JP2003191369A - Decorative film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a decorative film which is extremely thin and highly pliable and further, shows a low tack before application and a high adhesive force after application and further, are attached and firmly fixed, with satisfactory and increased operating efficiency, to an adherend having a three- dimensional curved surface. <P>SOLUTION: The decorative film includes a decorative material layer covered with a protecting layer formed of a transparent resin and an adhesive layer. In addition, the film shows a 20% modulus stress of 1 to 20 MPa and a tack value of 0.01 to 3.50 N. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a decorative film, and more specifically, it relates to a decorative film with an adhesive layer which is used by being attached to various adherends for the purpose of obtaining a decorative effect or a design effect. The decorative film of the present invention is extremely thin, has excellent flexibility, and has a controlled adhesive strength consisting of low tackiness before sticking and high adhesive strength after sticking, so that it has a three-dimensional curved surface. It can be attached and adhered to an adherend or other adherends with good and improved workability. The decorative film of the present invention can thus be advantageously used in vehicles such as automobiles, motorcycles and trains, or any other adherend.

[0002]

2. Description of the Related Art As is well known, a decorative film (also called a marking film or a sticker) attached to the side surface of a vehicle to bring out a decorative effect or a design effect.
In the past, many types have been marketed. Many of these decorative films are of considerable thickness (about 8
0 μm), the appearance after sticking is inferior, and the sticking work requires a high degree of skill because the adhesive strength of the adhesive is large. Further, there is a problem that the thickness is bad and it is very difficult to attach the adherend to a part having a three-dimensional curved surface.

Particularly, the ability of the decorative film to follow a three-dimensional curved surface is an important issue. This is because, in recent years, there is a demand for sticking a decorative film to a tighter portion having a curved shape than ever before, mainly in the exterior field of a fuel tank of a motorcycle, a fender and the like. A conventional decorative film cannot sufficiently meet this demand. In other words, in parts with complicated shapes such as fuel tanks and fenders, as the area of the part increases, the sticking work must be carefully performed so that wrinkles do not occur and bubbles are not taken in. This is because the workability of pasting is significantly reduced.

In order to solve the problem of three-dimensional followability and other problems, a method using a slide transfer material has been proposed. For example, JP-A-1-125298 discloses a transfer sheet in which an adhesive layer is provided on a base sheet via a water-soluble resin, and a pattern is printed with a coloring ink, and then a cover coat of a synthetic resin is provided. It is disclosed. In the case of this transfer sheet, the water-soluble resin is dissolved and removed in water, the base sheet is peeled off, the adhesive layer is brought into close contact with the molded article, the cover coat is peeled off, and the exposed ink layer is removed by the resin. By coating, a transfer painting method can be carried out. Further, in Japanese Unexamined Patent Publication No. 10-203094, a design layer is transferred onto an undercoated automobile body using a slide transfer material having at least a water-soluble resin layer and a design layer formed on a base sheet, Disclosed is a method for decorating an automobile body, which is characterized by applying an overcoat layer from above.

However, in the method using the slide transfer material as described above, not only the attaching work is very complicated, but also when the transfer material is peeled from the base material sheet and when it is attached to the adherend. However, it is necessary to use water or hot water to dissolve the water-soluble resin, which causes a serious problem in equipment. In addition, it takes time to extrude water from the transfer material during the sticking work, water remains between the adherend and the adhesive layer, which lowers the performance. Due to the active groups contained in the adhesive, the transfer material There is also a problem that there is a storage time limit.

On the other hand, Japanese Unexamined Patent Publication No. 2001-11396 discloses a method for applying a decorative film, which is characterized by using an aqueous emulsion type heat-sensitive adhesive composition. However, in the case of this method, there is a problem that a pre-heating step is necessary because the pressure-sensitive adhesive used has no initial tackiness, and that the adhesive force developed after heating is not sufficient at about 5 N / 25 mm. Further, in the case of this method, since the adhesive is water-based, there is an important problem that it cannot be used outdoors.

[0007]

SUMMARY OF THE INVENTION The object of the present invention is to solve the above-mentioned problems of the prior art and to be extremely thin, excellent in flexibility, low in tackiness before application and after application. It has a controlled adhesive strength consisting of a high adhesive strength, and therefore can be applied to an adherend with a three-dimensional curved surface or other adherends with good and improved workability. , To provide a marking film or other decorative film that can be fixed.

The object of the invention is also to withstand outdoor use,
In particular, it is to provide a decorative film which can be advantageously used in vehicles such as automobiles, motorcycles and trains, or any other adherend.

These and other objects of the invention are
It will be readily understood from the detailed description below.

