JP2021070300A - Decorative film, method for producing decorative film, decorative molding, and method for producing decorative molding - Google Patents

Abstract

To provide a decorative film which enables preforming when being stuck to a three-dimensional molding, facilitates modification of a stuck position, and has good adhesion performance after sticking, a method for producing a decorative film, a decorative molding, and a method for producing a decorative molding.SOLUTION: There are provided a decorative film that has a skin layer, a base material layer, an adhesive layer and an adhesive layer protective sheet in this order, in which the adhesive layer is an adhesive layer or a hot-melt adhesive containing at least one selected from ethylene-vinyl acetate, an acrylic resin, an urethane resin, an olefin resin and polyester, has a thickness of 10 μm-80 μm, and has an initial peeling strength obtained by peeling the adhesive layer protective sheet from the decorative film, sticking it to a stainless steel plate, and measuring it according to 180° peeling test of an adhesive tape according to JIS Z 0237 (2009) of 0.1 N/cm to 5 N/cm, and is used in decoration of a three-dimensional molding; and its application.SELECTED DRAWING: Figure 1

Description

The present disclosure relates to a decorative film, a method for producing a decorative film, a decorative molded product, and a method for producing a decorative molded product.

Decorative films for changing the appearance of a vehicle such as an automobile or giving a desired design to the vehicle are known. By attaching a decorative film to the roof, side of the body, etc. of an automobile, it is possible to easily give a design without painting, and it is possible to easily change the appearance of the vehicle, which is attracting attention. There is.
Various decorative films for vehicle exteriors have been proposed, and there are commercially available products, but most of them are films in which a flexible decorative film is attached while following the shape of the vehicle, and such a film is applied to the vehicle. It took skill to adapt it to the three-dimensional shape and paste it without spoiling the appearance.

Therefore, for the purpose of improving the stickability to the vehicle exterior having a three-dimensional shape, a decorative film having a release layer, an adhesive layer, and a skin layer, and the release layer having a shape-retaining layer has been proposed. (See Patent Document 1 and Patent Document 2). Since the release layer of the decorative film includes a shape-retaining layer, the decorative film can be preformed in advance according to the three-dimensional shape of the adherend, and the preformed decorative film can be decorated in a flat shape. Compared to a film, it is said that it is easier to align with the unevenness of the surface of the adherend.
When the decorative film that can be preformed is attached to the adherend, it is preformed and trimmed, and the release layer is peeled off from the decorative film and attached to the adherend. Generally, when the decorative film is attached to the adherend, at least the surface of the adherend and the surface of the decorative film on the side having the adhesive layer are at least for the purpose of facilitating the correction of the attachment position to the adherend. Water is sprayed on either.

The peeling layer is peeled off, and the decorative film sprayed with water is placed on the surface of the adherend and aligned, and then the adherend and the adhesive layer in the decorative film are brought into close contact with each other while extruding water with a squeegee. .. When the adherend has fine irregularities such as a bead shape, water may stay between the decorative film and the slight recesses of the adherend, and it may be difficult to completely push out the water.
If water remains between the adherend and the decorative film, there is a concern that the remaining portion of the water may swell over time and the appearance may be significantly impaired.
On the other hand, when the decorative film is attached to the adherend without spraying water, it is difficult to peel off the decorative film from the once arranged position and correct the attached position. Furthermore, if the sticking position is corrected, slight wrinkles may occur due to the stress associated with the decorative film, and there is a concern that the surface of the molded product may have gloss unevenness due to fine wrinkles of the decorative film, resulting in poor appearance. is there.

Japanese Unexamined Patent Publication No. 2016-198900 Japanese Unexamined Patent Publication No. 2016-203434

The decorative films described in Patent Documents 1 and 2 are provided with a shape-retaining layer as a release layer, and by pre-molding the decorative film, a film having a shape more suitable for the three-dimensional shape of the adherend can be obtained in advance. However, when the release layer is peeled off when the film is attached to the molded body, the shape-retaining layer is also peeled off together with the release layer, the obtained sheet is not rigid, and the film itself is flexible and easily deformed. Therefore, when the decorative films described in Patent Documents 1 and 2 are attached to the three-dimensional molded body, if water is not sprayed, the adherend is decorated without leaving air. It is difficult to attach the film. Further, in the decorative films described in Patent Document 1 and Patent Document 2, gloss unevenness is likely to occur when the position is corrected once the film is attached, and there is still room for improvement from the viewpoint of workability.

An object of an embodiment of the present invention is that pre-molding is possible when affixed to a three-dimensional molded body, and the affixing position can be easily corrected even when affixed to a molded body by a dry method. It is an object of the present invention to provide a decorative film having good adhesion performance after sticking and a method for producing the decorative film.
Another object of another embodiment of the present invention is to provide a decorative molded article having a good appearance and a method for producing the decorative molded article, in which the surface of the molded article having a three-dimensional shape is decorated with a decorative film. It is to be.

Means for solving the problem include the following embodiments.
<1> The skin layer, the base material layer, the adhesive layer, and the adhesive layer protective sheet are provided in this order.
The adhesive layer contains an adhesive or hot melt adhesive containing at least one selected from ethylene vinyl acetate, acrylic resin, urethane resin, olefin resin, polyester, polyamide, and synthetic rubber, and has a thickness of 10 μm to 80 μm. The adhesive layer has an initial peel strength in the range of 0.1 N / cm to 5 N / cm measured by the following test method (I).
A decorative film used to decorate a molded product having a three-dimensional shape.
(Test method (I))
The adhesive layer protective sheet is peeled off from the decorative film, attached to a stainless steel plate, and the peeling strength is measured according to the 180 ° peeling test of the adhesive tape specified in JIS Z 0237 (2009).
<2> The decorative film according to <1>, which has a shape-retaining layer on a surface of the adhesive layer protective sheet opposite to the side having the adhesive layer.
<3> The decorative film according to <1> or <2>, which has irregularities fitted to the adhesive layer on the side of the adhesive layer protective sheet in contact with the adhesive layer.

<4> The decorative film according to any one of <1> to <3>, wherein the adhesive layer has a peel strength of 7 N / cm or more after a lapse of time measured by the following test method (II).
(Test method (II))
The adhesive layer protective sheet is peeled off from the decorative film, attached to a stainless steel plate, held at 20 ° C. for 24 hours, and then peeled strength according to the 180 ° peeling test of the adhesive tape specified in JIS Z 0237 (2009). To measure.

<5> The decorative film according to any one of <1> to <4>, wherein the base material layer contains a polyvinyl chloride resin.
<6> The adhesive layer protective sheet contains at least one resin selected from polypropylene (PP), polyethylene terephthalate (PET), polyethylene naphthalate (PEN) and polyethylene (PE), <1> to <5>. The decorative film according to any one of the above.
<7> The decorative film according to any one of <1> to <6>, which can be heat-molded.

<8> A step of preparing a skin layer containing a fluororesin, a step of forming a base material layer containing a polyvinyl chloride resin using a resin composition containing a polyvinyl chloride resin, and a step of forming the base material layer of the base material layer. An adhesive or hot melt adhesive containing at least one selected from ethylene vinyl acetate, acrylic resin, urethane resin, olefin resin, polyester, polyamide, and synthetic rubber is contained on the surface opposite to the side having the layer. A step of forming an adhesive layer having a thickness of 10 μm to 80 μm, a step of preparing an adhesive layer protective sheet, a step of bringing the adhesive layer protective sheet into contact with the adhesive layer, and covering the adhesive layer with the adhesive layer protective sheet. A method of manufacturing a decorative film, including steps.
<9> Further, a step of forming a shape-retaining layer using a thermoplastic resin composition containing at least one resin selected from an acrylonitrile / butadiene / styrene copolymer and a polyvinyl chloride resin, and obtained. The method for producing a decorative molded article according to <8>, which comprises a step of adhering a shape-retaining layer to a side of the adhesive layer protective sheet opposite to the adhesive layer side via an adhesive.
<10> The step of preparing the adhesive layer protective sheet includes a step of embossing the resin sheet to prepare an adhesive layer protective sheet having irregularities to be fitted to the adhesive layer, <8> or <9>. > The method for manufacturing a decorative film.

<11> A decorative molded body having a molded body having a three-dimensional shape and a decorative laminated body in which the adhesive layer protective sheet is peeled off from the decorative film according to any one of <1> to <7>. ..

<12> The step of pre-molding the decorative film according to any one of <1> to <7> into a shape suitable for the shape of the molded body to which the decorative film is attached by a vacuum molding method. The step of peeling off the adhesive layer protective sheet of the decorative film, the decorative laminate derived from the decorative film from which the adhesive layer protective sheet has been peeled off, has a three-dimensional shape via the adhesive layer of the decorative laminate. A method for producing a decorative molded article, which comprises a step of attaching to the surface of the molded article and a step of pressing the decorative laminate attached to the surface of the molded article.
<13> The method for producing a decorative molded body according to <12>, further comprising a step of heating the decorative laminated body attached to the surface of the molded body.

According to an embodiment of the present invention, pre-molding is possible when sticking to a three-dimensional molded body, and even when sticking to a molded body by a dry method, it is easy to correct the sticking position, and It is possible to provide a decorative film having good adhesion performance after sticking and a method for producing the decorative film.
Further, according to another embodiment of the present invention, there is provided a decorative molded article having a good appearance and a method for producing the decorative molded article, in which the surface of the molded article having a three-dimensional shape is decorated with a decorative film. can do.

It is the schematic sectional drawing which shows one aspect of the decorative film of this disclosure. FIG. 5 is a schematic cross-sectional view showing an aspect of a state in which the adhesive layer protective sheet and the shape-retaining layer are peeled off from the decorative film of the present disclosure shown in FIG. It is the schematic sectional drawing which shows one aspect of the decorative molded article of this disclosure.

