WO2019225386A1

WO2019225386A1 - Decorative film, decorative film production method, decorative molded body and decorative molded body production method

Info

Publication number: WO2019225386A1
Application number: PCT/JP2019/018984
Authority: WO
Inventors: 忠彦稲垣; 治之石津
Original assignee: 共和レザー株式会社
Priority date: 2018-05-22
Filing date: 2019-05-13
Publication date: 2019-11-28
Also published as: JP2019202448A

Abstract

The invention provides a decorative film having a surface layer, a base material layer, a shape-holding layer, an adhesive layer, and an adhesive layer protection sheet, in this order, and used for decorating a molded body having a three-dimensional shape. The invention also provides a decorative film production method, a decorative molded body, and a decorative molded body production method.

Description

Decorative film, manufacturing method of decorative film, decorative molded body, and manufacturing method of decorative molded body

The present disclosure relates to a decorative film, a method for manufacturing a decorative film, a decorative molded body, and a method for manufacturing a decorative molded body.

A decorative film for changing the appearance of a vehicle such as an automobile or imparting a desired design to the vehicle is known. By pasting the decorative film on the roof of the automobile, the side of the body, etc., the design can be easily applied without painting. In addition, since the appearance of the vehicle can be easily changed by using the decorative film, the decorative film has attracted attention in recent years.
Various decorative films for vehicle exteriors have been proposed and there are commercially available products, but most of them are films that are pasted while following the shape of the vehicle with a flexible decorative film, adapted to the three-dimensional shape of the vehicle, It took skill to apply it so as not to damage the appearance.

Therefore, a surface protective film using a polyurethane having a specific tensile rupture elongation and a crosslinked structure is proposed as a decorative film that can be attached to various surface shapes and has good followability to curved surfaces. (See JP 2010-260942 A).
Further, a decorative film having a base material layer, a colored layer, and a pressure-sensitive adhesive layer and containing a non-spherical particle filler in the base material layer has been proposed (see Japanese Patent Application Laid-Open No. 2006-192609). .

For the purpose of improving the attachment property to a vehicle exterior having a three-dimensional shape, it has a release layer, an adhesive layer, and a skin layer, and the release layer includes a shape-retaining layer, so that it can be used as an object to be attached in advance. There have been proposed decorative sheets that can be preformed in accordance with the unevenness of the vehicle (see Japanese Patent Application Laid-Open Nos. 2016-198900 and 2016-203434).
By preliminarily molding the decorative film, it is said that the positioning to the vehicle exterior becomes easier than the flat decorative film.

However, the films described in Japanese Patent Application Laid-Open Nos. 2010-260942 and 2006-192609 can be applied to the decorative film while heating the decorative film, even when the shape followability is improved. There has been a demand for a decorative film having no simple improvement in workability and having a simpler pasting property.

The decorative film described in Japanese Patent Application Laid-Open Nos. 2016-198900 and 2016-203434 is provided with a shape-retaining layer in the release layer, and is more suitable for the three-dimensional shape of the adherend by preforming the decorative film. A shaped film is obtained in advance. However, if the release layer is peeled off when being applied to the molded body, the shape-retaining layer is also peeled off together with the release layer, and the resulting sheet is not rigid, and the film itself is flexible and easily deformed. For this reason, there is still room for improvement from the viewpoint of workability when the decorative film is attached to a three-dimensional shaped product.

The problem of an embodiment of the present invention is that, when affixed to a three-dimensional shaped product, it can be applied without performing manual stretching work, and the film is difficult to be deformed at the time of application. It is providing the manufacturing method of the decorating film which can be affixed easily, and a decorating film.
Moreover, the subject of another embodiment of this invention provides the manufacturing method of the decorative molded body with the favorable external appearance by which the surface of the molded object which has a three-dimensional shape was decorated by the decorative film, and a decorative molded body It is to be.

Means for solving the problems include the following embodiments.
<1> A decorative film that has a skin layer, a base material layer, a shape retention layer, an adhesive layer, and an adhesive layer protective sheet in this order, and is used for decorating a molded body having a three-dimensional shape.
<2> The decorative film according to <1>, wherein the decorative film is disposed on the surface of the molded body as a preformed body at a temperature of 80 ° C. to 150 ° C.
<3> The decorative film according to <1> or <2>, wherein the shape maintaining layer includes at least one resin selected from acrylonitrile / butadiene / styrene copolymer and polyvinyl chloride.
<4> The decorative film according to any one of <1> to <3>, wherein the skin layer includes a fluororesin.
<5> The decorative film according to any one of <1> to <4>, wherein the base material layer includes a polyvinyl chloride resin.

<6> The decorative film according to any one of <1> to <5>, wherein the skin layer has unevenness on a surface opposite to the base material layer.
<7> The decorative film according to any one of <1> to <6>, wherein the base material layer includes a colorant.

<8> The decorative film according to any one of <1> to <7>, wherein the shape-retaining layer has a thickness of 100 μm to 500 μm.
<9> The decorative film according to any one of <1> to <8>, further including a primer layer between the shape maintaining layer and the adhesive layer.

<10> A step of forming a base material layer containing a polyvinyl chloride resin using a resin composition containing a polyvinyl chloride resin, an acrylonitrile / butadiene / styrene copolymer on one surface of the base material layer, and A step of forming a shape-retaining layer using a thermoplastic resin composition comprising at least one resin selected from polyvinyl chloride, an adhesive layer on the surface of the shape-retaining layer opposite to the side having the base material layer A step of coating the surface of the adhesive layer opposite to the shape-retaining layer side with an adhesive layer protective sheet, a step of preparing a skin layer containing a fluororesin, the skin layer and the base material layer And a step of laminating the shape retention layer and the adhesive layer in this order to obtain a laminated body, and applying a laminate embossing process using a squeezing roll on the skin layer side of the obtained laminated body, Said substrate layer of layer The manufacturing method of a decorating film including the process of forming an uneven | corrugated pattern in the surface on the opposite side to the side.
<11> The method for producing a decorative film according to <10>, further including a step of forming a primer layer between the shape retaining layer and the adhesive layer.

<12> A molded body having a three-dimensional shape and an adhesive layer from which the adhesive layer protective sheet has been peeled off from the decorative film according to any one of <1> to <9>, are attached to the surface of the molded body. A decorative molded body having a laminated body.

<13> A step of preforming the decorative film according to any one of <1> to <9> into a shape suitable for the shape of a molded body to which the decorative film is pasted by a vacuum forming method, The process of peeling the adhesive layer protective sheet of the decorative film, and the decorative laminate derived from the decorative film, from which the adhesive layer protective sheet was peeled off, have the three-dimensional shape through the adhesive layer of the decorative laminate. The manufacturing method of the decorative molded object including the process affixed on the surface of the molded object to have.

According to an embodiment of the present invention, when affixed to a three-dimensional shaped product, it can be affixed without performing a manual stretching operation, and the film is hardly deformed at the time of affixing. A decorative film that can be easily attached and a method of manufacturing the decorative film can be provided.
In addition, according to another embodiment of the present invention, a decorative molded body having a good appearance and a method of manufacturing the decorative molded body, in which the surface of the molded body having a three-dimensional shape is decorated with a decorative film, are provided. can do.