[0010]

According to the present invention, the above-mentioned object is a decorative film used by being attached to an adherend, which comprises a decorative material layer coated with a protective layer made of a transparent resin. The decorative film comprises at least an adhesive layer, and the decorative film has a 20% modulus stress of 1 to 20 MPa and a probe tack when measured at a pulling speed of 200 mm / min in accordance with the standard specified in JIS-K7127. A tack of 0.01 to 3.50 N when measured by a test (stainless steel probe diameter: 5 mm, contact load: 9.8 N / cm ² , contact time: 10 seconds, peeling speed: 10 mm / second). Can be achieved by a decorative film characterized by having a value of

As will be easily understood from the detailed description below, the decorative film of the present invention is 1) extremely thin, and a high-quality finish with little sticking feeling is obtained, and 2) an adhesive layer is formed. By using an adhesive that has a low initial tack value and excellent sticking workability, and that can exhibit high adhesive strength over time or after heating, sufficient adhesive strength for outdoor applications can be obtained, and 3) follows a three-dimensional curved surface. 4) The weatherability, solvent resistance, and water resistance sufficient for outdoor use can be obtained. Furthermore, 5) The transparent resin is overcoated after pasting to further enhance the decorative treatment. It can be carried out.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The preferred embodiments of the present invention will be described below.

The decorative film according to the present invention can be advantageously used in a wide variety of applications. Suitable applications are not limited to those listed below, but include, for example, decorative films for vehicles and decorative films for outdoor advertising media. The decorative film of the present invention can be advantageously used as a decorative film for a vehicle, in particular, because it is extremely thin and flexible. Here, the "vehicle" is, for example, a car such as a passenger car, a truck, a bus, a hire, a motorcycle such as a motorcycle or a scooter, a train, a water bike, a snowmobile, an ATV (all-terrain vehicle). The attachment site of the decorative film in these vehicles is arbitrary, for example, the side of a bus, the side of a motorcycle tank,
And so on.

FIG. 1 is a sectional view schematically showing a preferred example of the decorative film according to the present invention. As shown in the figure, the decorative film 10 supports a decorative material layer (here, two ink layers) 2 covered with a protective layer (top coat layer) 1 made of a transparent resin, and a decorative material layer 2. The transparent substrate 3 and the adhesive layer 4 disposed on the lower surface of the transparent substrate 3, and the adherend 1 is provided with the adhesive layer 4 interposed therebetween.
1 is configured to be attached.

In the illustrated decorative film 10, the decorative material layer 2 is shown as an example composed of two ink layers, but as will be made clear below, it may be a single layer or three layers. The above-mentioned multilayer may be used. Further, the decorative material layer 2 is formed so that it occupies a substantially central region of the decorative film 10, but if desired, the edge portion thereof extends to the edge portion of the decorative film. Good. That is, the decorative film 10 may have a raised central portion, or may have a substantially flat surface. Furthermore, the decorative material layer 2
If the desired decorative effect can be obtained,
It may be formed of a material other than ink, or may be formed of a combination of ink and another material.

In the illustrated example, the decorative material layer 2 is shown as being supported by the transparent base material 3 which is usually made of a transparent resin, but in the present invention, as will be described below, these layers are formed. Both or one may be omitted. That is, the basic structure of the decorative film of the present invention is as follows: Structure 1 ... Transparent protective layer + Adhesive layer structure 2 ... Transparent protective layer + Decorative material layer + Adhesive layer structure 3 ... Transparent protective layer + Transparent substrate + Adhesive Layer Structure 4 ... A transparent protective layer + decorative material layer + transparent base material + adhesive layer can be provided. As can be easily understood, the decorative film 10 in FIG. 1 described above shows an example of the configuration 4.

Further, an example of the configuration 2 is as shown in FIG. As shown in the figure, the decorative film 10 includes a decorative material layer (here, two ink layers) 2 covered with a protective layer (top coat layer) 1 made of a transparent resin,
It has an adhesive layer 4 arranged on the lower surface of the decorative material layer 2, and is configured to be attached to the adherend 11 via the adhesive layer 4. In this decorative film 10, if the function of the decorative material layer 2 can be assigned to the transparent protective layer 1 above it and / or the adhesive layer 4 below it, the decorative material layer 2 is omitted. Thus, the decorative film having the configuration 1 can be provided. Further, the decorative material layer 2 can be omitted when the decorative effect does not depend on the decorative material layer 2 but depends on the pattern of the adherend itself. Although not shown, the decorative film of configuration 3 can also be provided with necessary modifications based on the same recognition as above.

The decorative film of the present invention may have various modifications and improvements within the scope of the present invention in addition to the above four constitutions.

For example, as shown in FIG. 2, for example, the decorative film of the present invention may be designed such that after the decorative film 10 is attached to the adherend 11, the whole is overcoated with the transparent resin 5. it can. That is, the decorative film 10 can further have the overcoat layer 5 on the uppermost layer thereof. The overcoat layer 5 has an effect of protecting the decorative film 10 and improving its appearance.

