JP2012131087A - Concavo-convex hard coat film, production process thereof and decorative body using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a concavo-convex hard coat film with an embossed surface which has superior hardness and abrasion resistance of hard coat layer surface and curl resistance of the film itself, and to provide a production process of concavo-convex hard coat film with embossed surface, that is highly adhesive between a plastic film and the hard coat layer and has wide options in selecting a matrix member to be used.SOLUTION: The concavo-convex hard coat film is composed of a hard coat layer comprising an ultraviolet curable resin and laminated on at least one side surface of the plastic film. A silica hybrid type urethane acrylate is used in the ultraviolet curable resin, and the ultraviolet is applied from the side of plastic film in curing the ultraviolet curable resin.

Description

The present invention is an uneven hard coat film having irregularities on the surface, excellent hard coat properties and scratch resistance on the surface of the hard coat layer, excellent curl resistance of the hard coat film itself, and a plastic film and a hard coat layer. The present invention relates to a concavo-convex hard coat film having a rugged surface and a method for producing the same, and a decorative body obtained using the same.

Conventionally, in order to differentiate it from luxury products and other products, audio products, other home appliances, PCs, mobile phones and other molded products such as casings and parts, paper container packages, seal labels, etc. There are many hairline patterns, mat patterns, and other patterns with unique irregularities.

As a method of forming irregularities on the surface of various molded products, paper container packages, seal labels, etc., a method of forming irregularities by directly performing hairline processing, mat processing, etc., various molded products such as plastic film with irregularities previously formed, paper containers A method of forming irregularities by sticking to the surface of an object to be attached such as a package or a seal label.

Patent Document 1 discloses a lamination process in which a photocurable resin composed of any one or more of urethane acrylate, epoxy acrylate, or polyester acrylate is applied to a plastic film as a base material, and a photocurable layer is laminated in advance. A step of obtaining a laminate by sticking the uneven surface of the stamper film whose surface is substantially uneven to the surface of the photocurable layer, and an irradiation step of irradiating light from the stamper film side in order. A method for producing a laminate comprising a peeling step in which the stamper film is peeled from the laminate is described, and irregularities are formed on the surface of the photocurable layer of the resulting laminate.

Patent No. 4022241

However, since the laminate having irregularities formed on the surface of the photocurable layer produced by the production method described in Patent Document 1 uses urethane acrylate or the like for the photocurable resin, the laminate has the following: There were such drawbacks.

-Since the surface of the photocurable layer is inferior in hard coat property and scratch resistance, the surface of the photocurable layer is easily scratched, and there is a defect that the irregularities are easily lost and the design properties are impaired.

[2] Since the laminate itself in which the photocurable layer is laminated curls and is inferior in curling resistance, the laminate itself is subjected to post-processing such as metal vapor deposition, printing, and adhesive application on the laminate. However, there was a drawback that it was difficult to handle and the post-processability was poor.

Specifically, when an adhesive layer made of an adhesive is laminated on the laminate and stuck to the adherend, the laminate itself curls, and it is difficult to stick the laminate to the target location of the adherend. In addition, when post-processing is performed on the laminate, the laminate itself is curled and easily folds during processing, resulting in a problem that many defective products are generated during post-processing, resulting in poor productivity.

Furthermore, when curing a photo-curing resin, the stamper film must irradiate light such as ultraviolet rays because the stamper film side irradiates light such as ultraviolet rays. Therefore, the stamper film must be transparent. However, fabrics that do not transmit light, various molded products, metals, and the like cannot be used, and there is a drawback in that when a stamper film is selected, there are limitations and lack of diversity.

The present invention eliminates all the above-mentioned drawbacks, the hard coat layer surface is excellent in hard coat properties and scratch resistance, the curl resistance of the hard coat film itself is excellent, and further, the plastic film and the hard coat layer An uneven hard coat film and a method for producing the same, and a decorative body obtained using the same are provided.

[1] The present invention is a hard coat film in which a hard coat layer made of an ultraviolet curable resin is laminated on at least one surface of a plastic film, which satisfies the following conditions (1) and (2): It is an uneven hard coat film.
(1) The ultraviolet curable resin is a silica hybrid type urethane acrylate (2) The hard coat layer surface is uneven.

[2] The concavo-convex hard coat film according to [1] is a concavo-convex hard coat film with a cover material, wherein a cover material is laminated on the hard coat layer.

[3] The present invention is a method for producing an uneven hard coat film with a shaping material,
(Step A-1) A step of laminating a hard coat layer made of an ultraviolet curable resin on at least one surface of a plastic film,
(Step B-1) A step of laminating a shaping material having a concavo-convex pattern on at least one surface on the hard coat layer so that the concavo-convex pattern surface is in contact with the hard coat layer,
(C step) a step of irradiating the ultraviolet ray to cure the ultraviolet curable resin, transferring the concavo-convex pattern of the shaping material to the surface of the hard coat layer to form the concavo-convex;
The steps of (A-1 step), (B-1 step), and (C step) are carried out in this order, and the ultraviolet curable resin is a silica hybrid type urethane acrylate. This is a method for producing a film.