It is a schematic sectional drawing which shows one aspect | mode of the decorating film of this indication. It is a schematic sectional drawing which shows the one aspect | mode of the decorative molded body of this indication. It is the schematic which shows the one aspect | mode of the manufacturing method of the decorating molded object using the decorating film of this indication, and shows the state which preformed the decorating film. It is the schematic which shows the state which peeled the contact bonding layer protection sheet from the preformed decorating film obtained by FIG. 3A, and was set as the decorating laminated body. It is the schematic which shows the aspect which has arrange | positioned the decoration laminated body obtained by FIG. 3B to the roof of the motor vehicle which is a molded object.

Hereinafter, the decorative film of the present disclosure, the method of manufacturing the decorative film, the method of manufacturing the decorative molded body, and the decorative molded body will be described in detail.
The constituent elements described below may be described based on typical embodiments of the present disclosure, but the present disclosure is not limited to such embodiments.
In the present disclosure, “to” indicating a numerical range is used in a sense including numerical values described before and after the numerical value as a lower limit value and an upper limit value.
In the numerical ranges 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 description. . Further, in the numerical ranges described in the present disclosure, the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples.
In the present disclosure, a 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 there is a specific indication when there are a plurality of substances corresponding to each component in the composition. means.
In the present disclosure, the term “step” is not limited to an independent step, and is included in the term if the intended purpose of the step is achieved even when it cannot be clearly distinguished from other steps.

The “layer containing a resin” in the present disclosure refers to a “layer formed including a resin that is a main component of the layer”. That is, the “layer containing a resin” in the present disclosure is a resin layer containing only a resin and a resin composition further containing optional components such as a plasticizer, a colorant, and an ultraviolet absorber in addition to a resin as a main component. It is used to include both formed layers.
In addition, the “resin that is a main component” in the present disclosure refers to a resin that is contained in an amount of 60% by mass or more based on 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. An acrylonitrile / butadiene / styrene copolymer may be referred to as an ABS resin.
Further, in the present disclosure, the “molded body having a three-dimensional shape” or “molded body” refers to a molded body before decoration (base of the molded body), and the “decorated molded body” refers to the decorative body of the present disclosure. It refers to a molded body decorated with a film.
A laminate obtained by peeling the adhesive layer protective sheet from the decorative film, which is used for attaching to the adherend, that is, a laminate having a skin layer, a base material layer, a shape retention layer and an adhesive layer is “decorative laminate” Called.

The decorative film of the present disclosure has a skin layer, a base material layer, a shape retention layer, an adhesive layer, and an adhesive layer protective sheet in this order, and is used for decorating a molded body having a three-dimensional shape. It is done.
When the decorative film is used for decorating a molded body having a three-dimensional shape, the shape-retaining layer suppresses the shrinkage of the adhesive layer protective sheet when the decorative film is preformed by vacuum forming or the like, and is preliminarily designed. We believe that it will contribute to the molding. Furthermore, it is considered that the shape at the time of preforming is easily maintained by the function of the shape-retaining layer even after the pressure at the time of preforming is removed. The decorative film of the present disclosure is a form of a decorative molded body after peeling the adhesive layer protective sheet after vacuum forming, that is, a decorative laminate having a skin layer, a base material layer, a shape retention layer, and an adhesive layer. Even if it is a form, in order to maintain the shape which adapts to the molded object which has the three-dimensional shape which is a to-be-adhered body, it can stick to a molded object easily.
Therefore, by using the decorative film of the present disclosure, the decorative laminate derived from the decorative film can be easily attached to a molded body having a three-dimensional shape.
By using the decorative film of the present disclosure, for example, a decorative molded body in which the appearance of a vehicle such as an automobile can be easily changed, and various designs are applied to the surface of various molded bodies having a three-dimensional shape. Can be easily manufactured.

Hereinafter, the decorative film of the present disclosure, the method for manufacturing the decorative film, the method for manufacturing the decorative molded body, and preferred embodiments of the decorative molded body 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, a shape retention layer, an adhesive layer, and an adhesive layer protective sheet in this order.

The decorative film of the present disclosure will be described with reference to FIG. FIG. 1 is a schematic cross-sectional view illustrating a preferred embodiment of the layer configuration of the decorative film 10 of the present disclosure.
A decorative film 10 shown as an example in FIG. 1 is provided on a surface opposite to the surface having an uneven surface layer 12 (hereinafter referred to as a skin layer, as appropriate) having an uneven surface on one surface. The obtained base material layer (hereinafter referred to as a base material layer as appropriate) 14, shape retention layer 16, adhesive layer 20, and adhesive layer protective sheet 22 covering adhesive layer 20 are provided in this order.
In addition, the unevenness | corrugation of equal intervals in the skin layer 12 shows the fine uneven | corrugated pattern formed in the skin layer 12 typically.
“Having each layer in this order” means that the respective layers exist in the order described, and does not deny the presence of any layer further provided as necessary.
In FIG. 1, a primer layer 18 that is a resin layer that improves the adhesion between the shape-retaining layer 16 and the adhesive layer 20 is provided between the shape-retaining layer 16 and the adhesive layer 20. Any layer provided.
In one embodiment of the decorative film 10 shown in FIG. 1, a laminate (decorative laminate) having an outer skin layer 12, a base material layer 14, a shape retaining layer 16, a primer layer 18, and an adhesive layer 20 in order. Body) 24 structure. As shown in FIG. 1, the surface of the skin layer 12 opposite to the base material layer 14 side may have a concavo-convex pattern also referred to as a texture pattern.
Since the surface having the uneven pattern of the skin layer is located on the outermost surface when the decorative film is arranged in a molded body to be described later and used as a decorative molded body, it may be hereinafter referred to as a surface. The concavo-convex pattern is a pattern that characterizes the appearance of the surface of the molded body by a decorative film, typified by a natural leather-like concavo-convex pattern, and is provided as necessary.
Moreover, the base material layer 14 can provide arbitrary hues to the decorative film 10 by including a colorant, for example. For this reason, a desired hue can be easily provided to the decorative molded body to which the decorative film 10 of the present disclosure is applied.
In FIG. 1 to FIG. 3C, components indicated by using the same reference numerals mean the same components.

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

(1. Skin layer)
The skin layer of the decorative film is formed of a resin. Especially, it is preferable that a skin layer contains a fluororesin. When the skin layer contains a fluororesin, the durability of the decorative film is improved, and if desired, when the concave / convex pattern is formed on the surface opposite to the substrate layer side, the retainability of the concave / convex pattern Will be 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 polymerizing an olefin containing a fluorine atom. The resin obtained is preferable.
Examples of the fluororesin include a resin that includes a polymerization component selected from ethylene tetrafluoride, trifluoroethylene chloride, vinyl fluoride, and vinylidene fluoride. More specifically, a trifluoride chloride is a homopolymer of a polymer component containing a fluorine atom, such as a tetrafluoroethylene resin, a vinyl fluoride resin, or a vinylidene fluoride resin, and a copolymer containing the polymer component. Examples thereof include an ethylene-vinylidene fluoride copolymer, a vinylidene fluoride-6-propylene fluoride copolymer, and a vinylidene fluoride-6-propylene-4-tetrafluoroethylene copolymer. Among these, from the group consisting of ethylene trifluoride-vinylidene fluoride copolymer, vinylidene fluoride-6-propylene fluoride copolymer, and vinylidene fluoride-6-propylene-4-tetrafluoroethylene copolymer It is preferable to include at least one selected fluororesin.