In the decorative film of the present invention, as shown in FIG. 4, for example, a sticking auxiliary member (here, an application film) 6 for assisting the work of sticking the decorative film 10 to the adherend 11 is provided with a transparent protective layer. Can further have one above. Moreover, in order to improve the handleability of the decorative film and to perform the sticking work smoothly, a release member (here, release paper) 7 having the adhesive layer 4 laminated thereon can be further included. Of course, the sticking assisting member 6 and the release member 7 may be used independently of each other or may be used in combination.

An outline of the decorative film of the present invention will be apparent from the above description with reference to the accompanying drawings. continue,
Details of the constituent features and constituent elements of the present invention will be described.

In order to achieve the intended effect, the decorative film according to the present invention needs to satisfy at least the following requirements in addition to having at least a transparent protective layer and an adhesive layer.

In the decorative film of the present invention, first, JIS
1 to 20 MPa when measured at a pulling speed of 200 mm / min according to the standard specified in K7127.
It is necessary to have a 20% modulus stress of That is, when the decorative film is viewed as a whole including the adhesive layer, the stress value at 20% extension is 1 to 20 M.
By having a modulus stress in the range of Pa, it is possible to ensure good followability to a three-dimensional curved surface. here,
If the decorative film has a 20% modulus stress of 1 MPa
When it is below the range, the film itself is too soft, so that the film is easily worn and the shape cannot be maintained. On the contrary, 2
When the 0% modulus stress exceeds 20 MPa, the film itself becomes hard, and therefore, when the decorative film is attached to the three-dimensional curved surface, it is unsuitable because it may be curled or wrinkled.

Further, in the decorative film of the present invention, when its tack value (initial tack value) is measured by the probe tack test, it is 0.01-3.
It is necessary to have a tack value of 50N. Here, the probe tack test is, as is well known, JIS-Z.
It is used as an adhesive force test method in connection with the regulations of 0237, and the test method is as follows. (1) Clean the surface of the stainless steel probe of the probe tack tester. (2) After attaching the test piece to the weight ring, it is set in the test device. (3) After the probe is brought into contact with the adhesive surface of the test piece for a certain period of time while applying a constant load, the force required for peeling the probe from the adhesive surface in the vertical direction is determined and used as the value of the probe tack. The test conditions applied in the present invention are
Diameter of stainless steel probe: 5 mm, contact load:
9.8 N / cm ² , contact time: 10 seconds, and peeling speed: 10 mm / second.

The decorative film of the present invention has a content of 0.01
By having a tack value in the range of up to 3.50 N, good workability can be secured. Here, if the tack value of the decorative film is less than 0.01 N, the adhesion is poor when the film is attached, and a problem of air intake occurs between the adherend and the film. Problems such as this occur. On the other hand, if the tack value exceeds 3.50 N, problems such as tearing or failure to maintain the shape occur when it is necessary to peel again after the completion of application.

Further, in the decorative film of the present invention, it is preferable that the peripheral edge region of the film has a smaller thickness as compared with the main region occupying the central portion of the decorative film. In such a decorative film, the thickness of the peripheral edge region is preferably in the range of 1.5 to 50 μm. Otherwise, in the decorative film of the present invention, if a satisfactory function and effect comparable to the above-mentioned form can be obtained, the entire decorative film has a substantially uniform thickness, The range may be 1.5 to 50 μm. The thickness of the decorative film referred to here is the structure 1 in which the decorative film has the minimum number of constituent elements.
It is the thickness of the film peripheral edge region in the case of (transparent protective layer + adhesive layer), and of course, in the case where additional components are included as necessary, the thickness of the added components is also of course. It must be added to the above thickness.

If the thickness of the decorative film of the present invention is less than 1.5 μm, it will be too thin and the work of attaching the film will be difficult. On the contrary, the thickness of the decorative film is 50
When the thickness exceeds μm, the effect of making the film extremely thin according to the present invention is diminished, and, for example, the end surface of the film is conspicuous
The appearance after pasting deteriorates.

In order to satisfy the above-mentioned essential or preferable requirements, the protective layer used in the decorative film of the present invention is made of a transparent resin material. The resin material used for forming the protective layer, in addition to being transparent,
Glossy for decorative film, characteristics suitable for outdoor use,
For example, it is preferable to have properties sufficient to impart weather resistance, solvent resistance, water resistance and the like. Further, in the case where the transparent resin is overcoated after the decoration film is attached, it is preferable that the transparent resin has good adhesion to the transparent resin.