[4] The present invention is a method for producing an uneven hard coat film with a shaping material,
(Step A-2) A step of forming a hard coat layer made of an ultraviolet curable resin on the concavo-convex pattern surface of the shaping material having a concavo-convex pattern on at least one side,
(Step B-2) A step of laminating a plastic film on the hard coat layer,
(C step) a step of irradiating the ultraviolet ray to cure the ultraviolet curable resin, transferring the concavo-convex pattern of the shaping material to the surface of the hard coat layer to form the concavo-convex;
The steps of (A-2 step), (B-2 step), and (C step) are carried out in this order, and the ultraviolet curable resin is a silica hybrid type urethane acrylate. This is a method for producing a film.

  [5] The method according to [3] or [4], wherein the ultraviolet curable resin is irradiated with ultraviolet rays from the plastic film side when the ultraviolet curable resin is cured. It is.

[6] The present invention further comprises a step (D) of removing the shaping material in the method for producing a hard-coated film with a shaping material according to any one of [3] to [5]. It is a manufacturing method of the uneven | corrugated hard coat film characterized.

  [7] The present invention is an uneven hard coat film with a shaping material produced by the production method according to any one of [3] to [5].

  [8] The present invention is an uneven hard coat film produced by the production method according to [6].

  [9] The present invention is a decorative body characterized in that the surface on which the unevenness of the uneven hard coat film according to [1] is not formed is attached to the surface of an adherend.

  [10] The present invention is a decorative body characterized in that the surface on which the unevenness of the uneven hard coat film with cover material according to [2] is not formed is attached to the surface of the adherend.

  [11] The present invention is a decorative body characterized in that the surface of the adherend to which the unevenness of the uneven hard coat film with a shaping material according to [7] is not formed is attached.

  [12] The present invention is a decorative body characterized in that a surface on which an uneven surface of the uneven hard coat film according to [8] is not formed is attached to the surface of an adherend.

The uneven hard coat film of the present invention has a hard coat layer made of an ultraviolet curable resin laminated on at least one surface of a plastic film, and uses a silica hybrid urethane acrylate for the ultraviolet curable resin.
(1) The hard coat layer surface is excellent in hard coat properties and scratch resistance, and the hard coat layer surface is not easily scratched and has no irregularities, so that the design is not impaired.

Specifically, the hard coat property and the scratch resistance of the uneven hard coat film of the present invention were evaluated by the hard coat test and the scratch resistance test (both described in the examples described in detail later). It is sufficient that the layer surface is not scratched at all.
However, there is no practical problem as long as the hard coat layer surface is slightly scratched when evaluated by the hard coat property test and the scratch resistance test, and the above hard coat property and resistance of the uneven hard coat film of the present invention. The scratch resistance is at a level that causes no problem in practical use.

(2) The concave / convex hard coat film itself has excellent curl resistance, and is easy to handle and folds during processing when post-processing such as metal vapor deposition, adhesive coating and printing is performed on the concave / convex hard coat film of the present invention. The occurrence of wrinkles is also suppressed, the productivity is low and post-processability is good, and the uneven hard coat film of the present invention is applied to the surface of an object to be bonded such as various molded products, paper container packages, seal labels, Even when sticking via an adhesive layer made of an adhesive or a double-sided tape (hereinafter referred to as an adhesive layer), it is easy to stick and workability is good.

Specifically, the curl resistance of the concavo-convex hard coat film of the present invention is practically used when the height of warpage is 1 mm or less when evaluated by a curl resistance test (explained in Examples described later in detail). There is no problem, and the uneven hard coat film of the present invention maintains a substantially flat state without curling, and is at a level that does not cause a problem in practice.

Further, when the ultraviolet curable resin is cured, if the ultraviolet ray is irradiated from the plastic film side, the adhesive force between the plastic film and the hard coat layer becomes stronger.

Furthermore, when curing ultraviolet curable resin, if the ultraviolet light is irradiated from the plastic film side, the cover material and the shaping material used in the present invention do not necessarily need to be a material that transmits ultraviolet light, and a transparent plastic film. In addition to materials that transmit ultraviolet light, such as fabrics, various molded products, and materials that do not transmit ultraviolet light, such as metal, can be laminated to form an uneven hard coat film with a cover material or an uneven hard coat film with a shaping material. Therefore, when selecting a cover material or a shaping material, there are various selections.

In order for the uneven hard coat film of the present invention to obtain all of the above effects, it is optimal to use the production method of the present invention.

Moreover, the decorative body of the present invention in which the surface of the uneven hard coat film of the present invention on which the unevenness is not formed is adhered to the surface of the object to be adhered is the effect that the uneven hard coat film of the present invention has. Holding everything.

The plastic film used for the uneven hard coat film of the present invention is not particularly limited, and various plastic films such as a polyethylene terephthalate film, a polycarbonate film, a polyethylene film, a polypropylene film, and a polyamide film can be used.

The plastic film may be non-stretched, uniaxially stretched, or biaxially stretched, and may contain various additives such as an antistatic agent, a colorant, and a heat stabilizer.

In addition, when the uneven hard coat film of the present invention is attached to the surface of an adherend such as various molded products, paper container packages, seal labels, etc. via an adhesive layer or the like, it is applied in advance to the surface of the adherend. In addition to forming irregularities while maintaining the design properties such as the color tone and printed pattern, as will be described in detail later, in order to strengthen the adhesion between the plastic film and the hard coat layer, ultraviolet irradiation is applied to plastic. Since it is desirable to carry out from the film side, the plastic film is preferably transparent to transmit ultraviolet rays.