When a skin layer contains a fluororesin, it may contain only 1 type of fluororesin, and may use 2 or more types together.
When the skin layer contains two or more kinds of fluororesins, for example, vinylidene fluoride resin, trifluoroethylene chloride-vinylidene fluoride copolymer, vinylidene fluoride-6 fluoropropylene copolymer, and fluoride It is also a preferred embodiment to use a mixture of two or more kinds of resins selected from the group consisting of vinylidene-6 fluoropropylene-4 fluoroethylene copolymer.

When the skin layer includes two or more kinds of resins, in addition to the aspect in which the skin layer is a mixture of two or more kinds of resins as described above, it is possible to take a form of a laminated structure of two or more kinds of resins. For example, as the skin layer, the outermost surface, that is, the surface corresponding to the outside when the decorative film is disposed on the molded body is a layer containing a fluororesin, and the adhesion between the skin layer and the base material layer is further improved. For the purpose, the skin layer can be positioned on the surface in contact with the base material layer as a two-layer structure of a layer containing a fluororesin and a layer containing an acrylic resin.

The skin layer may be formed by a known sheet forming method, for example, an extrusion method by extruding with a T die, a calendar method, a casting method, or the like, or may be formed by applying a commercially available film.
Examples of the commercially available film that can be used for the skin layer include KCF film manufactured by Kureha Extech Co., Ltd., Acryprene (registered trademark) FBS006 manufactured by Mitsubishi Chemical Corporation. The KFC film is a multilayer film having a laminated structure of a polyvinylidene fluoride layer and an acrylic resin layer. Acryprene is a multilayer film having a laminated structure of a fluororesin-containing layer and an acrylic resin-containing layer.

The thickness of the skin 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 viewpoints of strength and ruggedness pattern retention when the rugged pattern is formed.
Here, the thickness of the skin layer refers to the distance from the top of the convex portion of the surface on which the concavo-convex pattern is formed to the bottom surface of the skin layer.
The thickness of the skin layer is determined from the distance between the bottom of the concave portion of the concave / convex pattern and the top of the convex portion from the viewpoint of retaining the concave / convex pattern formed on the side opposite to the surface of the base layer of the skin layer. Is also preferably large. For example, when forming a concavo-convex pattern in which the depth of the concave portion is 1 μm or less, the thickness of the skin layer can be about 5 μm, and it has a shallow concave portion and a deep concave portion like a natural leather-like pattern. However, in the case of forming a concavo-convex pattern having deep concave portions of 2 μm to 5 μm, the thickness of the skin layer is preferably 10 μm or more.
Note that the thickness of the skin layer when the skin layer has a laminated structure of two or more layers as described above refers to the total thickness of a 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 perpendicular 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 for forming the skin layer on the surface of the base material layer opposite to the surface on the shape retaining layer side is arbitrary. For example, a preformed skin layer and a base material layer may be adhered, and after forming the skin layer, the base material layer may be formed on one surface of the skin layer.

In addition, there is no particular limitation on the method of forming a concavo-convex pattern on the surface of the skin layer opposite to the surface on the base material layer side, and known methods can be applied. Known methods include a method of forming a skin layer on a release paper having a concavo-convex pattern, a method of first forming a skin layer having a smooth surface, and then embossing using a squeeze roll.

(2. Base material layer)
The base material layer is formed of a resin. It is preferable that a base material layer contains PVC resin as resin.
When the base material layer contains the PVC resin, the thermal stress related to the skin layer is relieved, and the retainability of the uneven pattern formed on the skin layer as desired is improved.
There is no restriction | limiting in particular as a PVC resin, A well-known film forming PVC resin can be selected suitably, and can be used.

The base material layer may contain other components in addition to the PVC resin as a preferred resin. Examples of other components that can be included in the base material layer include colorants, plasticizers, fillers, lubricants, and processing aids. In addition, other components can be used in the range which does not reduce the heat workability of a base material layer.

The base material layer can contain a colorant.
When the base material layer contains a colorant, the hue, design, etc., originally possessed by the molded body that is the substrate to be adhered is the area of the decorated molded body in the region where the decorated laminate is affixed in the production of the decorated molded body. It can suppress giving an influence on an external appearance, and can give arbitrary hues to the decoration laminated body derived from a decoration film, and by extension, the decoration molded object which affixes a decoration laminated body.
When the said skin layer contains a fluororesin and transparency is favorable, the hue of a base material layer can characterize the external appearance of a decorating film by including a coloring agent in a base material layer.
For example, the adhesive layer protective sheet is peeled from the decorative film using a decorative film having a base material layer containing a silver colorant having a different hue only on the roof portion of a red vehicle as a molded body. By attaching the decorative laminate to the roof of the vehicle and decorating, the car body is red, only the roof with the decorative laminate attached is a silver vehicle, and the place where the decorative laminate is attached is Red, which is the original hue of the molded body, is concealed.

There is no restriction | limiting in particular in the coloring agent in case a base material layer contains a coloring agent, Dye, a pigment, etc. can be selected suitably and can be used.
Colorants include titanium white (titanium dioxide), zinc white, ultramarine blue, cobalt blue, petal, vermilion, yellow lead, titanium yellow, carbon black and other inorganic pigments, quinacridone, permanent red 4R, isoindolinone, and hansa yellow. A, organic pigments or dyes such as phthalocyanine blue, indanthrene blue RS, 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 powders And nacreous (pearl) pigments selected from the group. Among these, a pigment that is a colorant having excellent weather resistance and durability is preferable, and black pigments such as carbon black, aniline black, and perylene black are more preferable from the viewpoint that the molded body can be effectively concealed.
The base material layer may contain extender pigments (fillers) such as calcium carbonate, silica (silicon dioxide), alumina (aluminum oxide), and barium sulfate as necessary.

When a base material layer contains a coloring agent, only 1 type of coloring agents may be included and 2 or more types may be included for the purpose of toning.
There is no particular limitation on the content of the colorant in the resin composition used for forming the base material layer, and the type and content of the colorant to be used depending on the target hue and decorativeness of the molded product in the decorative film. What is necessary is just to select quantity etc. suitably.
The content of a general colorant when using a colorant is preferably 1% by mass to 20% by mass with respect to the total solid content of the resin composition constituting the base material layer, and preferably 2% by mass to More preferably, it is 10 mass%. In addition, solid content means the total amount of the component except the solvent in all the components of the resin composition which comprises a base material layer here.

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

There is no restriction | limiting in particular in the formation method of a base material layer, A well-known sheet forming method, for example, the extrusion method extrusion-molding with a T die etc., a calendar method, a casting method, etc. are applicable.
Of these, the calendar method is preferable in terms of ease of production and easy maintenance of the apparatus. In particular, when the base material layer contains a colorant, a softened resin and a solid colorant can be supplied to a calender roll and formed into a sheet or film, so that groups containing various colorants can be used. The material layer can be easily manufactured.
In addition, by applying the calendar method, it is possible to more easily clean the inside of the apparatus required when changing the type and amount of the colorant compared to a molding method such as an extrusion method. For this reason, by applying a calendering 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 film Suitable for production.