The resin material suitable for forming the transparent protective layer is not particularly limited as long as the material can satisfy the above requirements. Suitable resin materials are, for example, vinyl chloride resin, vinyl acetate resin, vinyl chloride vinyl acetate copolymer resin, urethane resin, olefin resin such as polyethylene and polypropylene, epoxy resin, polyester and the like. These resins may be used alone or in combination of two or more.

The transparent protective layer may contain, if necessary, an additive commonly used in the top coat layer of the decorative film. Suitable additives are, for example, UV absorbers, light stabilizers, antioxidants and the like.

Although the thickness of the transparent protective layer can be widely changed depending on the desired function and effect, it is preferable that the total thickness of the decorative film (1.
5 to 50 μm) is satisfied. The thickness of the transparent protective layer is usually preferably at least 0.5 μm. When the thickness of the transparent protective layer is less than 0.5 μm,
This is because it becomes easier to scrape and the base is exposed. The upper limit of the thickness of the transparent protective layer is determined in consideration of the thickness of the adhesive layer used in combination, but it is usually preferably within 5 times the thickness of the adhesive layer. This is because if the thickness is more than 5 times the thickness of the adhesive layer, the heat shrinkability of the transparent protective layer deteriorates.

The adhesive layer used in combination with the above-mentioned transparent protective layer for forming the decorative film preferably has a low initial tack value, but after the decorative film is attached to the adherend, it is further heated at room temperature ( When left at (20 ° C) for 48 hours, or when heated at 80 ° C for 10 minutes, the adhesive layer shows 8N / 25
The adhesive force of mm or more can be expressed.
That is, it is preferable that the adhesive strength of the adhesive layer increases with the lapse of time after the film is attached, and it is particularly preferable that the increase of the adhesive strength is promoted by the heat treatment for the rapid increase of the adhesive strength. In addition, this adhesive force, if it is planned to use a sticking auxiliary member such as an application film to the decorative film, it is necessary to peel off the sticking auxiliary member from the decorative film in the final work stage. It is necessary that it is larger than the adhesive force of the application auxiliary member to the decorative film.

The adhesive used for forming the above-mentioned adhesive layer is not particularly limited as long as the adhesive can satisfy the above-mentioned requirements, and therefore, the heat-sensitive material generally used in this technical field. Adhesives or pressure sensitive adhesives can be used to form the adhesive layer.

For example, the heat-sensitive adhesive suitable for forming the adhesive layer is not limited to those listed below, but is not limited to the following: ethylene-acrylic resin type, ethylene-vinyl acetate copolymer resin type, polyester type, Polyurethane type,
Adhesion of reaction hardening type such as epoxy resin type, phenol resin type, polyurethane type, polyester type, polyamide type, etc., including vulcanized and solidified type such as rubber type mainly composed of styrene-butadiene (SBR) etc. It is an agent. Similarly, a pressure sensitive adhesive suitable for forming an adhesive layer is
Although not limited to those listed below, conventionally-used widely used acrylic adhesives, rubber-based adhesives containing styrene-butadiene rubber (SBR) as a main component, silicone-based adhesives, hot melts. Type adhesive.

In the practice of the present invention, pressure sensitive adhesives can be used particularly advantageously for forming the adhesive layer.
Further, when forming the pressure-sensitive adhesive layer, it is possible to advantageously use a pressure-sensitive adhesive compounded with a crystalline polymer.
Suitable crystalline polymers include, but are not limited to, those listed below, for example polycarbonates, polyesters, polyurethanes and the like. Suitably, for example, polycaprolactone. The blending amount of these crystalline polymers can be changed in a wide range depending on the desired effect level and the like, but is usually about 5 to 5 based on the total amount of the pressure sensitive adhesive and the crystalline polymer. It is in the range of 60% by mass. Regarding the blending of the crystalline polymer with the pressure sensitive adhesive, refer to the related description in JP-A-2000-119624, if necessary.

In addition to the crystalline polymer, it is preferable to add a crosslinking agent to the pressure sensitive adhesive. The presence of the cross-linking agent can prevent undesired wrinkles from being generated in the pressure-sensitive adhesive layer, and as a result, the overcoat property and the punching property of the decorative film are improved. Suitable crosslinking agents are, for example, isocyanate-based, aziridine-based, epoxy-based and metal chelate-based crosslinking agents.

The adhesive layer can be formed in the desired amount of the heat-sensitive adhesive or the pressure-sensitive adhesive as described above using a conventional coating method. However, as mentioned above, the total thickness requirement of the decorative film (1.5
To 50 μm) is preferable.
The adhesive layer typically preferably has a thickness of at least 1.0 μm. This is because the thickness of the adhesive layer is 1.
This is because if it is less than 0 μm, sufficient adhesive force cannot be obtained. On the contrary, if the thickness of the adhesive layer is too large, the punching property of the decorative film may deteriorate, which is not desirable. The thickness of the adhesive layer is preferably 5 to 30.
It is in the range of μm.