Hereinafter, the decorative film of the present disclosure, the method for producing the decorative film, the method for producing the decorative molded body, and the decorative molded body will be described in detail.
The description of the components described below may be based on the representative embodiments of the present disclosure, but the present disclosure is not limited to such embodiments.
In the present disclosure, "~" indicating a numerical range is used to mean that the numerical values described before and after the numerical range are included as the lower limit value and the upper limit value.
In the numerical range described stepwise in the present disclosure, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of another numerical range described stepwise. Further, in the numerical range described in the present disclosure, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples.
In the present disclosure, the combination of preferred embodiments is a more preferred embodiment.
In the present disclosure, the amount of each component in the composition is the total amount of the plurality of substances present in the composition unless otherwise specified, when a plurality of substances corresponding to each component are present in the composition. means.
In the present disclosure, the term "process" is included in this term not only as an independent process but also as long as the intended purpose of the process is achieved even if it cannot be clearly distinguished from other processes.

The "layer containing a resin" in the present disclosure refers to a "layer formed containing a resin which is a main component of the layer". That is, the "layer containing a resin" in the present disclosure is a resin composition containing only a resin and an optional component such as a plasticizer, a colorant, and an ultraviolet absorber in addition to the resin as the main component. It is used to include both of the formed layers.
The "resin as the main component" in the present disclosure refers to a resin contained in an amount of 60% by mass or more with respect to the total amount of the resin composition containing the component.
Hereinafter, in the present disclosure, the polyvinyl chloride resin may be referred to as a PVC resin. Further, the acrylonitrile / butadiene / styrene copolymer may be referred to as ABS resin.
Further, in the present disclosure, the "molded body having a three-dimensional shape" or the "molded body" refers to a molded body (base of the molded body) before decoration, and the "decorative molded body" is the decoration of the present disclosure. Refers to a molded product decorated with a film.
In the present disclosure, the side having the skin layer of the decorative film may be referred to as a front surface, and the side having an adhesive layer may be referred to as a back surface, respectively.
A laminate having a skin layer, a base material layer, and an adhesive layer, which is used for attaching the adhesive layer protective sheet from the decorative film to an adherend, is referred to as a decorative laminate.
When the adhesive layer protective sheet is peeled from the decorative film, it is peeled off at the interface between the adhesive layer and the adhesive protective sheet. Therefore, even when the decorative film has a shape-retaining layer as an arbitrary layer, it is peeled off at the interface between the adhesive layer and the adhesive protective sheet, and the shape-retaining layer adjacent to the adhesive layer protective sheet is the adhesive layer protective sheet. It is peeled off at the same time. Therefore, by peeling off the adhesive layer protective sheet, a decorative laminate having a skin layer, a base material layer, and an adhesive layer can be obtained.
Even if not only the shape-retaining layer but also any other layer is provided on the surface of the adhesive layer protective sheet opposite to the surface in contact with the adhesive layer, the adhesive layer protective sheet can be peeled off from the adhesive layer. Layer is also peeled off at the same time.

The decorative film of the present disclosure has a skin layer, a base material layer, an adhesive layer, and an adhesive layer protective sheet in this order, and the adhesive layer includes ethylene vinyl acetate, acrylic resin, urethane resin, and olefin. It contains a pressure-sensitive adhesive or hot-melt adhesive containing at least one selected from resin, polyester, polyamide, and synthetic rubber, has a thickness of 10 μm to 80 μm, and is initially peeled as measured by the above test method (I). It is a decorative film that is an adhesive layer having a strength in the range of 0.1 N / cm to 5 N / cm, and is used for decorating a molded body having a three-dimensional shape.
It is preferable that the adhesive layer protective sheet has irregularities fitted to the adhesive layer on the side in contact with the adhesive layer from the viewpoint that it is easier to correct the sticking position.

By having the adhesive layer protective sheet in the decorative film of the present disclosure, premolding suitable for the surface shape of the molded body to be decorated by the decorative film can be performed, and after the premolding, the adhesive layer protective sheet is used. The decorative laminate obtained by peeling can be easily attached to the molded body.
The adhesive layer of the decorative film contains an adhesive or hot melt adhesive containing at least one selected from ethylene vinyl acetate, acrylic resin, urethane resin, olefin resin, polyester, polyamide, and synthetic rubber. The initial adhesiveness when affixed to the surface of a hard molded body is specifically suppressed to a low range of 0.1 N / cm to 5 N / cm in the initial peel strength measured by the above test method (I). , The obtained decorative laminate can be easily reattached. Further, when the thickness of the adhesive layer is in the range of 10 μm to 80 μm, deformation such as elongation of the decorative laminate during reattachment is suppressed, and even when slight irregularities are present on the surface of the molded body. , It is easy to absorb the unevenness.

One preferred embodiment of the decorative film is an aspect in which the shape-retaining layer is provided on the surface of the adhesive layer protective sheet opposite to the side having the adhesive layer. By having the shape-retaining layer adjacent to the adhesive layer protective sheet, the preformability of the decorative film becomes better. Details of the shape-retaining layer will be described later.

In another preferred embodiment of the decorative film, the presence of irregularities on the surface of the adhesive layer protective sheet allows the adhesive layer in the decorative laminate after the adhesive layer protective sheet to be peeled off to adhere to the adhesive layer. Due to the unevenness of the layer protective sheet, the uneven shape is transferred to the adhesive layer protective sheet side. Then, the adhesive layer having irregularities has a smaller contact area when bonded to the surface of the molded body and has lower adhesiveness than the adhesive layer having no irregularities, so that the adhesive layer can be easily reattached. Can be done.
As described above, the adhesive layer is a pressure-sensitive adhesive or hot-melt adhesive containing a specific polymer compound, and when the decorative film is attached to the molded product and positioning is completed, it is pressed to adhere to the adhesive layer. The property is improved and it is stably fixed to the surface of the molded product. Further, since the thickness of the adhesive layer is in the range of 10 μm to 80 μm, even if the adhesive layer has irregularities, the irregularities are pressed by pressure, and the adhesive layer is deformed to follow the shape of the surface of the molded product. It is believed that stable adhesion can be obtained by increasing the contact area.
When the adhesive layer contains a hot melt adhesive, it is preferable to further heat the decorative molded product bonded to the molded product in order to achieve more stable adhesion.
By using the decorative film of the present disclosure, a decorative laminate derived from the decorative film can be easily attached to a molded body having a three-dimensional shape without spraying water or the like by a dry method. The position after bonding can be easily corrected, and stable adhesion is achieved by pressurizing the decorative laminate after positioning.

Needless to say, the decorative film of the present disclosure can also be applied to water pasting, which is adhered to a molded product by spraying water. Even in the case of watering, the initial adhesiveness of the decorative laminate to the molded body is suppressed to a low level, and positioning is easy. Furthermore, by pressurizing the decorative laminate after positioning, between the adhesive layer and the molded body. The water remaining in the decorative laminate is quickly drained from the end of the decorative laminate, the water residue after application is suppressed, and high adhesion due to pressurization is achieved.
By pressurizing the decorative laminate after positioning, for example, even if the adhesive layer has irregularities, the adhesive layer becomes the shape of the surface of the molded body due to the stress when the decorative laminate is pressed against the molded body and pressed. It is deformed to follow and the uneven shape is smoothed, the contact area between the adhesive layer and the molded body becomes larger, and high adhesion is obtained by the action of intermolecular force.
By using the decorative film of the present disclosure, for example, the appearance of a vehicle such as an automobile can be easily changed, and various designs are applied to the surfaces of various molded bodies having a three-dimensional shape, resulting in excellent appearance. It becomes possible to easily manufacture a decorative molded product.

Hereinafter, the decorative film of the present disclosure, the method for producing the decorative film, the method for producing the decorative molded product, and the preferred embodiment of the decorative molded product will be described in detail. However, the present disclosure is not limited to the following embodiments.

<Decorative film>
The decorative film of the present disclosure has a skin layer, a base material layer, an adhesive layer, and an adhesive layer protective sheet in this order, and the adhesive layer is ethylene vinyl acetate, acrylic resin, urethane resin, or olefin resin. , A pressure-sensitive adhesive or a hot-melt adhesive containing at least one selected from polyester, polyamide, and synthetic rubber, having a thickness of 10 μm to 80 μm, and having an initial peel strength measured by the above test method (I). It is an adhesive layer in the range of 0.1 N / cm to 5 N / cm.
From the viewpoint of improving the preformability, the decorative film of the present disclosure preferably has a shape-retaining layer on the surface of the adhesive layer protective sheet opposite to the side having the adhesive layer.

The decorative film of the present disclosure will be described with reference to FIG. FIG. 1 is a schematic cross-sectional view showing a preferred embodiment of the layer structure of the decorative film 10 of the present disclosure.
The decorative film 10 has a skin layer (hereinafter, appropriately referred to as a skin layer) 12 having irregularities on one surface and a base material layer (hereinafter, hereinafter referred to as a base layer) provided on a surface opposite to the surface having irregularities on the skin layer. , Appropriately referred to as a base material layer) 14, an adhesive layer 18, an adhesive layer protective sheet 20 for covering the adhesive layer 18, and a shape-retaining layer 22 in this order.
The adhesive layer protective sheet 20 has irregularities fitted to the adhesive layer on the side in contact with the adhesive layer. As described above, the unevenness of the adhesive layer protective sheet is provided as desired, and the adhesive layer protective sheet does not necessarily have to have the unevenness.
As shown in FIG. 1, since the adhesive layer protective sheet has irregularities, irregularities are formed on the adjacent adhesive layer by transfer, and the adhesive layer after the adhesive layer protective sheet is peeled off and the adherend. The contact area with the surface of the molded body becomes smaller, and it becomes easier to correct the position of the decorative laminated body.
"Having each layer in this order" means that each layer exists in the order described, and does not deny the existence of any layer further provided as needed.
That is, in FIG. 1, a primer layer 16 which is a resin layer for improving the adhesiveness between the base material layer 14 and the adhesive layer 18 is provided, and the primer layer 16 is an arbitrary layer provided as desired. is there. Further, in FIG. 1, the shape-retaining layer 22 is provided adjacent to the adhesive layer protective sheet 20, and the shape-retaining layer 22 is an arbitrary layer provided as desired in order to further improve the preformability of the decorative film. is there.
In one embodiment of the decorative film 10 shown in FIG. 1, it is adhered to a laminate (decorative laminate) 24 having a skin layer 12, a base material layer 14, a primer layer 16, and an adhesive layer 18 in that order. It has a structure having a layer protection sheet 20 and a shape-retaining layer 22. As shown in FIG. 1, the surface of the skin layer 12 opposite to the base material layer 14 side may have an uneven pattern, which is also called a grain pattern.
On the side having the uneven pattern of the skin layer, when the decorative laminated body 24 in which the adhesive layer protective sheet 20 and the shape-retaining layer 22 are peeled off from the decorative film 10 is arranged in a molded body described later, the decorative molded body is formed. Since it is located on the outermost surface, it may be referred to as a surface below. The uneven pattern is a pattern that characterizes the appearance of the surface of the molded product made of the decorative film, which is typified by the uneven pattern like natural leather, and is provided as needed.
Further, the base material layer 14 can impart an arbitrary hue to the decorative film 10 by containing, for example, a colorant. Therefore, a desired hue can be easily imparted to the decorative molded product to which the decorative film 10 of the present disclosure is applied.
In addition, in FIG. 1, FIG. 2A and FIG. 2B, the constituent elements shown by using the same reference numerals mean that they are the same constituent elements.

