cm ² (high output UV device manufactured by Eye Graphics (model: US5). -X1802-X1202) UV conveyor) to form a cured film with a thickness (after drying) of 9 μm. The obtained cured film was peeled off from the transfer mold (T-1) to obtain a laminate in which the transferred object was formed on the primer layer of the polyester film.
The resulting transfer material had a wrinkled uneven structure and had good matte properties. The properties of this transfer material are shown in Tables 4 to 6.

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

[Example 14]
Example 7 was produced in the same manner as in Example 7 except that the transfer material curable composition shown in Table 2 was applied directly onto the transfer mold without providing a release layer, and the transfer material with the cured film was I got it. The properties of the obtained transfer materials are shown in Tables 4 to 6.

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

[Comparative example 3]
In Example 7, the transfer target was produced in the same manner as in Example 7 except that the composition of the transfer target curable composition was changed to the composition shown in Table 2, and a transfer target with a cured film was obtained. The obtained transferred object had a concave shape, which was different from the shape of the transfer mold. Other properties are shown in Tables 4 to 6.

Claims (15)

A transfer type having a cured film of a curable composition, the surface of the cured film forming a transfer surface,
After the surface side of the coating film of the curable composition is cured by irradiation with vacuum ultraviolet rays to form a cured film, the inside of the coating film is cured by irradiation with active energy rays other than vacuum ultraviolet rays, thereby curing the surface side of the coating film. The transfer surface has a wrinkle-like uneven structure formed by buckling the cured film,
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 (Sa) defined in ISO25178 is 0.1 to 1000 μm. Type. The transfer mold according to claim 1, wherein the average value (θa) of the local inclination angle of the transfer surface is 2° or more. The transfer mold according to claim 1 or 2, wherein the transfer surface has a 60° gloss of 50 or less. The transfer mold according to any one of claims 1 to 3, wherein the curable composition contains (meth)acrylate. The transfer mold according to any one of claims 1 to 4, having the cured film on a base material. The transfer mold according to claim 5, wherein the base material is a film. A curable composition is laminated on a substrate, and the surface side of the coating film of the curable composition is cured by irradiating vacuum ultraviolet rays to form a cured film, and then by irradiation with active energy rays other than vacuum ultraviolet rays. The method for manufacturing a transfer mold according to claim 5 or 6, wherein the inside of the coating film is cured. A transfer object having a wrinkle-like uneven structure on the transfer surface obtained by transferring the wrinkle-like uneven structure of the transfer surface of the transfer mold,
The wrinkle-like uneven structure of the transfer surface is obtained by curing the surface side of the coating film of the curable composition by irradiating vacuum ultraviolet rays to form a cured film, and then curing the coating film by irradiating active energy rays other than vacuum ultraviolet rays. It is an uneven structure formed by buckling the hardened film on the surface side by hardening the inside of the
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 (Sa) defined in ISO 25178 is 0.1 to 1000 μm. Transferee. The transferred object according to claim 8, wherein the average value (θa) of the local inclination angle of the transferred surface is 2° or more. The transferred object according to claim 8 or 9, wherein the 60° gloss of the transferred surface is 50 or less. The object to be transferred according to any one of claims 8 to 10, wherein the object to be transferred is a cured film of a curable composition. The object to be transferred according to claim 11, wherein the curable composition constituting the object to be transferred contains (meth)acrylate. The transferred object according to claim 11 or 12, which has the cured film on a base material. The transferred object according to claim 13, wherein the base material is a film. According to any one of claims 8 to 14, the wrinkle-like uneven structure of the transfer surface of the transfer mold according to any one of claims 1 to 6 is transferred as a negative pattern onto the transfer surface of the transfer object. A method for producing a transfer target.