The decorative film of the present invention is optional,
It can have a decorative material layer as one of its constituent elements. The decorative material layer can be formed, for example, by printing or spraying in the form of an ink layer using a pigment ink, a dye ink, or the like, as is commonly done in decorative films. The ink layer may be a single color or a multicolor of two or more colors. Moreover, the ink layer may be a single layer or a multilayer of two or more layers.
Further, the decoration material layer may be formed by using, for example, spraying of a paint, vapor deposition of metal, sticking of a metal foil, or the like in addition to the above-described application of ink.

The thickness of the decorative material layer can be varied over a wide range depending on the type and shape of the decorative material, but is usually in the range of 1 to 30 μm. In addition, it is desirable to consider the thickness of the decorative material layer so that the end face thereof is not as thick as possible, and therefore, as described above with reference to FIGS. It is preferable to selectively form the decorative material layer so that the decorative material layer does not extend to the above, in other words, only the transparent portion exists in such a portion. In such a case, if the thickness of the decoration material layer is 60 μm or less, it is possible to avoid the generation of an undesired step feeling.

The decorative film of the present invention may further have a transparent base material between the decorative material layer and the adhesive layer. When the transparent base material is present on the adhesive layer, the decorative film can be made to sit and the decorative material layer can be easily formed.

The transparent substrate is preferably formed of a transparent resin material. The resin material suitable for forming the transparent substrate is
There is no particular limitation as long as it does not adversely affect the effects of the present invention. Suitable resin materials are, for example, vinyl chloride resin, vinyl acetate resin, vinyl chloride vinyl acetate copolymer resin, urethane resin, olefin resin such as polyethylene and polypropylene, epoxy resin, polyester and the like. These resins may be used alone or in combination of two or more.

In the decorative film of the present invention, it is preferable to add a filler to the resin material used for forming the transparent base material. Suitable fillers are, for example, silica (Si
O ₂ ), titanium oxide (TiO ₂ ), aluminum oxide (Al ₂ O ₃ ) and other inorganic substances, and urethane resin particles, acrylic resin particles and other organic substances. These fillers have a function of preventing blocking of the decorative sheet, preventing sticking of the plate during printing, and improving handleability. Such a filler is usually preferably added in an amount of 3 to 50% by mass based on the total amount of the transparent substrate.

If necessary, additives other than the filler may be added to the above resin material. Suitable additives are, for example, UV absorbers, light stabilizers, antioxidants and the like.

Further, the decorative film of the present invention preferably further has a sticking auxiliary member for assisting the work of sticking the film to an adherend on the above-mentioned transparent protective layer. Various materials are included in the attachment auxiliary member that can be used in the practice of the present invention. A suitable application aid is an intermediate transfer member commonly referred to as an application film.

The sticking assisting member used in the present invention has, in particular, a value of 0. 0 when measured at a pulling speed of 200 mm / min according to the standard defined in JIS-K7127.
5-8 MPa, 10% modulus stress, 6-25 MPa
Of 100% modulus stress and the rate of change of the modulus stress of 3.0 or more (100% modulus stress / 10% modulus stress) are preferable.

The application assisting member, typically an application film, is configured to include a base material and an adhesive layer provided on one surface of the base material. The base material is, for example, a soft vinyl chloride resin, a urethane resin, an olefin resin such as polyethylene or polypropylene, or a polyester resin. The pressure-sensitive adhesive layer applied to one side of the substrate is made of an acrylic pressure-sensitive adhesive, a rubber pressure-sensitive adhesive, a urethane pressure-sensitive adhesive, a silicone pressure-sensitive adhesive, a vinyl acetate pressure-sensitive adhesive, a hot melt pressure-sensitive adhesive, or the like. An example of a useful application film is disclosed in, for example, Japanese Patent Laid-Open No. 10-287849.

Further, in the decorative film of the present invention, it is preferable that the adhesive layer further has a release member laminated thereon. The release member is preferably a release paper (also referred to as release paper) generally used in the field of decorative films. The release paper used here is not particularly limited, and therefore, those generally used in this technical field can be used. Suitable release papers include, for example, woven or non-woven fabrics, papers, plastics, and other sheets that have been subjected to a release treatment. Further, as a suitable release agent, for example, a silicone-based release agent can be mentioned.

Furthermore, in the decorative film of the present invention,
It is preferable that the decorative film is designed so that the whole film is overcoated with a transparent resin after being attached to the adherend. The overcoat layer can be formed by using various transparent resin materials. Examples of suitable resin materials include acrylic resins, urethane resins, polyesters, epoxy resins, silicone resins and the like. These resin materials are usually supplied in the form of organic solvent-based paint, water-based paint, powder paint, ultraviolet ray or electron beam curable paint. The overcoat layer can be formed by spraying these resin materials with a predetermined thickness by, for example, a spray coating method.