Hereinafter, the decorative film will be sequentially described together with the materials constituting the decorative film and the manufacturing method thereof.

(1. Epidermis layer)
The epidermis layer of the decorative film is formed of resin. Above all, the epidermis layer preferably contains a fluororesin. When the skin layer contains a fluororesin, the durability of the decorative film is improved, and if desired, the uneven pattern retention property is formed when the uneven pattern is formed on the surface opposite to the base material layer side. Is improved.

The fluororesin that can be used for the skin layer is not particularly limited as long as it is a resin obtained by polymerizing at least one monomer containing a fluorine atom as a polymerization component, but an olefin containing a fluorine atom is polymerized. The resulting resin is preferred.
Examples of the fluororesin include a resin composed of a polymerization component selected from ethylene tetrafluoride, ethylene trifluoride, vinyl fluoride, and vinylidene fluoride. More specifically, a homopolymer of a polymer component containing a fluorine atom such as ethylene tetrafluoride resin, vinyl fluoride resin, and vinylidene fluoride resin, and a copolymer containing the polymer component, chloride trifluoride. Examples thereof include ethylene-vinylidene fluoride copolymer, vinylidene fluoride-6 propylene fluoride copolymer, vinylidene fluoride-6 propylene fluoride-4 ethylene fluoride copolymer and the like. Among them, from the group consisting of ethylene trifluorochloride-vinylidene fluoride copolymer, vinylidene fluoride-6 propylene fluoride copolymer, and vinylidene fluoride-6 propylene fluoride-4 ethylene fluoride copolymer. It is preferable to contain at least one selected fluororesin.

When the epidermis layer contains a fluororesin, only one type of fluororesin may be contained, or two or more types may be used in combination.
When the skin layer contains two or more kinds of fluororesins, for example, vinylidene fluoride resin, ethylene trifluorochloride-vinylidene fluoride copolymer, vinylidene fluoride-6 propylene fluoride copolymer, and fluoride It is also a preferable embodiment to use a mixture of two or more kinds of resins selected from the group consisting of vinylidene-6 propylene fluoride-4 ethylene fluoropolymer.

When the skin layer contains two or more kinds of resins, in addition to the aspect of being a mixture of two or more kinds of resins as described above, the form of a laminated structure of two or more kinds of resins can be taken. For example, as the skin layer, the outermost surface, that is, the surface corresponding to the outside when the decorative film is placed on the molded body is made into a layer containing a fluororesin to further improve the adhesiveness between the skin layer and the base material layer. For the purpose, the epidermis layer has a two-layer structure of a layer containing a fluororesin and a layer containing an acrylic resin, and the layer side containing the acrylic resin can be positioned on a surface in contact with the base material layer.

The skin layer may be formed by a known sheet molding method, for example, an extrusion method of extrusion molding with a T-die, a calendar method, a casting method, or the like, or a commercially available film may be applied to form the skin layer.

The thickness of the epidermis layer is preferably in the range of 5 μm to 100 μm, more preferably in the range of 10 μm to 60 μm, from the viewpoint of strength and the unevenness pattern retention when the uneven pattern is formed.
Here, the thickness of the epidermis layer refers to the distance from the top of the convex portion of the surface on which the uneven pattern is formed to the bottom surface of the epidermis layer.
The thickness of the epidermis layer is based on the distance between the bottom and the top of the convex portion at the deepest part of the concave and convex pattern recess, from the viewpoint of retaining the uneven pattern formed on the side opposite to the surface of the epidermis layer on the base material layer side. Is also preferable. For example, when forming an uneven pattern such that the depth of the recess is 1 μm or less, the thickness of the epidermis layer can be about 5 μm, and there are shallow recesses and deep recesses like a natural leather-like pattern. However, when the deep recess is 2 μm to 5 μm, the thickness of the epidermis layer is preferably 10 μm or more.
The thickness of the epidermis layer when the epidermis layer has a laminated structure of two or more layers as described above refers to the total thickness of the plurality of layers.
The thickness of each layer in the decorative film of the present disclosure can be measured by observing a cut surface obtained by cutting the decorative film perpendicularly to the surface direction. Therefore, the film thickness of each layer in the decorative film in the present disclosure refers to the film thickness after drying.

The method of forming the epidermis layer on the surface of the base material layer opposite to the surface on the adhesive layer side is arbitrary. For example, the preformed skin layer and the base material layer may be adhered to each other, or the base material layer may be formed on one surface of the skin layer after the skin layer is formed.

Further, the method of forming the uneven pattern on the surface of the epidermis layer opposite to the surface on the base material layer side is not particularly limited, and a known method can be applied. Known methods include a method of forming an epidermis layer on a release paper having an uneven pattern, a method of first forming an epidermis layer having a smooth surface, and then a method of embossing using a drawing roll.

(2. Base material layer)
The base material layer is formed of resin. The base material layer preferably contains a PVC resin as the resin.
When the base material layer contains the PVC resin, the thermal stress related to the epidermis layer is relaxed, and the retention of the uneven pattern desired to be formed on the epidermis layer becomes better.
The PVC resin is not particularly limited, and a known film-forming PVC resin can be appropriately selected and used.

The base material layer may contain other components in addition to the PVC resin as a preferable resin. Other components that the substrate layer may contain include colorants, plasticizers, fillers, lubricants, processing aids and the like. The other components can be used within a range that does not reduce the thermal processability of the base material layer.

The base material layer can contain a colorant.
When the base material layer contains a colorant, in the area where the decorative laminate is attached, the hue, design, etc. originally possessed by the molded body, which is the adherend base, of the decorative molded body can be obtained in the area where the decorative laminated body is attached. It is possible to suppress the influence on the appearance and impart an arbitrary hue to the decorative laminate derived from the decorative film, and by extension, the decorative molded product to which the decorative laminate is attached.
When the skin layer contains a fluororesin and has good transparency, the hue of the base material layer can characterize the appearance of the decorative film by containing a colorant in the base material layer.
For example, the adhesive layer protective sheet is peeled off from the decorative film by using a decorative film having a base material layer containing a silver colorant having a different hue only on the roof portion of the red vehicle as a molded body. By pasting the decorative laminate on the roof of the vehicle and decorating it, the car body is red, only the roof on which the decorative laminate is pasted becomes a silver vehicle, and the place where the decorative laminate is pasted is The red color, which is the original hue of the molded product, is hidden.

When the base material layer contains a colorant, the colorant is not particularly limited, and dyes, pigments and the like can be appropriately selected and used.
Coloring agents include inorganic pigments such as titanium white (titanium dioxide), zinc flower, ultramarine blue, cobalt blue, petals, vermilion, yellow lead, titanium yellow, and carbon black, quinacridone, permanent red 4R, isoindolinone, and Hansa yellow. From organic pigments or dyes such as A, phthalocyanine blue, induslen blue RS, and aniline black, metal pigments selected from the group consisting of metal foil powders such as aluminum and brass, titanium dioxide-coated mica and basic lead carbonate foil powder. Examples thereof include pearl luster (pearl) pigments selected from the above group. Of these, pigments, which are colorants having excellent weather resistance and durability, are preferable, and black pigments such as carbon black, aniline black, and perylene black are more preferable from the viewpoint of being able to effectively conceal the molded product.
Further, the base material layer may contain an extender pigment (filler) such as calcium carbonate, silica (carbon dioxide), alumina (aluminum oxide), and barium sulfate, if necessary.

When the base material layer contains a colorant, only one type of colorant may be contained, or two or more types may be contained for the purpose of toning or the like.
The content of the colorant in the resin composition used for forming the base material layer is not particularly limited, and the type and content of the colorant to be used are determined according to the desired hue in the decorative film, the hiding property of the molded product, and the like. The amount and the like may be appropriately selected.
When a colorant is used, the content of the general colorant is preferably 1% by mass to 20% by mass, preferably 2% by mass or more, based on the total solid content of the resin composition forming the base material layer. More preferably, it is 10% by mass. Here, the solid content refers to the total amount of the components excluding the solvent in all the components of the resin composition forming the base material layer.

The thickness of the base material layer is preferably in the range of 50 μm to 400 μm, and more preferably in the range of 100 μm to 350 μm. When the thickness is within the above range, breakage due to melting of the decorative film when the decorative film is preformed by a vacuum forming method or the like is effectively suppressed, and further, the concealing property of the molded body which is an adherend is suppressed. Becomes better.

The method for forming the base material layer is not particularly limited, and a known sheet forming method, for example, an extrusion method for extruding with a T-die, a calendar method, a casting method, or the like can be applied.
Of these, the calendar method is preferable in that it is easy to manufacture and easy to maintain the device. In particular, when the base material layer contains a colorant, the softened resin and the solid colorant can be supplied to the calendar roll and molded into a sheet or a film, so that the group containing various colorants. The material layer can be easily manufactured.
Further, by applying the calendar method, it is possible to more easily clean the inside of the apparatus required when changing the type and the amount of the colorant added, as compared with the molding method such as the extrusion method. Therefore, by applying the calendar method when forming a layer containing a colorant as a base material layer, various base material layers having a desired hue can be easily produced, and a small lot of decorative films can be produced. Also suitable for production.