The thickness of the plastic film is not particularly limited, but is preferably 38 to 250 μm from the viewpoint of plasticity, thermal stability and the like. If the thickness of the plastic film is less than 38 μm, it will be difficult to handle the uneven hard coat film itself because it will not only curl but also become wrinkled when the hard coat layer is laminated or when the uneven hard coat film is handled. Therefore, it is not preferable. In addition, if the thickness of the plastic film is greater than 250 μm, ultraviolet rays are absorbed and diffused in the plastic film, and the ultraviolet irradiation amount necessary for curing the ultraviolet curable resin cannot be obtained, and the ultraviolet curable resin is cured. When it becomes inadequate and it is set as an uneven | corrugated hard coat film, since the adhesive force of a plastic film and a hard-coat layer becomes weak, it is unpreferable.

The ultraviolet curable resin used in the uneven hard coat film of the present invention is a resin that is cured when irradiated with ultraviolet rays. By using silica hybrid urethane acrylate, the hard coat of the uneven hard coat film of the present invention is used. The surface of the layer is preferable because it has excellent hard coat properties and scratch resistance, and the uneven hard coat film itself has excellent curl resistance.
The molecular weight of the ultraviolet curable resin is not particularly limited, but the surface of the hard coat layer of the concavo-convex hard coat film of the present invention can be hard-coated and scratch-resistant by using silica hybrid urethane acrylate having a molecular weight of 20000 or more. Further, it is preferable because the uneven hard coat film itself is more excellent in curling resistance.

As a method of laminating a hard coat layer on the surface of a plastic film, a hard coat layer can be laminated by coating an ultraviolet curable resin by a conventionally known coating method such as a gravure coating method, a reverse coating method, a die coating method or the like.

The thickness of the hard coat layer made of an ultraviolet curable resin is preferably 2 to 20 μm.
If the thickness of the hard coat layer is less than 2 μm, desired hard coat properties and scratch resistance cannot be obtained. If the thickness is greater than 20 μm, the plastic film is not only curled by the stress of the hard coat layer, but generally Many UV curable resins have a high viscosity, so that it is difficult to coat the UV curable resin to a uniform thickness, and the hard coat layer is thinned, resulting in an appearance defect.

In order to further strengthen the adhesion between the plastic film and the hard coat layer, the surface of the plastic film may be subjected to surface treatment such as easy adhesion coating, anchor coating, corona treatment, plasma treatment or the like.

The cover material used for the uneven hard coat film with a cover of the present invention can cover the surface of the hard coat layer, and when the uneven hard coat film of the present invention is post-processed, the hard coat layer surface is contaminated. It is sufficient if it can be used for the purpose of protecting the hard coat layer such as prevention of appearance, prevention of appearance defects due to adhesion of foreign matters or the like to the hard coat surface, and prevention of damage to the hard coat layer surface.

Specifically, as long as the object can be achieved, the cover material can be used without limitation on the material, material, shape, etc. For example, plastic film, paper, fabric, nonwoven fabric, metal, etc. can be used. Furthermore, when the shape is long, it is preferable to use a roll shape because it is easy to handle.
In addition, the shaping | molding material explained in full detail later can be used also as a cover material of the uneven | corrugated hard-coat film of this invention besides using it for the purpose of transferring an uneven | corrugated pattern to the hard-coat layer surface.

The uneven hard coat film of the present invention can be used as an uneven hard coat film alone, or it can be used for audio products, other home appliances, personal computers, mobile phones, etc. In order to differentiate, the cover material is used by sticking to the surface of the adherend via an adhesive layer or the like, so the cover material is finally removed and used.

Further, a layer having releasability may be previously laminated on the surface of the cover material in contact with the hard coat layer by a treatment such as silicon coating, fluorine coating, wax coating, melamine coating or the like.

Although it will not specifically limit if an unevenness | corrugation can be formed in the hard-coat layer surface as a method of forming an unevenness | corrugation in the hard-coat layer surface of the uneven | corrugated hard-coat film of this invention, UV curable resin is perfect like the manufacturing method of this invention. Before curing to UV-curing resin by irradiating with ultraviolet light after laminating the concave-convex pattern surface of the shaping material having a concave-convex pattern on at least one side and the hard coat layer surface made of UV-curing resin. A method of forming the unevenness on the surface of the hard coat layer by curing and transferring the uneven pattern of the shaping material to the surface of the hard coat layer is preferable because of the variety of unevenness and also good workability.

In addition to the above method, methods for forming irregularities on the surface of the hard coat layer are exemplified below. However, these methods are only examples, and even if other methods can form irregularities on the surface of the hard coat layer, There is no limit to the method.
(1) A method of forming irregularities by scraping off an ultraviolet curable resin cured by rubbing sandpaper, a file or the like directly on the surface of the hard coat layer.
(2) A method of forming irregularities on the surface of the hard coat layer by hitting hard particles such as sand and pebbles on the surface of the hard coat layer and scratching the hard coat layer.
(3) A method of forming irregularities by corroding the surface of the hard coat layer with a chemical such as acid or alkali.
(4) A method of forming irregularities on the surface of the hard coat layer by pressing a so-called embossing roll having irregularities on the surface in advance.
Further, (1) to (4) may be performed alone or in combination.

The production method of the present invention, which is optimal for obtaining all of the above effects of the uneven hard coat film of the present invention, will be described below.