The decorative film according to the present invention can be easily manufactured by a simple method, and there is no failure during manufacturing. As a preferable example, for example, the decorative film 10 in FIG. 1 can be manufactured as shown in order in FIG.

First, as shown in step (A) of FIG. 5, a transparent resin substrate 3 having an adhesive layer 4 on one surface is prepared.
Here, the resin base material 3 is made of urethane resin, and the adhesive layer is made of acrylic adhesive polymer and crystalline polymer dispersed therein. Although not shown, the exposed surface of the adhesive layer 4 provided on the resin base material 3 is covered with release paper.

Then, as shown in the step (B), the ink layer 2 is formed on the substantially central portion of the base resin 3. In the illustrated example, two types of urethane-based pigment inks were used to sequentially perform screen printing to form an attractive ink layer 2.

After forming the ink layer 2, as shown in step (C), a urethane-based clear paint is applied to the surface of the resin base material 3 so as to cover the ink layer 2 and dried. The transparent protective layer 1 is formed, and thus the previously formed ink layer 2 is
Through this transparent protective layer 1, it was possible to observe with a beautiful appearance.

The decorative film 10 of FIG. 3 can be manufactured as shown in order in FIG.

First, as shown in step (A) of FIG. 6, an application film 16 comprising a base material and an adhesive layer.
After preparing, the transparent protective layer 1 is laminated on the pressure-sensitive adhesive layer. The transparent protective layer 1 is formed by applying urethane-based clear paint,
It is formed by drying.

Next, as shown in the step (B), the ink layer 2 is formed on the transparent protective layer 1 substantially in the center thereof. In the illustrated example, two types of urethane-based pigment inks were used to sequentially perform screen printing to form an attractive ink layer 2.

After forming the ink layer 2, as shown in step (C), the release paper 7 provided with the adhesive layer 4 prepared in advance.
And the laminated body formed in the previous step are integrated. The laminate is
The ink layer 2 is inverted and integrated so that the ink layer 2 is embedded in the adhesive layer 4. By pressing the two together, the decorative film shown in FIG. 3 was obtained, and the ink layer 2 previously formed could be observed through the transparent protective layer 1 with a beautiful appearance.

The decorative film of the present invention can be applied to and adhered to an adherend in the same manner as a conventional decorative film, but by a simpler method. At that time, if necessary,
It is recommended to use the following method. When attaching the decorative film, water or water containing a surfactant is sprayed on the adherend in advance by spraying or the like, and then the attaching work is performed. Such pretreatment is effective for removing dust and the like on the surface of the adherend. Further, instead of the surfactant, ethanol, methanol or the like may be dissolved in water. Furthermore, such an aqueous solution may be sprayed onto the surface of the adhesive layer of the decorative film.

[0058]

[Material used for forming pressure-sensitive adhesive layer]

Acrylic adhesive polymer: PSA-1 ... Phenoxyethyl acrylate / 2-hydroxy-3-phenoxypropyl acrylate / n-butyl acrylate / acrylic acid (weight ratio = 30: 15:
50: 5) Copolymer Phenoxyethyl acrylate used for the preparation of this copolymer is "Viscort #" manufactured by Osaka Organic Chemical Industry.
192 "(trade name), 2-hydroxy-3-phenoxypropyl acrylate is" Aronix M-5700 "(trade name) manufactured by Toagosei Kagaku, n-butyl acrylate is manufactured by Mitsubishi Chemical, and acrylic acid is Japanese It was made by Koujunyaku Kogyo. SK1310 ... Butyl acrylate adhesive polymer,
Product name “SK1310”, Soken Chemical Crystal Polymer: 2064-059 ... Obtained by reacting product name “Kuraray Polyol O2010” (Mw = 7,000) manufactured by Kuraray Co., Ltd. with IPDI at a molar ratio of 6: 5. Polyester polyurethane (Mw = 40,000) PCL-H1P ... Polycaprolactone (Mw = 25.0)
00), trade name “PLACCEL-H1P”, cross-linking agent manufactured by Daicel Chemical Industries: epoxy cross-linking agent, trade name “E-AX”, Soken Chemical Co., Ltd. Examples 1 to 4 and Comparative Examples 1 to 2 acrylic adhesive polymer The crystalline polymer and the cross-linking agent were mixed in the ethyl acetate / toluene mixed solvent in the combinations and blending amounts (solid content% by mass) described in Table 1 below. The obtained mixed solution was applied to a polyethylene terephthalate (PET) film which had been subjected to a release treatment, and dried in an oven at 100 ° C. for 5 minutes. A PET film with a pressure-sensitive adhesive layer having a thickness of 9 μm was obtained.