(3. Adhesive layer)
The decorative film is provided with an adhesive layer on the surface of the base material layer opposite to the skin layer side to improve the adhesiveness with the molded product. The adhesive layer in the present disclosure is a pressure-sensitive adhesive or hot-melt adhesive (hereinafter collectively referred to as a specific pressure-sensitive adhesive) containing at least one selected from ethylene vinyl acetate, acrylic resin, urethane resin, olefin resin, polyester, polyamide, and synthetic rubber. May be contained).
The adhesive layer can be formed by applying a specific pressure-sensitive adhesive to the surface of the base material layer opposite to the skin layer side.
As the specific pressure-sensitive adhesive used for forming the adhesive layer, a pressure-sensitive adhesive or a hot-melt adhesive is selected and used from the viewpoint of relatively low initial adhesiveness, such as a pressure-sensitive pressure-sensitive adhesive.
As the pressure-sensitive adhesive, a pressure-sensitive adhesive containing at least one selected from ethylene vinyl acetate, acrylic resin, urethane resin, olefin resin, polyester, polyamide, and synthetic rubber is selected. All of the above adhesives are preferable because they have relatively low initial adhesiveness and high adhesiveness after pressurization. Of these, a specific adhesive material containing an acrylic resin as a main agent is preferable because it has higher adhesion after sticking.

As the hot melt adhesive, a hot melt adhesive containing at least one selected from ethylene vinyl acetate, acrylic resin, urethane resin, olefin resin, polyester, polyamide, and synthetic rubber is selected and used. When forming the adhesive layer, the hot melt adhesive can be formed by heating the above resin and applying it to the surface of the base material layer in a fluid state. Stable adhesion is obtained after the temperature drops. Usually, the hot melt adhesive does not contain the solvent of the resin as the main agent, so that the heating and drying steps at the time of forming the adhesive layer are not necessarily required.
Among them, olefin resins such as polyethylene and polypropylene, urethane resins, acrylic resins, etc. are positioned and pressurized before the specific adhesive is completely cured, and good adhesion can be obtained after the temperature drops. preferable.
As a urethane resin, there is a specific adhesive called polyurethane reactive (PUR), which reacts with moisture in the air to improve curability and forms an adhesive layer having good heat resistance and cold resistance. , Can be used to form the adhesive layer in the present disclosure.

From the viewpoint that the specific adhesive has good adhesiveness and the initial adhesiveness can be suppressed to a low level, the weight average molecular weight of the resin is preferably 100,000 to 400,000, and 150,000 to 30. It is more preferable that it is 10,000.
The weight average molecular weight of the resin can be measured by a known measuring method such as gel permeation chromatography (GPC). Examples of the measuring device include the HLC-8220 series manufactured by Tosoh.

The glass transition temperature (Tg) of the specific pressure-sensitive adhesive is preferably −30 ° C. or higher, more preferably −25 ° C. or higher.
The glass transition temperature can be measured using a differential scanning calorimetry device (DSC) under the conditions of a nitrogen stream, a measurement sample of 10 mg, and a heating rate of 10 ° C./min. The inflection point of the DSC curve obtained as a result of the measurement is taken as the glass transition temperature of the resin.

It is preferable that the specific pressure-sensitive adhesive has a relatively low initial tackiness, and the stickiness is improved by pressurization, and the specific pressure-sensitive adhesive has physical properties of being stably immobilized.
As a preferred embodiment of the adhesiveness, the adhesive layer in the present disclosure has an initial peel strength (initial adhesiveness) measured by the following test method (I) in the range of 0.1 N / cm to 5 N / cm, and is 2 N / cm. It is preferably in the range of ~ 4N / cm.

(Test method (I))
The adhesive layer protective sheet is peeled off from the decorative film, attached to a stainless steel plate, and the peeling strength is measured according to the 180 ° peeling test of the adhesive tape specified in JIS Z 0237 (2009).
The test method (I) is a measure of the initial peel strength (initial adhesiveness). When the 180 ° peeling test is performed on a test piece having an adhesive layer formed on a substrate, the adhesiveness is 0.1 N / When the range is in the range of cm to 5 N / cm, the peel strength at the time of peeling after the test piece is once attached to the surface of the hard base material is suppressed to a low level, and the adhesive layer is stretched or wrinkled at the time of peeling. It is less likely to occur and can be easily reattached.
When a shape-retaining layer, which is an arbitrary layer, is provided adjacent to the adhesive layer protective sheet, both the adhesive protective sheet and the shape-retaining layer may be peeled off. Since the peeling is performed at the interface between the adhesive and the adhesive layer protective sheet, generally, the shape-retaining layer, which is an arbitrary layer, is also peeled at the same time as the adhesive layer protective sheet is peeled off.

The adhesive layer in the present disclosure preferably has an adhesiveness of 7 N / cm or more after pressurization measured by the following test method (II), and more preferably 8 N / cm or more.

(Test method (II))
The adhesive layer protective sheet is peeled off from the decorative film, attached to a stainless steel plate, held at 20 ° C. for 24 hours, and then peeled strength according to the 180 ° peeling test of the adhesive tape specified in JIS Z 0237 (2009). To measure.
The test method (II) is a guideline for showing the adhesiveness of the adhesive layer after curing (after aging). By adhering the test piece having the adhesive layer to the surface of the hard base material which is the adherend and curing it for 24 hours, the adhesion area between the hard base material and the adhesive layer becomes larger, and the intermolecular force between the two becomes stronger. It occurs at multiple points, the aging of the adhesive layer progresses, the strength of the adhesive layer itself is further improved, and the adhesive layer is more stably fixed on the hard base material.
Also in the test method (II), when the shape-retaining layer is an arbitrary layer, both the adhesive layer protective sheet and the shape-retaining layer may be peeled off.

Since it is difficult to take out only the adhesive layer from the decorative laminate from which the adhesive layer protective sheet has been peeled off from the decorative film of the present disclosure and evaluate it, a decorative laminate is used instead of the above test piece. The peelability may be evaluated. This is because, in the decorative film of the present disclosure, the only layer involved in the adhesion to the molded body, which is the adherend, is the adhesive layer.

The thickness of the adhesive layer is preferably in the range of 10 μm to 80 μm, and more preferably in the range of 30 μm to 60 μm, from the viewpoint of adhesiveness and ease of correction of the sticking position.
The thickness of the adhesive layer is measured by observing the cut surface obtained by cutting the decorative film perpendicularly to the surface direction with an optical microscope at a magnification of 50 to 100 times. In the present disclosure, the thicknesses of different parts are measured at five different points within the viewing angle of the optical microscope, and the arithmetic mean thereof is taken as the thickness of the adhesive layer.

When an adhesive layer is formed on the surface of the base material layer, a primer layer, which will be described later, is formed between the base material layer and the adhesive layer for the purpose of improving the adhesiveness, and the surface of the formed primer layer is formed. An adhesive layer can be formed by applying at least one of an adhesive and an adhesive.
As a method for imparting an adhesive layer on the base material layer or the primer layer, any known method such as a transfer method or a coating method can be used. From the viewpoint that an adhesive layer having a uniform thickness can be easily formed, it is preferable to use the transfer method.

(4. Adhesive layer protective sheet)
After the formation of the adhesive layer, the surface of the adhesive layer is covered with an adhesive layer protective sheet for the purpose of protecting the surface of the adhesive layer.
As the adhesive layer protective sheet used for forming the decorative film of the present disclosure, a sheet made of a releasable material, a sheet whose surface in contact with the adhesive layer of the base material has been released, and the like can be used. ..
The surface of the adhesive layer protective sheet on the side in contact with the adhesive layer may be smooth or may have irregularities.
Above all, it is preferable that the adhesive layer protective sheet has irregularities. Since the adhesive layer protective sheet has irregularities, the irregularities of the adhesive layer protective sheet and the adhesive layer are fitted in the decorative film, and after the adhesive layer protective sheet is peeled off from the adhesive layer, the irregularities are formed. Recesses are formed on the exposed surface of the adhesive layer after being transferred, and due to the formed recesses, the contact area between the adhesive layer and the molded body at the time of attachment is the case where the surface of the adhesive layer protective sheet is smooth. In comparison, it is smaller and has lower adhesion. Therefore, it is considered that the initial peel strength becomes smaller and it becomes easier to correct the position after pasting.
Further, since the adhesive layer has irregularities, the concave portions of the adhesive layer serve as a flow path for fluids such as air and water, and undesired fluids are discharged more quickly from the end portion of the decorative laminate, resulting in better stickability. It also has the advantage of improving.

The unevenness formed on the adhesive layer protective sheet preferably has a convex portion height of 15 μm or more, more preferably 17 μm or more, and further preferably 25 μm or more. The upper limit of the height of the convex portion can be 35 μm or more, preferably 40 μm or less, and more preferably 38 μm or less.
The height and width of the convex portion of the unevenness on the adhesive layer protective sheet can be measured by the same method as the thickness of the adhesive layer.

The material of the adhesive layer protective sheet is not particularly limited as long as the surface in contact with the adhesive layer has releasability. Examples thereof include resin films, mold-released papers, and resin-laminated papers.
When the adhesive layer protective sheet has irregularities, a resin film is preferable from the viewpoint of better shape retention and preformability of the convex portions.
Examples of the resin film that can be used as the adhesive layer protective sheet include a PP film and a PET film, and a PP film is preferable.
The thickness of the adhesive layer protective sheet is not particularly limited. From the viewpoint of good preformability, the range is preferably in the range of 20 μm to 80 μm, and more preferably in the range of 30 μm to 60 μm.
The adhesive layer protective sheet is peeled off when the decorative film is applied to the molded body after the pre-molding of the decorative film described later.

(5. Other layers)
The decorative film may have, in addition to the above-mentioned skin layer, base material layer, adhesive layer, and adhesive layer protective sheet, other layers as long as the effect is not impaired.
Examples of other layers include a shape-retaining layer, a primer layer, and a design layer.