(3. Shape retention layer)
A shape-retaining layer is provided on the surface of the above-described base material layer opposite to the skin layer side. The shape retaining layer is formed of a resin. The shape retention layer preferably contains at least one resin selected from ABS resin and PVC resin.
The shape holding layer is a layer having a function of holding the shape of the decorative film formed at the time of preforming as it is even when the temperature is lowered after the preforming.
That is, when the decorative film has a shape-retaining layer, the decorative film is preformed by a means such as vacuum forming under a temperature condition of 80 ° C. to 150 ° C., and then the temperature is lowered to room temperature (25 ° C.). However, the entire decorative film retains the preformed shape due to the function of the shape retaining layer, and further retains the shape even after the later-described adhesive layer protective sheet is peeled off.
A layer that gives the function of retaining the shape of the decorative film that has been preformed after preforming with heating is referred to as a shape-retaining layer in the present disclosure.

Here, “the shape is maintained” means that when a decorative film having a shape maintaining layer is preformed and the decorative film after the preliminary molding is fixed at one point in the corner, the unfixed portion is It means not to cause deformation such as sagging due to gravity.

The decorative film of the present disclosure has a shape retaining layer in addition to the skin layer and the base material layer. By selecting the resin contained in the base material layer, the thickness of the base material layer, etc., it is possible to give the base material layer a shape retention function. It is necessary to maintain the thickness and rigidity of the layer within a predetermined range. However, in order to increase the thickness or impart rigidity, there are limitations on the blending of the base material layer, which may affect the appearance quality and the like due to the dispersibility of the pigment.
However, apart from the base material layer, by providing a shape-retaining layer on the side opposite to the skin layer side of the base material layer, while maintaining the appearance quality attributed to the base material layer, the shape-retaining film is maintained. Can give function. For this reason, in the decorative film of this indication, a shape maintenance layer is provided as a layer different from a base material layer.

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 molding method or the like, the adhesive layer and the adhesive layer protective sheet to be laminated are contracted. In addition, the retention of the preformed shape is suppressed, and the local stretched portion at the time of the preforming is effectively suppressed from breaking due to stretching.
The ABS resin and the PVC resin may be used alone, or may be used by mixing with AS resin, polycarbonate (PC), polypropylene (PP), or the like. Moreover, you may use ABS resin and PVC resin together.
Especially, it is preferable to use ABS resin or PVC resin alone as a 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 a resin. preferable.
Only one ABS resin may be used, or two or more ABS resins having different copolymerization ratios may be used in combination.
There is no restriction | limiting in particular as a PVC resin, A well-known film forming PVC resin can be selected suitably, and can be used.

In addition to at least one resin selected from ABS resin and PVC resin, the shape retaining layer may contain other components as necessary as long as the effect is not impaired. Examples of other components that can be included in the shape-retaining layer include colorants, plasticizers, fillers, lubricants, processing aids, and the like.
When the shape-retaining layer contains a colorant, the decorative laminate obtained by peeling the adhesive layer protective sheet from the decorative film is disposed on the surface of the molded body, and when the decorative molded body is produced, the hue of the molded body is It can suppress more effectively affecting the external appearance of a decoration molded object, and decorating property improves more.

The colorant that can be contained in the shape-retaining layer is the same as the colorant that can be used in the base layer described above, and a desired color may be selected according to the purpose. The preferred content of the colorant when used in the shape-retaining layer can also be appropriately selected according to the purpose. From the viewpoint of layer uniformity, the content of the colorant is preferably 20% by mass or less based on the total solid content of the resin composition used for forming the shape-retaining layer.

The thickness of the shape retaining layer is preferably in the range of 100 μm to 500 μm, more preferably in the range of 200 μm to 400 μm, from the viewpoint that the preformed shape of the decorative film is easily maintained. When the thickness is in the above range and at least one kind of resin selected from ABS resin and PVC resin is included, the shape retention when the decorative film is preformed becomes better.

(4. Adhesive layer)
The decorative film includes an adhesive layer for improving the adhesion to the molded body on the surface of the shape-retaining layer opposite to the base material layer.
The adhesive layer can be formed by applying at least one of a known adhesive and pressure-sensitive adhesive to the surface of the shape-retaining layer opposite to the base material layer.
There is no restriction | limiting in particular as an adhesive agent used for formation of a contact bonding layer, According to the kind of molded object, it selects suitably. As the adhesive, for example, (1) a two-component curable polyester adhesive, (2) a two-component curable urethane adhesive, and (3) a two-component curable acrylic pressure-sensitive adhesive are preferably used.
The adhesive used for forming the adhesive layer is also available as a commercial product. For example, the Oliveline series [Toyo Ink Co., Ltd.], Welder Adhesive No. 3660 [two-component curable polyurethane adhesive: No Tape Industry Co., Ltd.], Daikarak 7250NT [two-component curable polyester adhesive: Daido Kasei Kogyo Co., Ltd.] and the like are suitable.
The thickness of the adhesive layer is preferably in the range of 20 μm to 80 μm, and more preferably in the range of 30 μm to 60 μm.

In addition, when forming an adhesive layer on the surface of the shape retention layer, a primer layer described later is formed between the shape retention layer and the adhesive layer for the purpose of improving adhesiveness, An adhesive layer can be formed by applying at least one of an adhesive and a pressure-sensitive adhesive.
As a method for applying an adhesive layer on the shape-retaining layer or 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 a transfer method.

(5. 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, a resin film, a release-treated paper, a resin-laminated paper, or the like can be used as appropriate. From the viewpoint of good preformability, a resin film is preferable. Examples of the resin film include a PP film and a PET film, and a PP film is preferable. Examples of the PP film include a CPP (unstretched polypropylene) film and an OPP (biaxially stretched polypropylene) film, and a CPP film is more preferable.
The thickness of the adhesive layer protective sheet is not particularly limited, but is preferably in the range of 30 μm to 100 μm and more preferably in the range of 40 μm to 70 μm from the viewpoint of good preformability.
The adhesive layer protective sheet is peeled off when applied to a molded body after preforming a decorative film to be described later.

(6. Other layers)
The decorative film may further include other layers as long as the effect is not impaired in addition to the above-described skin layer, base material layer, shape retention layer, and adhesive layer.
Examples of other layers include a primer layer and a design layer.

(6-1. Primer layer)
The decorative film has a resin layer as a primer layer between the adhesive layer and the shape retaining layer for the purpose of improving the adhesion between the adhesive layer provided adjacent to the shape retaining layer and the shape retaining 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 on the surface of the shape-retaining layer opposite to the substrate layer side, and drying.
The resin contained in the primer layer is a resin such as a polyester resin from the viewpoint of good affinity with the thermoplastic resin contained in the shape-retaining layer and the adhesive contained in the adjacent adhesive layer. It is preferable to form using.
There is no restriction | limiting in particular in the application quantity of the resin layer as a primer layer, According to the objective, it selects suitably. In general, from the viewpoint of the effect of improving adhesiveness, the range is preferably 1 g / m ² to 5 g / m ² , and more preferably 2 g / m ² to 3 g / m ² .