Then, on the adhesive layer of the obtained PET film, a pattern was printed using urethane pigment dispersion ink (manufactured by 3M) to form an ink layer. Further, a urethane-based top clear paint was applied onto the adhesive layer so as to completely cover the ink layer and dried. A decorative film having four layers of a PET film, an adhesive layer, an ink layer, and a transparent protective layer was obtained.

Subsequently, a PET film having a thickness of 50 μm coated with an adhesive having a thickness of 20 μm was attached to the transparent protective layer of the decorative film produced as described above, and then the adhesive force, probe tack value and The sticking workability was measured by the following method. Adhesion: 20 mm diameter of the decorative film through its adhesive layer
After sticking to a 0 mm melamine coated plate, it was heated in a hot air circulation oven at 120 ° C. for 5 minutes. After the decorative film was further left at room temperature (20 ° C.) for 1 hour, the adhesive force (N / 25 mm) was measured. The adhesive force here is 180 at a peeling speed of 300 mm / min.
It is the peel strength measured when peeled in the ° direction. Probe tack value: After setting the test piece of the decorative film in the probe tack test device (stainless steel probe diameter: 5 mm), contact load: 9.8 N / cm ² , contact time: 10 seconds, and peeling speed: The probe tack value was measured at 10 mm / sec. Workability of application: different temperature conditions (15, 25 and 35 ° C)
Then, a decorative film having a diameter of 50 mm was attached to the center of a melamine coated plate having a diameter of 200 mm. After 30 seconds,
When the decorative film was peeled off from the melamine coated plate, those that did not cause any problems were rated as "○", and those that caused streaks or were lifted due to insufficient adhesive strength after attachment were rated as "X". .

Table 1 below summarizes the above measurement results.

[0062]

[Table 1]

As can be seen from the measurement results (Examples 1 to 4) in Table 1, good tacking was achieved by setting the probe tack value in the range of 0.01 to 3.50 N in the temperature range of 15 to 35 ° C. It is possible to provide a decorative film having workability. It is also found that at that time, an adhesive force of 8 N / 25 mm or more can be obtained.

In contrast to these good results, Comparative Examples 1 and 2 in which the conventional acrylic pressure-sensitive adhesive was used alone showed high tackiness and poor sticking workability.
It can also be seen that when the amount of the crystalline polymer increases and the tackiness is lost, the sticking work becomes difficult. Examples 5 to 8 and Comparative Example 3 The procedure described in Example 1 was repeated, but in these examples, when the transparent resin layer was coated on the adhesive layer with the ink layer, a urethane-based top clear paint was used. Is applied alone,
Instead of drying, the top clear paint was replaced with silica powder (trade name "sy") as described in Table 2 below.
lysia 730 ", manufactured by Fuji Silysia Chemical Ltd., was dispersed in different amounts (mass% solid content), and the mixture was applied and dried.

The obtained decorative film was evaluated for blocking resistance and elongation of 100% or more (whether or not the decorative film extends 100% or more), and the evaluation results as shown in Table 2 below were obtained. It was

[0066]

[Table 2]

As can be seen from the evaluation results in Table 2, when silica is added to the transparent protective layer, the blocking resistance of the decorative film can be improved. Examples 9 to 12 and Comparative Example 4 The procedure described in Example 1 was repeated, but in these examples, the thickness of the peripheral edge region of each decorative film is shown in Table 3 below. In addition, in order to form the overcoat layer, a transparent urethane resin was spray-coated with a thickness of 50 μm and dried and cured. The step feeling of the obtained decorative film was visually evaluated, and the evaluation results as shown in Table 3 below were obtained.

[0068]

[Table 3]

In the column of "feeling of step" in Table 3 above, "◎" indicates that no feeling of step is felt,
The sample with a slight step feeling was evaluated as "○", and the sample with a remarkable step feeling was evaluated as "x".

[0070]

As described above, according to the present invention, it is possible to obtain a controlled adhesive force which is extremely thin and excellent in flexibility, and which has low tackiness before application and high adhesion force after application. Marking tapes and other decorations that have and therefore can be adhered to and adhered to an adherend having a three-dimensional curved surface or other adherends with good and enhanced workability. Can provide film. Therefore, by using the decorative film of the present invention, for example, even for a fuel tank of a motorcycle, a portion such as a fender having unevenness or a tight three-dimensional curved surface, without causing defects such as wrinkles and air bubbles. It can be easily pasted, and the workability is extremely good.

Further, since the decorative film of the present invention has low initial tackiness and develops a strong adhesive force with the passage of time or by heating, the workability of application is extremely good, and the alignment Therefore, it is easy to remove the film, and it is possible to avoid the inconvenience that the films stick to each other during the work.