(5-1. Shape retention layer)
In the decorative film of the present disclosure, it is preferable to provide a shape-retaining layer on the surface of the above-mentioned adhesive layer protective sheet opposite to the adhesive layer side.
By having the shape-retaining layer, the shape-retaining property at the time of preforming of the decorative film is further improved.
That is, when the decorative film has a shape-retaining layer, the decorative film is preformed by means such as a vacuum forming method under a temperature condition of 80 ° C. to 150 ° C., and then cooled to room temperature (25 ° C.). However, the entire decorative film retains the preformed shape due to the function of the shape-retaining layer.
A layer that gives the decorative film a function of retaining the preformed shape after preforming with heating is referred to as a shape retaining layer in the present disclosure.
Here, "the shape is retained" means that when a preformed 50 cm square decorative film is fixed at one point in a square corner, the unfixed portion is deformed from the fixed point by gravity. It means that it does not cause deformation such as hanging down.
In order to impart the function of retaining such a shape, the thickness of the shape-retaining layer when the decorative film of the present disclosure has a shape-retaining layer is preferably in the range of 100 μm to 500 μm, and is preferably 200 μm. More preferably, it is in the range of ~ 400 μm.

The decorative film of the present disclosure preferably has a shape-retaining layer in addition to the skin layer, the base material layer, the adhesive layer and the adhesive layer protective sheet from the viewpoint of improving preformability. It is also possible to impart a shape-retaining function to the base material layer by selecting, for example, the resin contained in the base material layer, the thickness of the base material layer, and the like without further providing the shape-retaining layer. When giving the base material layer a shape-retaining function, it becomes necessary to maintain the thickness and rigidity of the base material layer within a predetermined range. However, in order to increase the thickness of the base material layer or impart rigidity, the composition of the base material layer is restricted, which may affect the appearance quality due to the dispersibility of the pigment or the like. ..
In the decorative film, the base material layer is provided with a shape-retaining layer adjacent to the adhesive layer protective sheet provided on the side opposite to the skin layer side of the base material layer separately from the base material layer. It is possible to give the decorative film a shape-retaining function while ensuring the resulting appearance quality.

Therefore, in the decorative film of the present disclosure, it is preferable to further provide a shape-retaining layer as a layer separate from the base material layer. As a preferred embodiment of the decorative film of the present disclosure, by further having a shape-retaining layer adjacent to the adhesive layer protective sheet, when the adhesive layer protective sheet has irregularities, the shape of the formed irregularities is more effectively maintained. Has the advantage of being able to.
Therefore, by further providing the shape-retaining layer, the decorative film of the present disclosure has better heat molding and better preformability. Further, when the decorative film is attached to the molded body, it is necessary to peel off the adhesive layer protective sheet, but when the shape-retaining layer is provided on the surface opposite to the adhesive layer side of the adhesive layer protective sheet, it is adhered. Since the shape-retaining layer is also peeled off at the same time when the layer protection sheet is peeled off, there is also an advantage that a decorative laminate can be easily obtained.

The shape-retaining layer can be formed of resin. The shape-retaining layer preferably contains at least one resin selected from ABS resin and PVC resin.
When the shape-retaining layer contains at least one resin selected from ABS resin and PVC resin, when the decorative film is preformed by a vacuum forming method or the like, shrinkage of the laminated adhesive layer protective sheet is suppressed. In addition, the retention of the preformed shape is improved, and further, breakage of the locally stretched portion during premolding due to stretching is effectively suppressed.
The ABS resin and the PVC resin may be used alone or mixed with AS resin, polycarbonate (PC), polypropylene (PP) and the like. Further, the ABS resin and the PVC resin may be used in combination.
Among them, it is preferable to use ABS resin or PVC resin alone as the resin, or to use a mixture of PC and ABS resin (PC / ABS), and it is more preferable to use ABS resin or PVC resin alone as the resin. preferable.
Only one type of ABS resin may be used, or two or more types of ABS resins having different copolymerization ratios may be used in combination.
The PVC resin is not particularly limited, and a known film-forming PVC resin can be appropriately selected and used.

The shape-retaining layer may contain, if necessary, other components in addition to at least one resin selected from ABS resin and PVC resin, as long as the effect is not impaired. Other components that the shape-retaining layer may contain include plasticizers, fillers, lubricants, processing aids and the like.

(5-2. Primer layer)
The decorative film has a resin layer as a primer layer between the base material layer and the adhesive layer for the purpose of improving the adhesion between the adhesive layer provided adjacent to the base material layer and the base material layer. May be.
The primer layer can be formed by a coating method. That is, the primer layer can be formed by dissolving the resin for forming the primer layer with an appropriate solvent, applying the resin to the surface of the base material layer opposite to the epidermis side, and drying.
The resin contained in the primer layer is a resin such as a polyester resin from the viewpoint of having good affinity with the thermoplastic resin contained in the base material layer and the adhesive contained in the adhesive layer provided adjacently thereto. Is preferably formed using.
The amount of the resin layer applied as the primer layer is not particularly limited, and is appropriately selected depending on the intended purpose. In general, from the viewpoint of adhesiveness improving ^effect, is preferably in the range of ^{1g / m 2 ~5g / m 2} , more preferably in the range of ^{2g / m 2 ~3g / m 2} .

(5-3. Design layer)
The decorative film of the present disclosure may further have a design layer between the skin layer and the base material layer. The design layer is a layer that imparts a design to the decorative film, and may be a printing layer formed by printing, a colored layer containing a colorant, or a layer in which these are used in combination. ..
By providing the decorative film of the present disclosure with a design layer, various designs according to the use of the decorative film can be imparted to the molded body as desired, and the molded body can be given an appearance excellent in design. Can be done.

The design layer may be, for example, a printing layer formed by a printing method on the surface of the skin layer or the base material layer. Examples of the printing layer include a layer formed by a known printing method using a printing ink containing a resin. As the printing ink containing a resin, a printing ink containing an acrylic resin, a vinyl chloride-vinyl acetate copolymer, or the like is preferable from the viewpoint of being able to form a clear printed image.
The printing method is not particularly limited, and any printing method such as gravure printing (intaglio printing), letterpress printing, offset printing, inkjet printing, and screen printing can be applied.
As the design layer, a printing ink layer containing at least one selected from an acrylic resin or a vinyl chloride-vinyl acetate copolymer is preferable.

The design layer may be a colored layer. Examples of the coloring layer include a layer formed of a resin composition containing an arbitrary coloring agent. For example, a resin composition containing an acrylic resin containing a colorant selected from those listed as colorants that can be used for the base material layer described above was formed into a film by a calendar method, an extrusion method, a casting method, or the like. The design layer and the like can be mentioned.

Specific examples of the acrylic resin that can be used for forming the design layer include polymers or copolymers of methacrylic acid or methacrylic acid ester represented by polymethylmethacrylate (PMMA), alkyl methacrylate and alkyl acrylate. From the viewpoint of moldability, a copolymer of alkyl methacrylate, alkyl acrylate and styrene, and a mixture of methyl methacrylate and methyl acrylate are preferable.

The acrylic resin has excellent weather resistance and stretchability, and has good adhesion to other resin layers provided adjacent to the acrylic resin.
Further, since the acrylic resin has good transparency, it can be added by adding a colorant or the like to the acrylic resin or by adding a light-scattering colorant such as a pigment having a metallic luster or a pearl pigment. It is possible to arbitrarily impart a desired good hue, a design having excellent gloss, and the like to the decorative film.
Further, when a printing ink layer is formed by using a printing ink containing an acrylic resin, a more complicated arbitrary design can be imparted to the decorative film by printing characters, images, and the like.

When the decorative film of the present disclosure has a design layer, the thickness of the design layer is preferably in the range of 1 μm to 15 μm, more preferably in the range of 2 μm to 10 μm, and preferably in the range of 2 μm to 5 μm. More preferred. When the thickness is in the above range, a desired design can be imparted to the decorative film, and a good correlation between the skin layer and the base material layer is maintained when the decorative film is preformed. , The retention of the uneven pattern of the epidermis layer becomes better.

A preferred embodiment of the decorative film of the present disclosure is an embodiment in which the skin layer has irregularities on one surface and a layer containing a fluororesin and having good heat resistance. In the skin layer containing a fluororesin, the uneven pattern formed on one surface is less likely to be deformed by heating if desired. Further, the epidermis layer is preferably laminated with a base material layer containing a PVC resin. Further, the adhesive layer protective sheet contains at least one resin selected from PP, PET, PEN and PE suitable for preforming, and is adjacent to the adhesive layer protective sheet, preferably selected from ABS resin and PVC resin. It has a shape-retaining layer containing at least one resin. The decorative film having these layers has better shape retention when premolded by a vacuum forming method or the like.
In a preferred embodiment, the skin layer and the base layer containing the PVC resin adjacent to the skin layer are both flexible and easily deformed, and are further selected from the ABS resin and the PVC resin formed adjacent to the adhesive layer protective sheet as desired. When the shape-retaining layer containing at least one kind of resin is provided, shrinkage of the adhesive layer protective sheet during vacuum forming is suppressed due to these layers, and pre-molding as designed can be performed more easily.
Further, even after the pressurization during preforming is removed, the shape of the concave portion of the adhesive layer formed by the unevenness of the adhesive layer protective sheet can be easily maintained. Therefore, even after the adhesive layer protective sheet is peeled off to form a decorative laminate after vacuum forming, the skin layer, the base material layer, and the decorative laminate having the adhesive layer are the adherends to be attached. A shape that fits a molded body having a certain three-dimensional shape is better maintained.
When the adhesive layer has irregularities, the contact area between the molded body and the adhesive layer becomes smaller once the adhesive layer is attached to the molded body. Therefore, even when the position is corrected after pasting, when the decorative laminated body is peeled off, the decorative laminated body is less likely to be stretched and wrinkled, and the position can be corrected more easily.

The decorative film of the present disclosure has a skin layer having excellent transparency and durability, good retention of uneven patterns during heating, and a base material layer having excellent heat processability on the outermost surface. , And an adhesive layer protective sheet. Therefore, the decorative laminate obtained by pre-molding the decorative film into a shape suitable for the unevenness of the molded body having a three-dimensional shape and then peeling off the adhesive layer protective sheet is the uneven pattern of the skin layer and the adhesive layer. Has good retention of the recesses, and has good retention of the preformed shape while having a certain degree of flexibility.
In addition, it becomes easier to correct the position once it is pasted. Therefore, when the preformed decorative laminate is attached to the surface of the molded body having a three-dimensional shape, the decorative laminate can be easily positioned and the position can be easily corrected once the decorative laminate is attached. Therefore, an arbitrary design can be easily formed on the molded body. By further providing a shape-retaining layer adjacent to the adhesive layer protective sheet, the shape-retaining property of the decorative film can be improved.
The decorative molded product obtained by pasting the decorative laminate on the surface has an excellent appearance and excellent durability such as solvent resistance, reflecting the design of the decorative film.
Therefore, the decorative film of the present disclosure can be applied to various uses as a decorative film that imparts design to the surface of a molded product having an uneven shape.