A step of forming a hard coat layer made of an ultraviolet curable resin on at least one side of a plastic film (step A-1), and a forming material having a concavo-convex pattern on at least one side is formed on the hard coat layer. Step of laminating so as to be in contact with the coat layer (step B-1), step of irradiating ultraviolet rays to cure the ultraviolet curable resin, and transferring irregularities of the shaping material to the hard coat layer surface to form irregularities By performing each step of (C step) in the order of (A-1 step), (B-1 step) and (C step), the uneven hard coat film with a shaping material of the present invention can be produced.

Also, a step of forming a hard coat layer made of an ultraviolet curable resin on the concavo-convex pattern surface of the shaping material having at least one concavo-convex pattern (step A-2), a step of laminating a plastic film on the hard coat layer (B-2 process), each process of the process (C process) of irradiating an ultraviolet-ray, hardening the said ultraviolet curable resin, and transferring the uneven | corrugated pattern of the said shaping material to the said hard-coat layer surface, and forming an unevenness | corrugation. By performing the steps (A-2 step), (B-2 step) and (C step) in this order, the uneven hard coat film with a shaping material of the present invention can be produced.

The method of laminating the shaping material on the hard coat layer in the (B-1 step) and the method of laminating the plastic film on the hard coat layer in the (B-2 step) are preferably performed by a laminating method. Other methods may be used.

The concavo-convex hard coat film of the present invention can be produced by further performing a step (D step) of removing the shaping material from the concavo-convex hard coat film with a shaping material.

In the method for producing an uneven hard coat film of the present invention, when the ultraviolet curable resin is cured, the ultraviolet ray is irradiated from the plastic film side in order to increase the adhesion between the plastic film and the hard coat layer. Is preferred.

Specifically, the adhesion strength test between the plastic film and the hard coat layer was performed on the uneven hard coat film irradiated with ultraviolet rays from the shaping material side and the uneven hard coat film irradiated from the plastic film side (detailed later). When compared with the adhesive strength measured in Example 1), the adhesive strength between the plastic film and the hard coat layer was stronger when irradiated from the plastic film side.

As described above, the difference in the adhesion between the plastic film and the hard coat layer due to the difference in the direction of irradiating with ultraviolet rays is due to the fact that when ultraviolet rays are irradiated from the shaping material side, the ultraviolet rays become the shaping material and the hard coat layer. When it passes through, it is absorbed, blocked, or diffused in a minute amount by the shaping material or hard coat layer, and the UV irradiation amount necessary for curing the UV curable resin cannot be obtained, and the UV curable resin is cured. Is insufficient, the adhesion between the plastic film and the hard coat layer is weakened. In contrast, when UV light is irradiated from the plastic film side, UV light is not absorbed, blocked, or diffused by the plastic film, and the UV curing resin is less likely to be hardened. It is considered that the irradiation amount of ultraviolet rays can be obtained, and the adhesion between the plastic film and the hard coat layer is enhanced.

Even when irradiating ultraviolet rays from the shaping material side, it is possible to obtain the irradiation amount of ultraviolet rays necessary for curing the ultraviolet curable resin by increasing the irradiation amount of ultraviolet rays and increasing the irradiation time. Although it is possible to obtain a sufficient adhesion, it is preferable to irradiate from the plastic film side because the longer the irradiation time of ultraviolet rays, the longer the work time and the worse the workability.

The shaping material used in the method for producing a concavo-convex hard coat film of the present invention only needs to have a concavo-convex pattern on at least one surface, and can be used without limitation on materials, materials, shapes, etc., for example, plastic film, glass, Paper, fabric, non-woven fabric, metal, etc. can be used. Furthermore, when the shape is long, it is preferable to use a roll shape because it is easy to handle.
In addition, as described above, in order to strengthen the adhesion between the plastic film and the hard coat layer, it is preferable to irradiate ultraviolet rays from the plastic film side, so the shaping material does not necessarily need to transmit ultraviolet rays. In selecting a shaping material, there are various selections.

The shaping material can be used as the cover material in addition to the purpose of transferring the uneven pattern of the shaping material to the surface of the hard coat layer.

Examples of the method for forming the concavo-convex pattern on the surface of the shaping material are as follows. However, these methods are examples, and even if other methods can form the concavo-convex pattern on the surface of the shaping material, the method is used. There is no limit.
(1) A method of forming a concavo-convex pattern by directly rubbing sandpaper, a file or the like to scrape the surface.
(2) A method of forming a concavo-convex pattern on the surface by hitting the surface with hard particles such as sand or pebbles and scratching it.
(3) A method of forming a concavo-convex pattern by corroding the surface with a chemical such as acid or alkali.
(4) A method of forming a concavo-convex pattern on the surface by press-contacting a so-called embossing roll whose surface has been concavo-convex in advance.
(5) A method of forming a concavo-convex pattern by laminating a resin layer on which resin or the like is printed on the surface by a known method.
(1) to (5) may be performed alone or in combination.

For example, as an example of the combination of (1) and (5), the surface on which the hairline uneven pattern of the hairline film is formed by forming a hairline uneven pattern on the surface of the plastic film by scratching the hairline (line) with sandpaper. Further, a partial hairline film can be obtained by partially printing a water-based ink or a melamine resin with a thickness that fills and disappears the hairline uneven pattern, and laminates a resin layer.

In addition, when using the shaping material which formed the resin layer which printed the water-based ink and formed the uneven pattern, the water-based ink remains on the surface of the hard coat layer even after the step of removing the shaping material (D step). Therefore, it is necessary to add a step (E step) of washing and removing the water-based ink with water.