(6-2. Design layer)
The decorative film 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, may be a printed layer formed by printing, may be a colored layer containing a colorant, or may be a layer using these in combination. .
By providing a design layer on the decorative film of the present disclosure, various designs according to the use of the decorative film can be imparted to the molded body as desired, and an appearance having excellent design properties can be imparted to the molded body. Can do.

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 having a print image formed by a known printing method using a printing ink containing a resin. The printing ink containing a resin is preferably a printing ink containing an acrylic resin, a vinyl chloride-vinyl acetate copolymer, or the like from the viewpoint that a clear print image can be formed.
There is no restriction | limiting in particular in a printing method, Arbitrary printing methods, such as gravure printing (intaglio printing), relief 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. As a colored layer, the layer formed with the resin composition containing arbitrary coloring agents is mentioned. For example, a resin composition containing an acrylic resin and a colorant selected from those listed as the colorant that can be used in the base material layer described above was formed into a film by a calendar method, an extrusion method, a casting method, or the like. Examples include a design layer.

Specific examples of the acrylic resin that can be used for forming the design layer include, for example, a polymer or copolymer of methacrylic acid or a methacrylic ester represented by polymethyl methacrylate (PMMA), an alkyl methacrylate, and an 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 copolymer are preferred.

The acrylic resin is excellent in weather resistance and stretchability, and has good adhesion to other resin layers provided adjacent to each other.
Since 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 obtain a design layer that can arbitrarily give a desired excellent hue, a design having excellent gloss, and the like to the decorative film.
Moreover, when forming a printing ink layer using the printing ink containing an acrylic resin, compared with the case where the design layer as a monochromatic colored layer is applied to a decorative film by printing a character, an image, etc. Further, any more complicated design can be given.

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 in the range of 2 μm to 5 μm. Further preferred. When the thickness is in the above range, a desired design can be imparted to the decorative film, and good correlation between the skin layer and the base material layer is maintained when preforming the decorative film. The retention of the uneven pattern on the skin layer becomes better.

As a preferable aspect of the decorative film of the present disclosure, an aspect having an uneven surface on one surface and a layer having good heat resistance containing a fluororesin can be given as the skin layer. In the skin layer containing a fluororesin, the uneven pattern formed on one surface as desired is not easily deformed by heating. Further, the skin layer is preferably laminated with a base material layer containing a PVC resin and a shape holding layer containing at least one resin selected from ABS resin and PVC resin. When the decorative film having these layers is preformed by a vacuum forming method or the like, the shape retainability becomes better.
In a preferred embodiment, the base layer and the shape-retaining layer containing at least one resin selected from the ABS resin and the PVC resin adjacent to each other are both flexible and easily deformed, and at least one selected from the ABS resin and the PVC resin. Due to the shape-retaining layer containing the above resin, the shrinkage of the adhesive layer protective sheet during vacuum forming is suppressed, and the preforming as designed can be performed. Furthermore, the shape at the time of preforming is easily maintained even after the pressure at the time of preforming is removed and the temperature is lowered. Therefore, even after peeling the adhesive layer protective sheet after vacuum forming, the decorative laminate having the skin layer, the base material layer, the shape-retaining layer, and the adhesive layer has a three-dimensional shape that is an adherend to be attached. Since the shape suitable for the molded body is maintained better, it can be easily attached to the molded body.

The decorative film of the present disclosure has a skin layer that is excellent in transparency and durability on the outermost surface and has a good maintainability of the uneven pattern during heating, and excellent in heat workability. And a shape-retaining layer having excellent shape-retaining properties during preforming. For this reason, the decorative laminate obtained by pre-molding the decorative film into a shape suitable for the irregularities of the three-dimensional molded article and then peeling off the adhesive layer protective sheet is the retainability of the uneven pattern of the skin layer Is good, and retains the preformed shape with a certain degree of flexibility. Therefore, when a preformed decorative laminate is pasted on the surface of a three-dimensional shaped product, positioning can be easily performed, and any design can be easily formed on the molded product by the decorative laminate. .
The decorative molded body obtained by sticking the decorative laminate to the surface reflects the design of the decorative film and is excellent in appearance and excellent in durability such as solvent resistance.
Therefore, the decorative film of the present disclosure can be applied to various uses as a decorative film that imparts designability to the surface of a molded article having an uneven shape.
Furthermore, when the decorative film of the present disclosure is applied to the interior and exterior of an automobile, a preformed body having rigidity equivalent to that of an automobile assembly part can be obtained even though it is a film, so that construction in an automobile production line is possible. Has the advantage.

<Method for producing decorative film>
There is no restriction | limiting in particular in the manufacturing method of the decorating film of this indication as stated above, A well-known manufacturing method can be employ | adopted suitably.
Especially, it is preferable to manufacture with the manufacturing method of the decorating film of this indication mentioned later.

The method for producing a decorative film of the present disclosure includes a step of forming a base material layer containing a polyvinyl chloride resin using a resin composition containing a polyvinyl chloride resin (step (I)), A step of forming a shape-retaining layer on one surface using a thermoplastic resin composition containing at least one resin selected from acrylonitrile / butadiene / styrene copolymer and polyvinyl chloride resin (step (II)); A step of forming an adhesive layer on the surface of the shape-retaining layer opposite to the side having the base material layer (step (III)), and the surface of the adhesive layer on the side opposite to the shape-retaining layer side is the adhesive layer The step of covering with a protective sheet (step (IV)), the step of preparing a skin layer containing a fluororesin (step (V)), the skin layer, the base material layer, the shape retaining layer, and the adhesive layer, A process of stacking in this order to obtain a laminate (work (VI)), and laminate embossing is performed on the skin layer side of the obtained laminate using a squeezing roll, and a concavo-convex pattern is formed on the surface of the skin layer opposite to the shape retaining layer side. (Step (VII)).
The manufacturing method of the decorative film of this indication can further include the process (process (VIII)) which forms a primer layer between the said shape maintenance layer and the said contact bonding layer.

(Process (I))
In step (I), first, a base material layer containing a polyvinyl chloride resin is formed using a resin composition containing a polyvinyl chloride resin by a known method such as a calendering method, an extrusion method, or a casting method. Especially, it is preferable to form a base material layer by the calendar method from a viewpoint of workability. By forming the base material layer by a calendar method, for example, a base material layer having a uniform film thickness can be easily formed as compared with an extrusion method or the like. In addition, when the colorant is included in the base material layer, by applying the calendar method, it is easy to clean the inside of the device necessary when changing the type and amount of colorant used in the base material layer. It can be carried out.
If an example of the method of forming a base material layer using a PVC resin and a pigment as a colorant is given, a predetermined amount of the pigment is added to the PVC resin, and the PVC is colored by heating and mixing with a heat mixing roll. Examples include a method including obtaining a resin and forming a base material layer by a calendar method using the obtained colored PVC resin. When a colorant is not used, the base material layer can be formed in the same manner except that the pigment is not charged in the above method.