<Manufacturing method of decorative film>
The method for producing the decorative film of the present disclosure described above is not particularly limited, and a known production method can be appropriately adopted.
Among them, it is preferable that the decorative film is produced by the method for producing a decorative film of the present disclosure, which will be described later.

The method for producing a decorative film of the present disclosure includes a step of preparing a skin layer containing a fluororesin (step (I)), a base material containing a polyvinyl chloride resin using a resin composition containing a polyvinyl chloride resin. A step of forming a layer (step (II)), a step of laminating a skin layer containing a fluororesin on one surface of the base material layer (step (III)), and having the skin layer of the base material layer. An adhesive or hot melt adhesive containing at least one selected from ethylene vinyl acetate, acrylic resin, urethane resin, olefin resin, polyester, polyamide, and synthetic rubber on the surface opposite to the side, and the thickness is A step of forming an adhesive layer of 10 μm to 80 μm (step (IV)), a step of preparing an adhesive layer protective sheet (step V)), and contacting the adhesive layer protective sheet with the adhesive layer to protect the adhesive layer. The step (step (VI)) of coating the adhesive layer with a sheet is included.
The step of preparing the adhesive layer protective sheet (step (V)) is a step of embossing the resin sheet to form an adhesive layer protective sheet having irregularities to be fitted to the adhesive layer (step (V-2). )) Can be further included.

(Step (I))
In step (I), a skin layer containing a fluororesin is prepared. Preparing the epidermis layer includes both forming an epidermis layer containing a fluororesin and procuring a commercially available epidermis layer.
In the step (I), the epidermis layer containing the fluororesin can be formed by a calendar method, an extrusion method, a casting method, or the like.
When forming a skin layer having a laminated structure, a laminated film can be formed by a coextrusion method or the like of two or more kinds of resins.
Further, the step (I) includes preparing a commercially available film containing a fluororesin as the skin layer, as described above in the description of the decorative film.

(Step (II))
In step (II), a base material layer containing a polyvinyl chloride resin is formed by a known method such as a calendar method, an extrusion method, or a casting method using a resin composition containing a polyvinyl chloride resin. Above all, it is preferable to form the base material layer by the calendar method from the viewpoint of processability. By forming the base material layer by the calendar method, for example, a base material layer having a uniform film thickness can be easily formed as compared with the extrusion method or the like. In addition, by applying the calendar method when the base material layer contains a colorant, it is easy to clean the inside of the device, which is necessary when changing the type and amount of the colorant used in the base material layer. It can be carried out.
To give an example of a method of forming a base material layer using a PVC resin and a pigment as a colorant, a predetermined amount of the pigment is added to the PVC resin and heated and mixed with a hot mixing roll to color the PVC. Examples thereof include a method of obtaining a resin and forming a base material layer by a calendar method using the obtained colored PVC resin. When the colorant is not used, the process of adding the pigment can be omitted in the same manner.
Either the step (I) or the main step (II) may be performed first, and each step can be performed in parallel.

(Step (III))
In the step (III), the epidermis layer prepared in the step (I) is laminated on one surface of the base material layer obtained in the step (II).
Here, if desired, laminating embossing is performed on the side of the laminated epidermis layer opposite to the side having the base material layer by using a drawing roll, and the surface of the epidermis layer opposite to the base material layer side is subjected to laminating embossing. An uneven pattern may be formed.
In the step (III), if desired, the laminating of the epidermis layer and the base material layer and the formation of the uneven pattern on the epidermis layer can be performed at the same time. That is, the base material layer is laminated on one surface of the epidermis layer, and then the laminated body is laminated and embossed by using a drawing roll to perform heat-pressurization adhesion of each layer and desired on the surface of the epidermis layer. The uneven pattern can be formed at the same time.
In the present disclosure, the laminated embossing performed as desired is defined as embossing one of a pair of embossing rolls to be thermocompression bonded by using a drawing roll, and a plurality of resin-containing films are bonded by thermocompression bonding, and the resin-containing film is formed. It refers to forming irregularities on the surface by pressing the surface in contact with the drawing roll with the drawing roll. In step (III), when forming an uneven pattern on the epidermis layer, laminating embossing is performed by arranging a squeezing roll on the epidermis layer side and a smooth roll on the base material layer side. According to this method, the lamination of the two layers and the formation of the uneven pattern in the epidermis layer can be carried out sequentially or simultaneously in one step.
When the uneven pattern is not formed on the epidermis layer, laminating with a pair of smooth rolls may be performed at the time of laminating.

By laminating and embossing using a drawing roll in which an arbitrary uneven pattern such as a natural leather-like uneven pattern is previously formed on the surface of the epidermis layer, it is bonded to the base material layer and the epidermis layer is squeezed (unevenness). ) Is performed in one step, and the uneven pattern of any design such as natural leather-like unevenness is transferred to the outermost surface of the skin layer in the formed decorative film.
By selecting the shape of the uneven pattern to be formed on the drawing roll, it is possible to form not only a natural leather-like pattern but also a pattern having an arbitrary uneven shape on the surface of the decorative film.
In both embossing with a smooth roll and laminating embossing, the heating temperature during processing is preferably 100 ° C. to 190 ° C. The heating temperature is the surface temperature of the roll.
The method of forming irregularities on one surface of the epidermis layer is not limited to this. For example, when the epidermis layer is formed by the coating method, the composition for forming the epidermis layer is formed on a paper pattern on which the irregularities are formed in advance. It is also possible to apply and form the unevenness on the release paper by transferring it to the skin layer.

(Step (IV))
In step (IV), ethylene vinyl acetate, acrylic resin, urethane resin, olefin resin, polyester, polyamide, and It contains a pressure-sensitive adhesive or a hot-melt adhesive containing at least one selected from synthetic rubbers, and forms an adhesive layer having a thickness of 10 μm to 80 μm.
The adhesive layer can be formed by applying at least one of the above-mentioned specific pressure-sensitive adhesives to the surface of the base material layer opposite to the side having the skin layer.
Preferred examples of the specific pressure-sensitive adhesive used for forming the adhesive layer are as described in the above-mentioned decorative film, and the same applies to the preferred examples.
The thickness of the adhesive layer is in the range of 10 μm to 80 μm, preferably in the range of 20 μm to 60 μm.

(Process (V))
In step (V), an adhesive layer protective sheet is prepared. A resin film is preferably used as the adhesive layer protective sheet.
Examples of the resin film include PP film and PET film, and PP film is preferable.

The adhesive layer protective sheet is preferably an adhesive layer protective sheet in which irregularities are formed by embossing a resin film as a base material (step (V-2)).
A known method can be used as a method for obtaining an adhesive layer protective sheet by forming irregularities on the resin film. Generally, embossing is applied to form irregularities by heating and pressurizing with an embossing roll.
The embossing temperature can be appropriately selected depending on the type of resin film.

The thickness of the adhesive layer protective sheet is not particularly limited, but from the viewpoint of good preformability, it is preferably in the range of 20 μm to 80 μm, and more preferably in the range of 30 μm to 60 μm.
The adhesive layer protective sheet is peeled off together with an adjacent shape-retaining layer when it is applied to a molded product after pre-molding of a decorative film described later.

(Process (VI))
In the step (VI), the adhesive layer formed in the step (IV) is covered with the adhesive layer protective sheet prepared in the step (V).
As the adhesive layer protective sheet, as described above, a PP film as an easily peelable resin film is more preferable, and a PP film, which is an adhesive layer protective sheet having irregularities formed therein, is more preferable.
The step (VI) can be performed continuously with the step (III). That is, an adhesive is applied onto the base material layer to form an adhesive layer, and the adhesive layer is protected on the surface of the adhesive layer in a state where the adhesive layer is uncured, which is prepared in a separate step (V). A sheet can be applied and coated.

Through the above steps, a decorative film having an epidermis layer, a base material layer, an adhesive layer, and an adhesive layer protective sheet covering the adhesive layer is obtained in this order.
When the decorative film is attached to the molded body, the surface (exposed side) of the adhesive layer is brought into contact with the molded body in the state of the decorative laminated body in which the adhesive layer protective sheet is peeled off from the decorative film. ..

The method for producing a decorative film of the present disclosure may further include other steps.
For example, a method for producing a decorative film is a step of forming a shape-retaining layer using a thermoplastic resin composition containing at least one resin selected from an acrylonitrile / butadiene / styrene copolymer and a polyvinyl chloride resin (a step of forming a shape-retaining layer (). Step (VII)), a step of laminating the obtained shape-retaining layer on the side opposite to the adhesive layer side of the adhesive layer protective sheet via an adhesive (step (VIII)), a base material layer and an adhesive layer. A step of forming a primer layer (step (IX)) and a step of forming a design layer between the skin layer and the base material layer (step (X)) can be further included between the two.

When the decorative film has a shape-retaining layer which is an arbitrary layer, the shape-retaining layer is preferably formed by the following steps (VII) and (VIII).

(Process (VII))
In the step (VII), a shape-retaining layer is formed by a known method such as a calendar method, an extrusion method, or a casting method using a thermoplastic resin composition containing at least one resin selected from ABS resin and PVC resin. Above all, it is preferable to form the shape-retaining layer by the calendar method from the viewpoint of workability.
The method for forming the shape-retaining layer by the calendar method can be carried out in the same manner as the method for forming the base material layer in step (II), except that the resin used is different.

(Step (VIII))
In the step (VIII), the shape-retaining layer obtained in the step (VII) is bonded to the surface of the adhesive layer protective sheet opposite to the adhesive layer side via an adhesive.
As the adhesive, a silicone resin type adhesive is preferable. Further, the adhesive used for forming the adhesive layer can be used in the same manner.
The coating amount of the adhesive ^is preferably in the range of ^{20g / m 2 ~80g / m 2} .