When using non-woven fabrics, woven fabrics, knitted fabrics, etc. as the shaping material, they originally have a concavo-convex pattern on the surface and can be used as it is as a shaping material.

Further, a layer having releasability may be previously laminated on the surface of the shaping material in contact with the hard coat layer by a treatment such as silicon coating, fluorine coating, wax coating, melamine coating or the like.

The size of the shaping material can be used by cutting the shaping material into the desired shape as appropriate, and it may be partially laminated on the hard coat surface and cut to a size that can cover the entire hard coat layer. You may use it.
When the shaping material is cut into a desired shape and used, and when partially laminated on the surface of the hard coat layer, the uneven pattern of the shaping material is transferred only to the portion where the shaping material is laminated. The partially uneven hard coat film of the present invention in which unevenness is partially formed on the surface of the hard coat layer can be obtained.
Also, if the shaping material is used in a size that can cover all of the hard coat layer and is laminated on the hard coat layer surface, the uneven pattern of the shaping material is transferred to the entire hard coat layer surface, and the hard coat layer The uneven hard coat film of the present invention in which unevenness is formed on the entire layer surface can be obtained.

As the plastic film and the ultraviolet curable resin used in the method for producing an uneven hard coat film of the present invention, those described above can be used as they are.

The metal thin film layer may be provided with a desired design property by laminating a metal thin film layer, a printed layer, or the like by performing post-processing such as metal vapor deposition or printing on one side or both sides of the uneven hard coat film of the present invention. In addition, an uneven hard coat film with a metal thin film layer in which a printed layer or the like is laminated, an uneven hard coat film with a printed layer, etc. are also included in the uneven hard coat film of the present invention.

The decorative body of the present invention to which the uneven hard coat film of the present invention is attached is a molded product on the surface where the uneven surface of the uneven hard coat film is not formed for the purpose of differentiating from a high-class feeling or other products. It is attached to the surface of an object to be adhered such as metal, glass, ceramics, paper package, and seal label through an adhesive layer or the like.
In addition, using the uneven hard coat film with a cover material of the present invention and the uneven hard coat film with a shaping material, the decorative material with the cover material of the present invention is adhered to the surface of an object to be adhered via an adhesive layer or the like. A body and a decorative body with a shaping material can be obtained. By doing so, the cover material and the shaping material are removed and used in the final use, but the hard coat layer is used when handling the decorative body of the present invention or transporting. Protect the hard coat layer until just before using the decorative body of the present invention, such as prevention of contamination of the surface, prevention of appearance defects due to foreign matter adhering to the hard coat surface, prevention of damage to the hard coat layer surface, etc. Can do.
In addition, what is necessary is just to determine the thickness of an adhesive bond layer etc. suitably by the desired adhesive force, and an adhesive bond layer etc. may be laminated | stacked on either the uneven | corrugated hard coat film of this invention, or the surface of a to-be-adhered thing.

The concavo-convex hard coat film of the present invention to be adhered may be appropriately cut into a desired shape and adhered to a part of the surface of the adherend via an adhesive layer or the like. It may be cut to a size that can cover all of them, and may be attached to the entire surface of the adherend via an adhesive layer or the like.
When the uneven hard coat film of the present invention is used after being cut into a desired shape and adhered to the surface of the object to be adhered via an adhesive layer or the like, the color previously given to the surface of the object to be adhered In addition, the decorative body of the present invention in which unevenness is formed only on the portion where the uneven hard coat film of the present invention is adhered can be obtained while maintaining the design properties such as the print pattern and the like.
In addition, when the uneven hard coat film of the present invention is used in a size that can cover the entire surface of the adherend, and is attached to the surface of the adherend via an adhesive layer, the adherend The decorative body of the present invention in which irregularities are formed on the entire surface of the adherend can be obtained while maintaining the design properties such as the color tone and the printed pattern that are preliminarily applied to the surface.

As described above, in the concavo-convex hard coat film having irregularities on the surface, by using silica hybrid urethane acrylate as the ultraviolet curable resin for the hard coat layer, the hard coat layer surface has excellent hard coat properties and scratch resistance, The concavo-convex hard coat film of the present invention having excellent curl resistance of the concavo-convex hard coat film itself can be obtained.
Furthermore, it is perfectly safe to use a silica hybrid type urethane acrylate having a molecular weight of 20000 or more as an ultraviolet curable resin.

Moreover, when producing the uneven hard coat film of the present invention, the uneven hard coat film of the present invention having strong adhesion between the plastic film and the hard coat layer can be obtained by irradiating ultraviolet rays from the plastic film side. There is also a variety in the choice of shaping materials to be used.

[Create shaping material]
(Shaping material 1)
A hairline film (shaped material 1) in which a hairline pattern is formed by scratching one surface of a polyethylene terephthalate film with a thickness of 25 μm and a length of 4000 m with sandpaper in the length direction of the film with sandpaper. Got.

(Shaping material 2)
A melamine resin is printed on the surface of the hairline film obtained from the shaping material 1 on which the hairline unevenness pattern is formed and the thickness of the hairline unevenness disappears, and a resin layer is laminated. A partial hairline film (shaped material 2) having a hairline uneven pattern was obtained.