(Process (II))
In step (II), a known method such as a calendering method, an extrusion method, or a casting method is used using a thermoplastic resin composition containing at least one resin selected from ABS resin and PVC resin on one surface of the base material layer. A shape retention layer is formed by the method. Especially, it is preferable to form a shape retention layer by the calendar method from a viewpoint of workability.
The method for forming the shape-retaining layer by the calendar method can be performed in the same manner as the method for forming the base material layer in the step (I) except that the resin used is different.
Also in the shape-retaining layer, when a colorant is included, a predetermined amount of pigment is added to at least one resin selected from ABS resin and PVC resin, as in step (I), and a heat mixing roll To obtain at least one resin selected from colored ABS resin and PVC resin by heating and mixing, and to maintain the shape using at least one resin selected from the obtained colored ABS resin and PVC resin Forming the layer by a calendering method.
As described above, the thickness of the shape-retaining layer is preferably in the range of 100 μm to 500 μm, and more preferably in the range of 200 μm to 400 μm.

(Step (III))
In step (III), an adhesive layer is formed on the surface of the shape-retaining layer formed in step (II) on the side opposite to the side having the base material layer.
The adhesive layer can be formed by applying at least one of a known adhesive and pressure-sensitive adhesive to the surface of the shape-retaining layer opposite to the side having the base material layer.
There is no restriction | limiting in particular as an adhesive agent used for formation of a contact bonding layer, According to the kind of molded object, it selects suitably. As the adhesive, for example, (1) a two-component curable polyester adhesive, (2) a two-component curable urethane adhesive, and (3) a two-component curable acrylic pressure-sensitive adhesive are preferably used.
The adhesive used for forming the adhesive layer is also available as a commercial product. For example, the Oliveline series [Toyo Ink Co., Ltd.], Welder Adhesive No. 3660 [two-component curable polyurethane adhesive: No Tape Industry Co., Ltd.], Daikarak 7250NT [two-component curable polyester adhesive: Daido Kasei Kogyo Co., Ltd.] and the like are suitable.
The thickness of the adhesive layer is preferably in the range of 20 μm to 80 μm.

(Process (IV))
In step (IV), the adhesive layer formed in step (III) is covered with an adhesive layer protective sheet.
As the adhesive layer protective sheet, an easily peelable resin film is preferable as described above, and a CPP film is more preferable.
Step (IV) can be performed continuously with step (III). That is, an adhesive can be applied on the shape-retaining layer to form an adhesive layer, and the adhesive layer can be coated by applying the adhesive layer protective sheet to the surface of the adhesive layer in an uncured state.

(Process (V))
In the step (V), a skin layer containing a fluororesin is prepared. Preparing the skin layer includes both forming a skin layer containing a fluororesin and procuring a commercially available skin layer.
In the step (V), a skin layer containing a 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 coextrusion of two or more kinds of resins.
Moreover, a process (V) includes preparing the commercial film containing a fluororesin as already mentioned in description of a decorative film as a skin layer.

(Process (VI))
In step (VI), the skin layer prepared in step (V), the base material layer formed in step (I), the shape-retaining layer formed in step (II), and the adhesion formed in step (III) The adhesive layer protective sheet coated with the adhesive layer in the layer, step (IV) is laminated in the order of the skin layer, the base material layer, the shape retention layer, the adhesive layer and the adhesive protective sheet to obtain a laminate.
In the laminate, a base material layer and a shape retention layer are laminated in this order on one surface of the skin layer, and an adhesive layer is formed on the surface of the shape retention layer opposite to the base material layer side. It is formed by covering the surface (exposed side) with an adhesive layer protective sheet. Each laminated layer is pressurized and heated by a pair of rollers to form a laminate.

(Process (VII))
In step (VII), laminate embossing is applied to the skin layer side of the laminate obtained in step (VI) using a squeeze roll, and a concavo-convex pattern is formed on the surface of the skin layer opposite to the substrate side. Form.
Step (VI) and step (VII) can be performed simultaneously. That is, a base material layer, a shape-retaining layer, an adhesive layer, and an adhesive layer protective sheet are laminated in this order on one surface of the skin layer, and then laminated embossing is performed on the laminated body using a squeeze roll. The heating and pressing adhesion and the formation of a desired concavo-convex pattern on the surface of the skin layer can be performed simultaneously.
In the present disclosure, the laminate embossing is embossed by using a squeezing roll on one of a pair of embossing rolls for thermocompression bonding, and a plurality of resin-containing films are bonded together by thermocompression bonding, and in contact with the squeezing roll of the resin-containing film. It refers to forming irregularities on the surface by squeezing the surface with a squeeze roll. In the step (VII), laminate embossing is performed with an arrangement in which a squeeze roll is located on the skin layer side and a smooth roll is located on the substrate layer side. According to this method, lamination of each layer and formation of the uneven pattern in the skin layer can be performed sequentially or simultaneously in one step.

By laminating and embossing with a squeeze roll that has an irregular pattern such as a natural leather-like irregular pattern formed in advance on the surface of the skin layer, to one surface of the resin-containing film The squeezing and pressing are performed in one step, and a concavo-convex pattern of an arbitrary design such as a natural leather-like concavo-convex pattern is transferred to the outermost surface of the skin layer in the formed decorative film.
By selecting the shape of the concavo-convex pattern formed on the drawing roll, not only a natural leather-like pattern but also a pattern having an arbitrary concavo-convex shape can be formed on the surface of the decorative film.
The heating temperature in laminating embossing is preferably from 100 ° C to 190 ° C.
In addition, the method of forming unevenness on one surface of the skin layer is not limited to this. For example, when the skin layer is formed by a coating method, the composition for forming the skin layer is formed on a release paper on which the unevenness is formed in advance. It is also possible to adopt a method in which it is applied and formed by transferring the irregularities on the release paper to the skin layer.

The manufacturing method of the decorative film of this indication can contain other processes further.
For example, in the method for producing a decorative film, a step of forming a primer layer between the shape-retaining layer and the adhesive layer (step (VIII)), a step of forming a design layer between the skin layer and the base material layer ( Step (IX)) can be further included.

(Process (VIII))
In step (VIII), the primer layer can be formed by a coating method. That is, the primer layer can be formed by dissolving a resin for forming the primer layer with an appropriate solvent, applying the resin on the surface of the shape-retaining layer opposite to the substrate, and drying.
When forming the primer layer, the above-described step (III) may be performed after the step (VIII) to form an adhesive layer on the primer layer.

(Process (IX))
Step (IX) is an optional step of further forming a design layer in the method for producing a decorative film.
In step (IX), a design layer can be formed on one surface of the skin layer prepared in step (V) or the base material layer formed in step (I).
As a method for forming the design layer, for example, a method of adhering a pre-formed design layer to one side of the skin layer or the base material layer, an acrylic resin or vinyl chloride-vinyl acetate co-polymer 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.
Especially, it is preferable to form the design layer by printing because the degree of freedom of the design is high. As a design method of a design layer, in a design layer including a design, it is possible to apply a printing method. If the design layer is a colored layer, a resin composition containing a colorant can be obtained by a known method. The method etc. which shape | mold into a film form and use as a design layer are applicable.