Further, when the decorative film of the present invention is used, if the overcoat is provided on the uppermost layer, damage to the marking film after sticking can be avoided, and further the appearance can be changed. You can also plan.

[Brief description of drawings]

FIG. 1 is a sectional view schematically showing a preferred example of a decorative film according to the present invention.

FIG. 2 is a sectional view schematically showing another preferable example of the decorative film according to the present invention.

FIG. 3 is a cross-sectional view schematically showing still another preferable example of the decorative film according to the present invention.

FIG. 4 is a cross-sectional view schematically showing still another preferred example of the decorative film according to the present invention.

5A to 5C are cross-sectional views sequentially showing a preferable method for manufacturing the decorative film shown in FIG.

6A to 6C are cross-sectional views sequentially showing a preferable method for producing the decorative film shown in FIG.

[Explanation of symbols]

1 ... Transparent protective layer 2 ... Decoration material layer 3 ... Transparent base material 4 ... Adhesive layer 5 ... Overcoat layer 6 ... Sticking auxiliary member 7: Mold release member 10 ... Decorative film 11 ... Adherend 16 ... Application film

[Procedure amendment]

[Submission date] January 9, 2002 (2002.1.9)

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0062

[Correction method] Change

[Correction content]

[0062]

[Table 1]

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Takanobu Yorinobu             Sumitomo 3-8-8 Minami-Hashimoto, Sagamihara City, Kanagawa Prefecture             Within 3M Co., Ltd. (72) Inventor Hiroshi Sakaguchi             Sumitomo Three, 323 Tanato, Oyama-cho, Sunto-gun, Shizuoka Prefecture             Within M Corporation (72) Inventor Hiroshi Takeda             Sumitomo Three, 323 Tanato, Oyama-cho, Sunto-gun, Shizuoka Prefecture             Within M Corporation (72) Inventor Akihiko Nakayama             Sumitomo Three, 323 Tanato, Oyama-cho, Sunto-gun, Shizuoka Prefecture             Within M Corporation F-term (reference) 4F100 AK25 AK46 AL05 AN01A                       AN01C AR00A AT00C BA03                       BA07 CA02 CB00B CB03B                       CB05B GB32 HB00 JK01                       JL09 JL11 JL12B JL13B                       YY00B

Claims (12)

[Claims] 1. A decorative film used by being attached to an adherend, which comprises at least a decorative material layer covered with a protective layer made of a transparent resin and an adhesive layer, wherein the decorative film is 1 to 20 when measured at a pulling speed of 200 mm / min according to the standard defined in JIS-K7127.
When measured by 20% modulus stress of MPa and probe tack test (stainless steel probe diameter: 5 mm, contact load: 9.8 N / cm ² , contact time: 10 seconds, peeling speed: 10 mm / second) , 0.01-
A decorative film having a tack value of 3.50 N. 2. The decorative film has a peripheral edge region having a thickness smaller than that of a main region occupying the central portion of the decorative film, and the thickness is 1.5 to 5.
The decorative film according to claim 1, wherein the decorative film is in a range of 0 μm. 3. A transparent substrate is further provided between the decorative material layer and the adhesive layer.
Or the decorative film according to 2. 4. The decorative film according to claim 1, which does not have the decorative material layer. 5. When the decorative film is attached to an adherend and then left at room temperature (20 ° C.) for 48 hours or heated at 80 ° C. for 10 minutes, the adhesive layer has a thickness of 8 N / 25 mm. The decorative film according to any one of claims 1 to 4, which exhibits the above adhesive strength. 6. The decorative film according to claim 1, wherein the adhesive layer is made of a heat sensitive adhesive. 7. The decorative film according to claim 1, wherein the adhesive layer is made of a pressure sensitive adhesive. 8. The decorative film according to claim 1, wherein the adhesive layer comprises a pressure-sensitive adhesive compounded with a crystalline polymer. 9. The sticking auxiliary member for assisting the work of sticking the decorative film to an adherend is further provided on the protective layer, according to any one of claims 1 to 8. The decorative film described. 10. The sticking auxiliary member is JIS-K71.
Tension speed 20 according to the standard specified in 27
10% modulus stress of 0.5-8 MPa, 100% modulus stress of 6-25 MPa, and 3.0 when measured at 0 mm / min.
The decorative film according to claim 9, which has the above-described rate of change in modulus stress (100% modulus stress / 10% modulus stress). 11. The decorative film according to any one of claims 1 to 10, which is designed such that the whole body is overcoated with a transparent resin after being attached to the adherend. . 12. The decorative film according to any one of claims 1 to 11, which is a decorative film for vehicles.