(Shaping material 3)
On the surface of the hairline film obtained with the shaping material 1 on which the hairline uneven pattern is formed, a water-based ink is printed in a figure shape with a thickness that fills and disappears the hairline uneven pattern, and a resin layer is laminated. A partial hairline film (shaped material 3) having a hairline uneven pattern was obtained.

[Creation of uneven hard coat film]
[Example 1]
Thereafter, the (A-1 step), (B-1 step), (C step), and (D step) were sequentially performed to obtain the uneven hard coat film of the present invention having hairline unevenness on the entire surface of the hard coat layer.
(Step A-1) Silica hybrid urethane acrylate having a molecular weight of 20000 as an ultraviolet curable resin on a surface of an easy-adhesion coat of a polyethylene terephthalate film having a thickness of 125 μm whose surface has been previously provided with an easy-adhesion coat (manufactured by Aika Kogyo Co., Ltd .: high molding Precure UV hard coat agent, product number Z910-3L) was coated by a die coating method, and a hard coat layer having a thickness of 5 μm was laminated.
(Step B-1)) The surface on which the hairline uneven pattern of the hairline film of the shaping material 1 was formed on the hard coat layer was laminated by a laminating method so as to contact the surface of the hard coat layer.
(Step C) UV rays of 207 mJ / cm ² were irradiated from the plastic film side for 2 seconds to cure the UV curable resin, and the hairline uneven pattern of the shaping material 1 was transferred to the hard coat layer surface to form hairline unevenness. .
(Step D) The shaping material 1 was removed.

[Example 2]
Instead of the silica hybrid urethane acrylate having a molecular weight of 20000 used in Example 1 (Step A-1), a silica hybrid urethane acrylate having a molecular weight of 15000 (manufactured by Aika Kogyo Co., Ltd .: high-molding pre-cure UV hard coat agent, product number Z606-61) Except that it was used, in the same manner as in Example 1, an uneven hard coat film of the present invention in which hairline unevenness was formed on the entire surface of the hard coat layer was obtained.

[Example 3]
In the same manner as in Example 1 except that the partial hairline film of the shaping material 2 was used instead of the hairline film of the shaping material 1 used in Example 1 (Step B-1), on the surface of the hard coat layer. A partially uneven hard coat film of the present invention in which hairline-like unevenness was partially formed was obtained.

[Example 4]
A partially uneven hard coat film in the same manner as in Example 1 except that the partial hairline film of the shaping material 3 was used instead of the hairline film of the shaping material 1 used in Example 1 (Step B-1). Thereafter, a step (E step) of washing and removing the water-based ink with water was further performed to obtain a partially uneven hard coat film of the present invention in which hairline-like unevenness was partially formed on the surface of the hard coat layer.

[Comparative Example 1]
In place of the silica hybrid urethane acrylate having a molecular weight of 20000 used in Example 1 (Step A-1), urethane acrylate (manufactured by Nippon Kayaku Co., Ltd .: UV curable hard coat agent, product number KAYANOVA FOP1700) was used. In the step of curing the ultraviolet curable resin of (C step) and transferring the hairline uneven pattern of the shaping material 1 to the surface of the hard coat layer, except that ultraviolet rays were irradiated from the hairline film (shaped material 1) side, In the same manner as in Example 1, an uneven hard coat film of Comparative Example 1 in which hairline-like unevenness was formed on the entire surface of the hard coat layer was obtained. (Equivalent to the laminate described in Patent Document 1)

[Comparative Example 2]
In the step of curing the ultraviolet curable resin of Example 1 and transferring the hairline uneven pattern of the shaping material 1 to the surface of the hard coat layer to form the hairline unevenness, ultraviolet rays are applied to the hairline film (shaped material). 1) An uneven hard coat film of Comparative Example 2 in which hairline unevenness was formed on the entire surface of the hard coat layer was obtained in the same manner as in Example 1 except that irradiation was performed from the side.

[Create decoration]
[Example 5]
The adhesive layer is laminated by coating an adhesive on the surface of the uneven hard coat film of the present invention obtained in Example 1 on which the hairline-like irregularities are not formed, and an adhesive layer having a thickness of 25 μm is laminated. After obtaining the uneven hard coat film, cut the uneven hard coat film to the same size as the seal label on the surface of the seal label on which the pattern has been printed in advance, and pass through the adhesive layer A sticker label was obtained by sticking to the seal label and sticking the concave-convex hard coat film as the decorative body of the present invention.

[Example 6]
The surface of the partially uneven hard coat film of the present invention obtained in Example 3 on which the hairline-like unevenness is not formed is coated with an adhesive and an adhesive layer having a thickness of 25 μm is laminated, and the adhesive layer is laminated. After obtaining the partially uneven hard coat film, cut the partially uneven hard coat film into a desired shape on the surface of the seal label on which the pattern has been printed in advance, and through the adhesive layer A seal label having a partially uneven hard coat film that is a decorative body of the present invention was obtained by sticking to a seal label.

[Example 7]
An adhesive layer having a thickness of 25 μm is laminated by coating an adhesive on the surface of the partially uneven hard coat film of the present invention obtained in Example 4 on which the hairline-like irregularities are not formed, and the adhesive layer is laminated. After obtaining the partially uneven hard coat film, cut the partially uneven hard coat film to the same size as the PC part on the surface of the PC part, and attach it to the PC part through the adhesive layer. A personal computer component to which a partially uneven hard coat film as a decorative body of the invention was attached was obtained.