The printing method is a method of printing a design on one surface of a skin layer or a base material layer with a printing ink containing a resin. Examples of the printing ink containing resin include printing ink containing acrylic resin, vinyl chloride-vinyl acetate copolymer and the like. Examples of the printing method include a method in which a printing ink containing the resin is printed and formed by a known printing method, for example, gravure printing (intaglio printing), relief printing, offset printing, ink jet printing, screen printing, or the like.
As an example of the printing method, specifically, a method of printing on one surface of the skin layer using a printing ink containing an acrylic resin by gravure printing, or the like can be given. 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 on one side of the skin layer or base material layer.
Since the design layer which is an arbitrary layer can be independently formed as desired on one surface of the skin layer or the base material layer, a layer having a desired design can be formed with an arbitrary hue and an arbitrary design. . Therefore, by providing the design layer, various designs can be imparted to the decorative film.

<Decorated molded body>
The decorative molded body of the present disclosure is a decorative laminate that is bonded to the surface of the molded body via a molded body having a three-dimensional shape and an adhesive layer from which the adhesive layer protective sheet is peeled off from the decorative film. And having.
FIG. 2 is a schematic cross-sectional view illustrating an example of a layer configuration of the decorative molded body of the present disclosure.
As shown in FIG. 2, the decorative molded body 30 is a decorative laminated body in which the adhesive layer protective sheet is peeled off from the decorative film of the present disclosure, which is arranged on the surface of the molded body 26 and the molded body to be decorated. 24. The decorative laminate 24 has the same layer configuration as the decorative film of the present disclosure described above, except that the decorative laminate 24 does not have an adhesive layer protective sheet. That is, as shown in FIG. 2, the decorative laminate 24 includes a skin layer 12, a base material layer 14, a shape retention layer 16, a primer layer 18, and an adhesive layer 20 having irregularities on the surface. In FIG. 2, the primer layer 18 provided for improving the adhesion between the shape-retaining layer 16 and the adhesive layer 20 is an arbitrary layer as described above.

<Method for producing decorative molded body>
The decorative film of the present disclosure as described above is suitably used for the purpose of imparting a design to the surface of the molded body when producing a molded body by heat molding.
The manufacturing method of the decorative molded body of the present disclosure includes a step (step (i) in which the decorative film of the present disclosure described above is preformed by a vacuum molding method into a shape that matches the shape of the molded body to which the decorative film is attached. )), The step of peeling the adhesive layer protective sheet of the preformed decorative film (step (ii)), and the decorative laminate derived from the decorative film from which the adhesive layer protective sheet was peeled off, The process (process (iii)) affixed on the surface of the molded object which has a three-dimensional shape through the contact bonding layer of a decoration laminated body is included.
Drawing 3A, Drawing 3B, and Drawing 3C are schematic diagrams showing an example of a process of a manufacturing method of a decoration fabrication object of this indication.

In step (i), as shown in FIG. 3A, the decorative film 10 of the present disclosure is preformed by a vacuum forming method using a mold that matches 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 a preformed decorative film (preliminarily molded decorative film). A known method can be applied to the vacuum forming method. 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 10 is arranged on the surface of the mold 25 having a shape conforming to the molded body having a three-dimensional shape, vacuum-drawn by a conventional method, and preformed along the mold 25, A preform of the decorative film 10 is obtained. In FIG. 3A, the gas flow direction in vacuum forming is schematically shown by arrows.
Since the decorative film of the present disclosure has the above-described layer configuration, it is quickly preformed by a vacuum forming method, and the obtained preform has good shape retention.

In step (ii), as shown in FIG. 3B, the adhesive layer protective sheet 22 of the decorative film 10 preformed is peeled off. Then, the decorative laminate 24 is obtained in a state where the adhesive layer protective sheet 22 is peeled off and the adhesive layer is exposed. The decorative laminate 24 has a shape-retaining layer containing at least one resin selected from ABS resin and PVC resin, so that the shrinkage of the adhesive layer protective sheet at the time of preforming is suppressed, and the shape of the preformed body is reduced. Good retention.

FIG. 3C is a schematic view showing an aspect in which the decorative laminate 24 obtained in FIG. 3B is arranged on the roof of the automobile which is the molded body 26.
In step (iii), as shown in FIG. 3C, the decorative laminate 24 derived from the decorative film, which is the adhesive layer protective sheet 22 peeled off in step (ii), is used as the adhesive layer of the decorative laminate 24. Then, it is affixed on the surface of the molded body 26 having a three-dimensional shape. Since the decorative laminate 24 has a good shape retention capability, it can be placed in the molded body 26 as it is.
Then, the decorative molded body (automobile) decorated by the decorative laminated body 24 is obtained by affixing the decorative laminated body 24 to the molded body 26 via an adhesive layer.

The decorative molded body of the present disclosure can be manufactured by a simple method as described above. Since different hues, designs, and the like can be easily imparted to the same molded body, it can be applied to various uses. Moreover, since the decorative laminated body obtained by preforming and peeling the adhesive layer protective sheet is excellent in shape retention, it can be applied to an industrial production line as one of the parts. For this reason, it is suitable for small-lot production of decorative molded bodies with different designs.
Examples of the molded body that can be applied to the decorative molded body include vehicles such as automobiles and railways, furniture, airplanes, ships, building, and wall coverings, and can be suitably used for decorating various molded bodies.

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]
(Manufacture of decorative film)
First, 100 kg of PVC resin [TH800 (trade name), Taiyo PVC Co., Ltd.] is charged with 2 kg of pigment [PV MAF 725 (trade name), Dainichi Seika Kogyo Co., Ltd.] and heated to 200 ° C. with a calendar. By the method, the base material layer was obtained by forming into a sheet shape so that the thickness after drying was 150 μm (step (I)).
On one surface of the base material layer, 100 kg of ABS resin [TM-30G6 (trade name), UMG-ABS Co., Ltd.] is heated to 200 ° C. while being heated to 200 ° C., and the thickness after drying becomes 300 μm. Thus, it shape | molded in the sheet form and formed the shape maintenance layer (process (II)).
On the shape-retaining layer, a urethane resin [Rezaroid (trade name), Dainichi Seika Kogyo Co., Ltd.] is applied to form a primer layer with a dry film thickness of 3 μm (step (VIII)), and on the primer layer Acrylic adhesive [Olivein BPS (trade name), Toyochem Co., Ltd.] was applied in such an amount that the film thickness after drying was 40 μm and dried to form an adhesive layer having a thickness of 40 μm (step (III )).
The surface of the formed adhesive layer was covered with an adhesive layer protective sheet (non-stretched PP film having a thickness of 60 μm: 40SBK0A (trade name), Fujiko Co., Ltd.) (step (IV)).

KFC film FT-50Y (trade name), Kureha Extec Co., Ltd. (a laminate of a polyvinylidene fluoride-containing layer that is a fluororesin and a polymethylmethacrylate-containing layer that is an acrylic resin) was prepared as a skin layer (process) (V)).
On the polymethyl methacrylate-containing layer side in the skin layer, a preformed base material layer, a shape retention layer, an adhesive layer, and an adhesive protective sheet were laminated in this order (step (VI)).
Using the embossed roll, which is a drawn roll in which one of a pair of embossed rolls has a drawn pattern, the skin layer side is brought into contact with the drawn roll, the laminate is embossed, and the surface has a drawn pattern. A decorative film of Example 1 having a skin layer was obtained (step (VII)). As for the temperature condition in the lamination embossing, the laminate surface temperature was 170 ° C., and the lamination embossing was performed at a speed of 10 m / min, and the decorative film of Example 1 was obtained.