(Process (IX))
In the step (IX), the formation of the primer layer can be performed by a coating method. That is, the primer layer can be formed by dissolving the resin for forming the primer layer with an appropriate solvent, applying the resin to the surface of the base material layer opposite to the epidermis layer side, and drying.
When forming the primer layer, the above-mentioned step (IV) may be carried out after the step (IX) to form an adhesive layer on the primer layer.

(Step (X))
The step (X) is an arbitrary step of further forming a design layer in the method for manufacturing a decorative film.
In the step (X), the design layer can be formed on one side of the skin layer prepared in the step (I) or the base material layer formed in the step (II).
Examples of the method of forming the design layer include a method of adhering a preformed design layer to one side of the skin layer or the base material layer, and an acrylic resin or vinyl chloride-vinyl acetate on one side of the skin layer or the base material layer. Examples thereof include a method of printing using a printing ink containing a polymer.
Above all, it is preferable to form the design layer by printing because the degree of freedom of the design is high. As a method for forming the design layer, a printing method may be applied to the design layer including the design, and if the design layer is a coloring layer, a resin composition containing a coloring agent may be prepared by a known method. A method of forming into a film to form a design layer can be applied.

The printing method is a method of printing a known pattern with a printing ink containing a resin, and a printing ink containing a resin, for example, a printing ink containing an acrylic resin, a vinyl chloride-vinyl acetate copolymer, or the like is used as a known printing method. For example, a method of forming by printing by gravure printing (concave printing), letterpress printing, offset printing, inkjet printing, screen printing, or the like can be mentioned.
Specific examples of the printing method include printing on one side of the skin layer by gravure printing using a printing ink containing an acrylic resin. By adjusting the engraving size of the print roll used for gravure printing, printing can be performed while adjusting the amount of printing ink applied, and various designs can be formed.
Since the design layer, which is an arbitrary layer, can be formed independently on one surface of the skin layer or the base material layer as desired, a layer having a desired design with an arbitrary hue and an arbitrary design can be formed. .. Therefore, by providing the design layer, various designs can be imparted to the decorative film.

<Decorative molding>
The decorative molded body of the present disclosure includes a molded body having a three-dimensional shape and a decorative laminated body in which the adhesive layer protective sheet is peeled off from the decorative film. When the shape-retaining layer is provided adjacent to the adhesive layer protective sheet, the shape-retaining layer adjacent to the adhesive layer protective sheet is also peeled off by peeling the adhesive layer protective sheet from the adhesive layer of the decorative film. A decorative laminate can be obtained.
FIG. 2A is a schematic cross section showing an example of a state in which the adhesive layer protective sheet and the shape-retaining layer are peeled off from the decorative film of the present disclosure shown in FIG. 1 and attached to the surface of the molded body 28. FIG. 2B is a schematic cross-sectional view showing an example of a state in which the decorative laminated body 24 is pressed and brought into close contact with the molded body 28 to form the decorative molded body 30.
As shown in FIG. 2B, the decorative molded body 30 peels off the adhesive layer protective sheet and the shape-retaining layer from the molded body 28 to be decorated and the decorative film of the present disclosure arranged on the surface of the molded body. It has a decorative laminated body 24 and the like. The decorative laminate 24 has the same layer structure as the decorative film of the present disclosure described above, except that it does not have an adhesive layer protective sheet and a shape-retaining layer. That is, as shown in FIGS. 2A and 2B, the decorative laminate 24 has a skin layer 12, a base material layer 14, a primer layer 16, and an adhesive layer 18 which may have irregularities on the surface. In FIGS. 2A and 2B, the primer layer 16 provided for improving the adhesion between the base material layer 14 and the adhesive layer 18 is an arbitrary layer as described above.

<Manufacturing method of decorative molded product>
The decorative film of the present disclosure described above is preferably used for the purpose of imparting a design to the surface of a molded product when producing a molded product by heat molding.
The method for producing a decorative molded product of the present disclosure is a step of preforming the above-mentioned decorative film of the present disclosure into a shape suitable for the shape of the molded product to which the decorative film is attached by a vacuum forming method (step (i). )), The step of peeling off the adhesive layer protective sheet of the preformed decorative film (step (ii)), the decorative laminate derived from the decorative film from which the adhesive layer protective sheet has been peeled off, is subjected to the decorative laminate. A step of sticking to the surface of the molded body having a three-dimensional shape (step (iii)) and a step of pressing the decorative laminate stuck to the surface of the molded body (step iv) via the adhesive layer of the body. Including.

In the step (i), the decorative film of the present disclosure is premolded by a vacuum forming method using a mold suitable for the three-dimensional shape of the molded body as the adherend substrate.
As a method for preforming, a vacuum forming method is applied from the viewpoint of shape retention of the preformed decorative film (preformed body of the decorative film). As the vacuum forming method, a known method can be applied. As described above, the heating conditions for preforming the decorative film by vacuum forming are preferably in the temperature range of 80 ° C. to 150 ° C.
In the step (i), the decorative film is placed on the surface of the molding die having a shape suitable for the molded body having a three-dimensional shape, evacuated by a conventional method, preformed along the molding die, and the decorative film is formed. To obtain a preformed body of.
Since the decorative film of the present disclosure has the above-mentioned layer structure, it is quickly preformed by a vacuum forming method, and the obtained preformed body has good shape retention. Further, by having a shape-retaining layer adjacent to the adhesive layer protective sheet, the preformability of the decorative film becomes better.

In the step (ii), the adhesive layer protective sheet of the preformed decorative film is peeled off. Then, the adhesive layer protective sheet is peeled off to obtain a decorative laminated body in a state where the adhesive layer is exposed. Due to the function of the adhesive layer protective sheet, the decorative laminated body has recesses formed in the adhesive layer due to the unevenness of the adhesive layer protective sheet.
By further having a shape-retaining layer or the like adjacent to the adhesive layer protective sheet, the decorative film further suppresses shrinkage of the adhesive layer protective sheet during premolding, and is formed into the shape-retaining property of the premolded body and the adhesive layer. The shape retention of the formed concave portion becomes better.
When a shape-retaining layer is further adjacent to the adhesive layer protective sheet, when the adhesive layer protective sheet is peeled from the adhesive layer of the decorative film, the shape-retaining layer adjacent to the adhesive layer protective sheet is also peeled off at the same time, and the decorative laminate is formed. The body is obtained.

In the step (iii), the decorative laminate 24 derived from the decorative film, from which the adhesive layer protective sheet and the shape-retaining layer provided as desired are peeled off in the step (ii), is molded from the decorative laminate 24. It is attached to the surface of the molded body 28 having a three-dimensional shape via the adhesive layer 18 in which the recess 26 is formed on the surface in contact with the body. (See Fig. 2A)
In the step (iii), the step of attaching the decorative laminate derived from the decorative film to the surface of the molded body 28 having a three-dimensional shape via the adhesive layer of the decorative laminate 24 is the step of attaching the decorative laminate 28 to the surface of the adhesive layer 18. It is preferably performed while the shape of the recess 26 formed by the adhesive layer protective sheet provided on the side in contact with the molded body is maintained.
Since the decorative laminate 24 has good shape retention of the recesses 26 formed in the adhesive layer, it can be directly attached to the molded body and arranged. When the decorative laminate 24 is attached to the molded body 28 via the adhesive layer 18, the contact area between the adhesive layer 18 and the molded body 28 is determined by the recesses 26 formed in the adhesive layer 18 to be the surface of the adhesive layer. Is smaller than when is smooth.
Therefore, when the decorative laminated body 24 is once pasted and then the pasting position is corrected, the decorative laminated body 24 can be easily peeled off again, and the pasting position is easily corrected. be able to. Therefore, failures such as elongation and wrinkles caused by re-peeling of the decorative laminated body 24 are suppressed, and a decorative molded body 30 having a good appearance decorated by the decorative laminated body can be obtained.
After that, as shown in FIG. 2B, by pressing the decorative laminate 24 for which positioning has been completed toward the molded body 28, the specific adhesive contained in the adhesive layer 18 is stressed to form the surface shape of the molded body 28. The concave portion formed in the adhesive layer 18 by being deformed along the line is leveled to form a uniform adhesive layer 18 in close contact with the molded body 28 as shown in FIG. 2B. Therefore, due to the action of the specific pressure-sensitive adhesive, the decorative laminated body 24 adheres to the molded body 28 via the adhesive layer 18 and is stably fixed.

The method for producing a decorative laminate of the present disclosure may further include a step (step iv) of heating the decorative laminate attached to the surface of the molded product.
By heating the decorative laminate 24 after the decorative laminate 24 and the molded body 28 are in close contact with each other in the state shown in FIG. 2B, the curing of the specific adhesive contained in the adhesive layer 18 is promoted. The shape followability of the adhesive layer 18 to the surface of the molded body 28 is improved, the contact area is further improved, and the like, so that the decorative laminated body 24 is firmly adhered to the molded body 28.
Further, when a hot melt adhesive is used as the specific adhesive, the adhesive layer 18 in the decorative laminated body 24 is softened again, and the shape followability of the adhesive layer 18 to the surface of the molded body 28 is improved, resulting in close contact. Improves sex. After that, when the heating is finished and the temperature drops to room temperature, the decorative laminated body 24 and the molded body 28 are more firmly adhered to each other.

As described above, the decorative molded article of the present disclosure can be produced by a simple method. Since different hues, designs, etc. can be easily applied to the same molded product, it can be applied to various uses. Further, since the decorative laminate obtained by pre-molding and peeling off the adhesive layer protective sheet is flexible and has excellent fluid removability, various designs can be decoratively molded by a simple method and have a good appearance. You can get a body. Therefore, the method for producing a decorative molded product of the present disclosure is also suitable for small lot production of decorative molded products having different designs.
Examples of the molded product that can be applied to the decorative molded product include vehicles such as automobiles and railways, furniture, aircraft, ships, construction, and wall covering, and can be suitably used for decorating various molded products.

Hereinafter, the decorative film of the present disclosure will be specifically described with reference to examples, but the present disclosure is not limited thereto.