[Example 8]
A black printing ink was used on the surface of the uneven hard coat film of the present invention obtained in Example 1 where the hairline-shaped unevenness was not formed, and a printing layer having a thickness of 8 μm was laminated on the figure by screen printing. After obtaining an uneven hard coat film with a printing layer, the uneven hard coat film with a printing layer is cut into the same size as the mobile phone part on the surface of the mobile phone part, and the printing is performed via a double-sided tape having a thickness of 50 μm. The cellular phone part was obtained by being attached to the cellular phone part so that the layer and the surface of the cellular phone part were in contact with each other, and the concavo-convex hard coat film with a printed layer, which is a decorative body of the present invention.

[Hard coat test]
(Test sample)
The concavo-convex hard coat film of the present invention obtained in Examples 1 to 4, the partially concavo-convex hard coat film, and the concavo-convex hard coat film obtained in Comparative Example 1 are formed into a 5 cm × 15 cm rectangle (the hairline direction is parallel to the short side). Five cuts were prepared and used as test samples.
(Measuring method)
Each test sample is tested in accordance with JIS K 5400-5-4 method (pencil scratch test method) in the direction perpendicular to the hairline direction of the hairline irregularities on the surface of the hard coat layer, and scratched with a pencil hardness of H. The hard coat properties are compared, ◎ if all five test samples are not scratched, ◎, if one or two test samples are scratched, ○, if more than three test samples Those with scratches were marked with ×. (Example 3 and Example 4 measured hairline-shaped uneven portions.)
(Test results)
Table 1 shows.

[Abrasion resistance test]
(Test sample)
The concavo-convex hard coat film of the present invention obtained in Examples 1 to 4, the partially concavo-convex hard coat film, and the concavo-convex hard coat film obtained in Comparative Example 1 are formed into a 3 cm × 20 cm rectangle (the hairline direction is parallel to the short side). One cut sample was prepared for each test sample.
(Measuring method)
Apply a load of 800 g to steel wool (# 0000) with the surface of each hard coat layer attached to a fixed terminal, and the test sample is 20 cm long in a direction perpendicular to the hairline direction of the hairline irregularities on the surface of the hardcoat layer. After reciprocating 20 times, the condition of the surface of the hard coat layer was confirmed, and the scratch resistance was visually compared. If the scratch was not observed on the surface of the hard coat layer, ◎, slightly scratched Was marked with ◯, and when many scratches were observed and the appearance of the hard coat film became white, x was marked. (Example 3 and Example 4 measured hairline-shaped uneven portions.)
(Test results)
Table 1 shows.

[Curl resistance test]
(Test sample)
The uneven | corrugated hard coat film of this invention obtained in Examples 1-4, the partially uneven | corrugated hard coat film, and the uneven | corrugated hard coat film obtained in Comparative Example 1 were each cut into a square of 5 cm × 5 cm to produce one sheet. A test sample was obtained.
(Measuring method)
Each test sample was left in an oven at 80 ° C. for 24 hours with the hard coat layer facing up, and then placed gently on a flat and horizontal measuring table with the hard coat layer facing up, and the four corners of the test sample were measured. Measure the height from the table (height of the warp) and compare the curl resistance. If the height of the warp of all four corners of the test sample is 1mm or less, the height of the warp is one of the four corners. What was 1 mm or more was set as x.
(Test results)
Table 1 shows.

As shown in Table 1, the concavo-convex hard coat film and the partially concavo-convex hard coat film of the present invention obtained in Examples 1 to 4, respectively, are the results of the hard coat property test and the scratch resistance test on the surface of the hard coat layer. The uneven hard coat film and the partially uneven hard coat film of the present invention obtained in Example 1, Example 3 and Example 4 were scratched on the surface of the hard coat layer in both the hard coat property test and the scratch resistance test. There were no defects on the surface and unevenness, and the hard coat property and scratch resistance were excellent.
Further, the uneven hard coat film of the present invention obtained in Example 2 was scratched on one of the five test samples in the hard coat property test, and a slight scratch was confirmed in the scratch resistance test. Scratches on the surface of the hard coat layer did not impair the design properties and were at a level causing no practical problems.
In contrast to the above results, the uneven hard coat film obtained in Comparative Example 1 was scratched on three of the five test samples in the hard coat property test, and many scratches were found on the hard coat layer surface in the scratch resistance test. As a result, the appearance was white, and irregularities and defects were observed on the surface of the hard coat layer, and the design was remarkably impaired, and the hard coat properties and scratch resistance were poor.

Moreover, also in curl resistance, the uneven | corrugated hard coat film of this invention obtained in Examples 1-4 and the partial uneven | corrugated hard coat film were respectively the height of the curvature of all the four corners of a test sample as a result of a curl resistance test. 1 mm or less, and the uneven hard coat film itself maintained a substantially flat state without curling and was excellent in curling resistance, whereas the uneven hard coat film obtained in Comparative Example 1 had a curl resistance As a result of the property test, the height of warpage was 5 mm at all four corners of the test sample, and the uneven hard coat film itself was curled and inferior in curling resistance.

[Adhesion test]
(Test sample)
Each of the concavo-convex hard coat film and the partially concavo-convex hard coat film obtained in Examples 1 to 4 and Comparative Example 2 was cut into a 10 cm × 10 cm square to prepare a test sample.
(Measurement content)
In accordance with JIS K 5600-5-6 method (adhesion-cross-cut method / 100 mass), the test sample was measured for the adhesion between the polyethylene terephthalate film and the hard coat layer, and the hard coat layer was completely peeled off. The case where there was no peeling and the case where the hard coat layer was peeled off were marked as x. (Example 3 and Example 4 measured hairline-shaped uneven portions.)
(Test results)
It shows in Table 2.