[Example 2]
A decorative film was obtained in the same manner as in Example 1 except that the resin used for the shape retention layer was changed to PVC resin as follows.
On one surface of the base material layer, a sheet of PVC resin [TH800 (trade name), Taiyo PVC Co., Ltd.] 100 kg is heated to 200 ° C. by a calendering method so that the thickness after drying becomes 300 μm. To form a shape-retaining layer (step (II)).

(Comparative Example 1)
A commercially available 3M product, scratch guard (trade name) was purchased and used as a decorative film of Comparative Example 1.

(Comparative Example 2)
A laminate having a skin layer, a base material layer, an adhesive layer, and an adhesive layer protective sheet was formed in the same manner as in Example 1 except that the shape retention layer was not provided.
As a separate process, the same thickness-retaining layer as in Example 1 was used, and the thickness after drying was 100% by the calender method while heating 100 kg of ABS resin [TM-30G6 (trade name), UMG-ABS Co., Ltd.] to 200 ° C. The sheet is formed into a sheet shape so as to have a thickness of 300 μm, a shape-retaining layer is formed, and the adhesive layer protective sheet is bonded to the surface opposite to the adhesive layer with a urethane-based adhesive. A decorative film was obtained.

(Evaluation of decorative film)
The obtained decorative film was preformed into a shape shown in FIG. 3A according to the shape of the molded body at a temperature condition of 110 ° C. using a vacuum forming apparatus.

(1. Pre-molding)
The decorative films of Example 1, Example 2 and Comparative Example 2 could be preformed. In Table 1, “possible” is described in the column of preforming.
Since the decorative film of Comparative Example 1 did not have a shape retaining layer, it could not be preformed. In Table 1, “impossible” is described in the column of preforming.

(2. Adhesiveness of decorative film)
Thereafter, the adhesive layer protective sheet of each decorative film that has been preformed or cannot be preformed is peeled off as shown in FIG. 3B to form a decorative laminate, and the adhesive layer side of the decorative laminate is molded. As a body side, it was made to contact a molded object and affixed on the surface of the molded object.
Ten workers as monitors evaluated the ease of positioning of the decorative laminated body with respect to the molded body at the time of attachment based on the following criteria. Among the 10 workers, the highest evaluation was adopted. When the evaluation results were the same number, better results were listed.
The results are shown in the “Positioning” column of Table 1 below.

(Easy positioning)
A to B are in a range where there is no practical problem, and A is preferable.
A: Extremely easy B: Easy C: Somewhat difficult D: Difficult

The decorative laminate from which the decorative film and the adhesive layer protective sheet of Example 1 and Example 2 were peeled off had good preformability.
Since the decorative film of Example 1 and Example 2 did not deform | transform, it was able to be positioned easily only by attaching to a molded object.

Since the decorative film of Comparative Example 1 did not have a shape retaining layer, it could not be preformed.
The decorative film itself is flexible, and the adhesive layer side was pasted on the surface of the molded body by an ordinary manual stretching method. Since it is a smooth film, positioning was somewhat difficult, and pasting was complicated by manual stretching.

The decorative film of Comparative Example 2 could be preformed because the adhesive layer protective sheet had a shape retention layer.
When the adhesive layer protective sheet was peeled off, the shape retention layer was also peeled off, and the decorative film itself was flexible and could not maintain the shape. Positioning when adhering the decorative laminate to the molded body was slightly better than the decorative film of Comparative Example 1 because the irregularities were formed in advance, but the addition of Example 1 and Example 2 Positioning was somewhat difficult compared to the decorative film.

From the above results, it is understood that a decorative molded body can be easily obtained by using the decorative film of the example.

[Explanation of symbols]
DESCRIPTION OF SYMBOLS 10 Decorative film 12 Skin layer 14 Base material layer 16 Shape retention layer 18 Primer layer (resin layer)
20 Adhesive Layer 22 Adhesive Layer Protection Sheet 24 Decorated Laminate 26 Molded Body (Molded Body Base)
30 Decorative molded body

The disclosure of Japanese Patent Application No. 2018-097920 filed on May 22, 2018 is incorporated into this disclosure by reference.
All documents, patent applications, and technical standards mentioned in this disclosure are as if they were specifically and individually stated that each individual document, patent application, and technical standard was incorporated by reference. Incorporated by reference in the disclosure.

Claims

A decorative film that has a skin layer, a base material layer, a shape retention layer, an adhesive layer, and an adhesive layer protective sheet in this order, and is used for decorating a molded article having a three-dimensional shape.
The decorative film according to claim 1, wherein the decorative film is disposed on a surface of the molded body as a preformed body under a temperature condition of 80 ° C to 150 ° C.
The decorative film according to claim 1 or 2, wherein the shape retaining layer contains at least one resin selected from acrylonitrile / butadiene / styrene copolymer and polyvinyl chloride.
The decorative film according to any one of claims 1 to 3, wherein the skin layer includes a fluororesin.
The decorative film according to any one of claims 1 to 4, wherein the base material layer includes a polyvinyl chloride resin.
The decorative film according to any one of claims 1 to 5, wherein the skin layer has irregularities on a surface opposite to the base material layer side.
The decorative film according to any one of claims 1 to 6, wherein the base material layer contains a colorant.
The decorative film according to any one of claims 1 to 7, wherein the shape-retaining layer has a thickness of 100 µm to 500 µm.
The decorative film according to any one of claims 1 to 8, further comprising a primer layer between the shape retaining layer and the adhesive layer.
Forming a base material layer containing a polyvinyl chloride resin using a resin composition containing a polyvinyl chloride resin;
Forming a shape-retaining layer on one surface of the base material layer using a thermoplastic resin composition containing at least one resin selected from acrylonitrile / butadiene / styrene copolymer and polyvinyl chloride resin;
Forming an adhesive layer on the surface of the shape-retaining layer opposite to the side having the base material layer;
A step of covering the surface of the adhesive layer opposite to the shape-retaining layer side with an adhesive layer protective sheet;
A step of preparing a skin layer containing a fluororesin,
A step of obtaining a laminate by laminating the skin layer, the base material layer, the shape retention layer, and the adhesive layer in this order; and
A decorative film including a step of laminating embossing using a squeezing roll on the skin layer side of the obtained laminate, and forming a concavo-convex pattern on the surface of the skin layer opposite to the substrate layer side Manufacturing method.
The method for producing a decorative film according to claim 10, further comprising a step of forming a primer layer between the shape retaining layer and the adhesive layer.
A molded body having a three-dimensional shape and an adhesive layer from which the adhesive layer protective sheet is peeled off from the decorative film according to any one of claims 1 to 9, are attached to the surface of the molded body. A decorative molded body having a laminated body.
A step of preforming the decorative film according to any one of claims 1 to 9 into a shape suitable for a shape of a molded body to which the decorative film is attached by a vacuum forming method,
Peeling the adhesive layer protective sheet of the preformed decorative film, and
The decorative molding which has the process of affixing the decoration laminated body derived from the said decorating film which peeled the contact bonding layer protective sheet on the surface of the molded object which has a three-dimensional shape through the adhesive layer of the said decorative laminated body. Body manufacturing method.