[Example 1]
(Manufacturing of decorative film)
As the skin layer, KFC film FT-50Y (trade name), Kureha Extec Co., Ltd. (laminate of polyvinylidene fluoride-containing layer, which is a fluororesin, and polymethylmethacrylate-containing layer, which is an acrylic resin, thickness: 50 μm). Prepared (step (I)).
2 kg of pigment [PV MAF 725 (trade name), Dainichi Seika Kogyo Co., Ltd.] was added to 100 kg of PVC resin [TH800 (trade name), Taiyo PVC Co., Ltd.], and the thickness after drying was increased by the calendar method. A base material layer was obtained by molding into a sheet so as to have a thickness of 150 μm (step (II)).
A base material layer is laminated on the polymethylmethacrylate-containing layer side of the epidermis layer, and the obtained laminate is used on the epidermis layer side by using an embossed roll in which one of the pair of embossed rolls has a squeezed pattern. It was brought into contact with a drawing roll and laminated embossed to form a drawing pattern on the surface of the epidermis layer (step (III)).
A urethane resin [Rezaroid (trade name), Dainichi Seika Kogyo Co., Ltd.] is applied to the surface of the base material layer of the laminate opposite to the skin layer side, and a primer layer having a dry film thickness of 3 μm is applied. It is formed (step (IX)), and an acrylic pressure-sensitive adhesive a [Tg: -20 ° C., molecular weight: 200,000] is applied onto the primer layer at a coating amount of 40 g / m ² , dried and dried to a thickness of 50 μm. An adhesive layer was formed (step (IV)).

A flat resin sheet (PP (Fujiko Corporation, BK0A (trade name), thickness: 60 μm)) is prepared as the base material of the adhesive layer protective sheet, and irregularities are formed under the condition that the surface temperature of the resin sheet is 150 ° C. The size of the convex portion whose cross section was measured with an optical microscope was (the width of the convex portion was 120 μm and the height was 25 μm (step (V)).
The surface of the adhesive layer formed in the step (IV) was covered with the adhesive layer protective sheet on which the irregularities obtained in the step (V) were formed (step (VI)).
100 kg of ABS resin [TM-30G6 (trade name), UMG-ABS Co., Ltd.] was formed into a sheet by a calendar method so that the thickness after drying was 250 μm to form a shape-retaining layer (step). (VII)).
The adhesive layer protective sheet covering the adhesive layer and the shape-retaining layer obtained in the step (VII) are combined with a silicone resin adhesive [Cemedine PM165-R (trade name), Cemedine Co., Ltd., coating amount 5 g / m ^2). ] To obtain the decorative film of Example 1 (step (VIII)).

(Comparative Example 1)
This was carried out except that the acrylic pressure-sensitive adhesive b [Tg: -52 ° C., molecular weight: 600,000] was used instead of the acrylic pressure-sensitive adhesive a, which is the specific pressure-sensitive adhesive used for forming the adhesive layer in the step (IV). A decorative film of Comparative Example 1 was obtained in the same manner as in Example 1.

(Comparative Example 2)
This was carried out except that the acrylic pressure-sensitive adhesive c [Tg: -47 ° C., molecular weight: 500,000] was used instead of the acrylic pressure-sensitive adhesive a, which is the specific pressure-sensitive adhesive used for forming the adhesive layer in the step (IV). A decorative film of Comparative Example 2 was obtained in the same manner as in Example 1.

(Comparative Example 3)
This was carried out except that the acrylic pressure-sensitive adhesive d [Tg: -35 ° C., molecular weight: 600,000] was used instead of the acrylic pressure-sensitive adhesive a, which is the specific pressure-sensitive adhesive used to form the adhesive layer in step (IV). A decorative film of Comparative Example 3 was obtained in the same manner as in Example 1.

(Evaluation of decorative film)
The obtained decorative film was premolded according to the shape of the molded product using a vacuum forming apparatus.
As the molded body, the roof side of the vehicle was applied. The unfolding rate during preforming was in the range of 100% to 300% of the area before preforming.

Then, the adhesive layer protective sheet and the shape-retaining layer of the preformed decorative film were peeled off, and the adhesive layer side was brought into contact with the molded body as the molded body side and attached to the surface of the molded body.
Ten workers as monitors evaluated the preformability of the decorative laminate with respect to the molded body at the time of pasting and the ease of position correction once pasted on the molded body by performing actual work.
In addition, the appearance of the decorative molded product after the decorative laminated body was attached was visually evaluated.
All evaluations were performed according to the following criteria.
Of the 10 workers, the highest evaluation was adopted. When the evaluation results were the same, better results were described.
The results are shown in Table 1 below. In both cases, A is a range in which there is no practical problem.

(Adhesion: Ball tack test)
JIS Z 0237 (2009) 14. The adhesiveness was evaluated according to the inclined ball tack test. The inclination angle was 30 °. The results are shown in Table 1 below.
It is preferable that the evaluation is 2 or less in the ball tack test from the viewpoint of low initial adhesiveness and easy reattachment.

(Easy to correct the pasting position)
A: Easy to correct B: Somewhat difficult to correct C: Correction is not possible, or wrinkles and twists occur in the modified decorative laminate.

(Adhesion to base material)
A: Good adhesion to the molded product after pasting B: Slight swelling due to re-pasting after pasting C: Many swelling due to re-pasting after pasting

(appearance)
A: No problem in appearance B: Slightly wrinkled or bulged, slightly problematic in appearance C: Wrinkled or bulged, problematic in appearance

When the decorative film of Example 1 was attached to the molded body as a decorative laminate after preforming, the ease of position correction was good, and the decorative film could be attached with good workability.
In addition, a decorative molded body having no wrinkles or swelling due to re-pasting after pasting and having good adhesion between the decorative laminated body and the molded body was obtained.

The decorative films of Comparative Examples 1 to 3 had strong initial adhesiveness and were difficult to reattach. In addition, there was a slight problem in appearance due to re-pasting.

From the above results, it can be seen that by using the decorative film of the example, a decorative molded product having a good appearance can be easily obtained.

10 Decorative film 12 Epidermis layer 14 Base material layer 16 Primer layer (resin layer)
18 Adhesive layer 20 Adhesive layer Protective sheet 22 Shape retention layer 24 Decorative laminate 26 Recesses (recesses) of the adhesive layer
28 Molded body (molded body base)
30 Decorative molding

Claims (13)

The skin layer, the base material layer, the adhesive layer, and the adhesive layer protective sheet are provided in this order.
The adhesive layer contains an adhesive or hot melt adhesive containing at least one selected from ethylene vinyl acetate, acrylic resin, urethane resin, olefin resin, polyester, polyamide, and synthetic rubber, and has a thickness of 10 μm to 80 μm. The adhesive layer has an initial peel strength in the range of 0.1 N / cm to 5 N / cm measured by the following test method (I).
A decorative film used to decorate a molded product having a three-dimensional shape.
(Test method (I))
The adhesive layer protective sheet is peeled off from the decorative film, attached to a stainless steel plate, and the peeling strength is measured according to the 180 ° peeling test of the adhesive tape specified in JIS Z 0237 (2009). The decorative film according to claim 1, wherein the adhesive layer protective sheet has a shape-retaining layer on a surface opposite to the side having the adhesive layer. The decorative film according to claim 1 or 2, which has irregularities fitted to the adhesive layer on the side of the adhesive layer protective sheet in contact with the adhesive layer. The decorative film according to any one of claims 1 to 3, wherein the adhesive layer has a peel strength of 7 N / cm or more after a lapse of time measured by the following test method (II).
(Test method (II))
The adhesive layer protective sheet is peeled off from the decorative film, attached to a stainless steel plate, held at 20 ° C. for 24 hours, and then peeled strength according to the 180 ° peeling test of the adhesive tape specified in JIS Z 0237 (2009). To measure. The decorative film according to any one of claims 1 to 4, wherein the base material layer contains a polyvinyl chloride resin. Any one of claims 1 to 5, wherein the adhesive layer protective sheet contains at least one resin selected from polypropylene (PP), polyethylene terephthalate (PET), polyethylene naphthalate (PEN) and polyethylene (PE). The decorative film according to item 1. The decorative film according to any one of claims 1 to 6, which is heat-moldable. The process of preparing the epidermis layer containing fluororesin,
A step of forming a base material layer containing a polyvinyl chloride resin using a resin composition containing a polyvinyl chloride resin,
A pressure-sensitive adhesive containing at least one selected from ethylene vinyl acetate, acrylic resin, urethane resin, olefin resin, polyester, polyamide, and synthetic rubber on the surface of the base material layer opposite to the side having the skin layer. Alternatively, a step of forming an adhesive layer containing a hot melt adhesive and having a thickness of 10 μm to 80 μm.
The process of preparing the adhesive layer protective sheet,
A step of bringing the adhesive layer protective sheet into contact with the adhesive layer and covering the adhesive layer with the adhesive layer protective sheet.
A method for manufacturing a decorative film including. Further, a step of forming a shape-retaining layer using a thermoplastic resin composition containing at least one resin selected from an acrylonitrile / butadiene / styrene copolymer and a polyvinyl chloride resin, and a step of forming a shape-retaining layer, and
The method for producing a decorative molded article according to claim 8, wherein the obtained shape-retaining layer is bonded to the side of the adhesive layer protective sheet opposite to the adhesive layer side via an adhesive. The eighth or ninth aspect of the present invention, wherein the step of preparing the adhesive layer protective sheet includes a step of embossing the resin sheet to prepare an adhesive layer protective sheet having irregularities to be fitted to the adhesive layer. How to make a decorative film. A decorative molded body having a three-dimensional shape and a decorative laminated body in which an adhesive layer protective sheet is peeled off from the decorative film according to any one of claims 1 to 7. A step of preforming the decorative film according to any one of claims 1 to 7 into a shape suitable for the shape of the molded body to be attached by a vacuum forming method.
The step of peeling the adhesive layer protective sheet from the preformed decorative film,
A step of attaching the decorative laminate obtained by peeling the adhesive layer protective sheet from the decorative film to the surface of the molded product having a three-dimensional shape via the adhesive layer of the decorative laminate, and
The process of pressurizing the decorative laminate attached to the surface of the molded product,
A method for manufacturing a decorative molded product having. The method for manufacturing a decorative molded body according to claim 12, further comprising a step of heating the decorative laminated body attached to the surface of the molded body.

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