As shown in Table 2, the concavo-convex hard coat film and partial concavo-convex hard coat film of the present invention obtained in Examples 1 to 4 showed no peeling of the hard coat layer as a result of the adhesion test, and the polyethylene terephthalate film and the hard coat. The concavo-convex hard coat film obtained in Comparative Example 2 was peeled off from the hard coat layer of 30 squares out of 100 squares, whereas the polyethylene terephthalate film and the hard coat layer were strong against the adhesive layer. The adhesion with was weak.

The seal label to which the uneven hard coat film which is the decorative body of the present invention obtained in Example 5 is attached is the effect of the present invention that the uneven hard coat film of the present invention obtained in Example 1 has. In addition to the seal label before sticking the uneven hard coat film of the present invention, in addition to the pattern pre-printed on the seal label, the entire surface of the uneven hairline film of the present invention is retained. The hairline-shaped irregularities were formed, and there was a high-class feeling and could be fully differentiated.

The seal label on which the partially uneven hard coat film, which is the decorative body of the present invention, obtained in Example 6 is attached, and the partially uneven hard coat film of the present invention obtained in Example 3 has the present invention. In addition to the pattern pre-printed on the seal label, the present invention has a desired shape as compared with the seal label before applying the partially uneven hard coat film of the present invention. The hairline-like unevenness of the partially uneven hairline film was formed and had a high-class feeling and could be sufficiently differentiated.

The personal computer part on which the partially uneven hard coat film, which is the decorative body of the present invention, obtained in Example 7 has the effect that the partially uneven hard coat film of the present invention obtained in Example 4 has. Compared with the PC parts before holding the partially uneven hard coat film of the present invention, the hairline shape of the partially uneven hairline film of the present invention in addition to the color that the PC parts had The unevenness was formed, and there was a high-class feeling and could be sufficiently differentiated.

The cellular phone part to which the uneven hard coat film with a printing layer which is the decorative body of the present invention obtained in Example 8 is attached has the uneven hard coat film of the present invention obtained in Example 1. It retains all of the effects, and compared with the mobile phone part before the application of the uneven hard coat film with printed layer of the present invention, the uneven hairline film of the present invention has a hairline-like unevenness on the entire surface of the mobile phone part. Further, the printed layer having a figure shape has a high-class feeling and can be sufficiently differentiated.

Claims (12)

A concavo-convex hard coat film, characterized in that a hard coat film made of an ultraviolet curable resin is laminated on at least one surface of a plastic film, wherein the following conditions (1) and (2) are satisfied.
(1) The ultraviolet curable resin is a silica hybrid type urethane acrylate. (2) The surface of the hard coat layer is uneven.   2. The uneven hard coat film with a cover material according to claim 1, wherein a cover material is laminated on the hard coat layer. A method for producing an uneven hard coat film with a shaping material,
(Step A-1) A step of laminating a hard coat layer made of an ultraviolet curable resin on at least one surface of a plastic film,
(Step B-1) A step of laminating a shaping material having a concavo-convex pattern on at least one surface on the hard coat layer so that the concavo-convex pattern surface is in contact with the hard coat layer,
(C step) a step of irradiating the ultraviolet ray to cure the ultraviolet curable resin, transferring the concavo-convex pattern of the shaping material to the surface of the hard coat layer to form the concavo-convex;
The steps of (A-1 step), (B-1 step), and (C step) are carried out in this order, and the ultraviolet curable resin is a silica hybrid type urethane acrylate. Film production method. A method for producing an uneven hard coat film with a shaping material,
(Step A-2) A step of forming a hard coat layer made of an ultraviolet curable resin on the concavo-convex pattern surface of the shaping material having a concavo-convex pattern on at least one side,
(Step B-2) A step of laminating a plastic film on the hard coat layer,
(C step) a step of irradiating the ultraviolet ray to cure the ultraviolet curable resin, transferring the concavo-convex pattern of the shaping material to the surface of the hard coat layer to form the concavo-convex;
The steps of (A-2 step), (B-2 step), and (C step) are carried out in this order, and the ultraviolet curable resin is a silica hybrid type urethane acrylate. Film production method. 5. The method for producing a concavo-convex hard coat film with a shaping material according to claim 3 or 4, wherein ultraviolet rays are irradiated from the plastic film side when the ultraviolet curable resin is cured.   A method for producing a hard coat film with a shaping material according to any one of claims 3 to 5, further comprising (D step) a step of removing the shaping material. Production method.   An uneven hard coat film with a shaping material, produced by the production method according to claim 3.   An uneven hard coat film produced by the production method according to claim 6.   A decorative body characterized in that a surface on which the unevenness of the uneven hard coat film according to claim 1 is not formed is attached to a surface of an adherend.   A decorative body characterized in that a surface on which the unevenness of the concavo-convex hard coat film with a cover material according to claim 2 is not formed is adhered to the surface of an adherend.   A decorative body characterized in that the surface of the surface of the adherend on which the unevenness of the uneven hard coat film with shaping material is not formed is attached.   A decorative body, wherein a surface of the surface of the adherend on which the unevenness of the uneven hard coat film is not formed is attached.