JP2003326629A - Marking film, receptor sheet and marking film for vehicle - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a marking film which is excellent in petroleum resistance and moistureproofness and especially suitable for an vehicle moving by using petroleum fuel. <P>SOLUTION: The marking film is provided with a receptor film having a front surface and a rear surface which respectively function as a coloring material-receiving surface, the coloring material received on the surface and an adhesive-containing adhesion layer arranged on the rear surface. The adhesion layer has a projected part formed on an adhesion surface and a recessed part around the projected part. A communicating route to the outside defined by the recessed part is formed between the surface of a body to be bonded and the adhesion surface of the adhesion layer. The receptor film has a surface becoming the coloring material-receiving surface and is composed of a thermalplastic resin film containing a petroleumproof resin selected from polyurethane having a polycarbonate polyol derived polyol unit or a polycaprolactone polyol derived polyol unit and a phenoxy resin, or the receptor film is a petroleumproof resin film containing a copolymer containing a 1-8C alkyl acrylate and methyl methacrylate. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an improvement of a marking film provided with a receptor film that receives a coloring material such as toner forming an image (image display layer) or a coloring layer, and an adhesive layer having an uneven adhesive surface. Regarding INDUSTRIAL APPLICABILITY The marking film of the present invention can be used as a marking film for vehicles, which is used by adhering it to the body surface of a vehicle that moves by using petroleum-based fuel, particularly light oil.

[0002]

2. Description of the Related Art A receptor sheet which can form an image (image display layer) or a colored layer by applying a toner or an ink as a coloring material on the surface thereof is used, for example, for producing a marking film. The receptor sheet is usually provided with a receptor film comprising a base layer and a receptor layer composed of a thermoplastic resin film arranged on the surface of the base layer. The back surface of the receptor film is usually provided with an adhesive layer for adhering the receptor sheet to an adherend.

The marking film is produced by forming an image or the like on the surface of a receptor sheet (receptor film) using, for example, electrostatic toner printing. When it is necessary to protect the printing surface (colorant receiving surface of the receptor layer), the printing surface is covered with a protective film. As the protective film, a polymer film having transparency through which toner (image and the like) is visible, for example, a film formed from a fluoropolymer, an acrylic polymer, a phthalate polyester (polyethylene terephthalate, etc.) is used. There is.

The thermoplastic resin film of the receptor layer is
It can be formed from various resin compositions. For example, Patent Document 1: JP-A-9-507309 discloses a polyurethane-acrylic latex copolymer rubber, an acrylic resin, and a vinyl chloride-based copolymer such as a vinyl chloride-vinyl acetate copolymer. The use of a flexible thermoplastic resin film containing a plasticizer as a receptor layer of a receptor film is disclosed. Further, Patent Document 2: Japanese Patent No. 3080674 discloses that acrylic resin, polyolefin, polyvinyl acetal, polyvinyl chloride, polyurethane and the like can be used as the material resin of the receptor layer and the base layer. Incidentally, it has not been known so far to use a phenoxy resin as a material resin for the receptor layer and the base layer.

A window film using a heat transferable polymethylmethacrylate film is disclosed in Patent Document 3: Japanese Patent Application Laid-Open No. 2000-242242.
No. 002-19309. But,
A general polymethylmethacrylate film is poor in flexibility and therefore has a low ability to follow a curved surface, and is therefore insufficient as a marking film that adheres to a curved surface such as a vehicle body surface.

In the adhesive layer of the marking film, in order to prevent air entrapment (residual air bubbles) between the adherend and the adhesive layer when adhering (constructing) the marking film (receptor film) to the adherend. It is also known to form unevenness on the adhesive surface. Such an adhesive layer has a convex portion,
In the state where the marking film is adhered to the adherend, it has a concave portion surrounding the convex portion, and a groove communicating with the outside defined by the concave portion between the adherend surface and the adhesive surface of the adhesive layer. That is, a communication path is formed.

The irregularities on the adhesive surface are usually formed by laminating a release paper (liner) having irregularities on the release surface and an adhesive layer. A marking film using such an uneven release paper is disclosed in Patent Document 4: International Publication WO00 / 6985.
Brochure, Patent Document 5: US Patent 6,203,885
Patent specification 6: Japanese Patent Publication No. 2001-507732, Patent Document 7: Utility Model Registration No. 2,503,717, Patent Document 8: Utility Model Registration No. 2,687,198 Has been done. It is also known that an elastic microsphere is contained in an adhesive layer, a convex portion including the elastic microsphere is formed on the adhesive surface, and a concave portion is effectively formed around the convex portion. A marking film using such elastic microspheres is disclosed in Patent Document 9: JP-A-8-113768.

[0008]

[Patent Document 1] Japanese Patent Publication No. 9-507309

[Patent Document 2] Japanese Patent No. 3080674

[Patent Document 3] Japanese Patent Laid-Open No. 2002-19309

[Patent document 4] International publication WO00 / 6985 pamphlet

[Patent Document 5] US Pat. No. 6,203,885

[Patent Document 6] Japanese Patent Publication No. 2001-507732

[Patent Document 7] Utility model registration No. 2,503,717

[Patent Document 8] Utility model registration No. 2,687,198

[Patent Document 9] Japanese Unexamined Patent Publication No. 8-113768

[0009]

By the way, in a marking film having a concavo-convex adhesive surface, the above-mentioned communicating passage is usually present between the adherend and the adhesive layer even after the film application is completed. Therefore, when used by adhering to the body surface of vehicles such as buses and trucks, the petroleum-based fuel spilled around the refueling port during refueling fills the communication passages due to the capillary phenomenon and adheres (adhered surface) Spread over a relatively large area. It was found that the fuel thus spread penetrates into the film through the adhesive layer and swells the film. The swelling of the film with such a fuel, especially light oil, causes a defective appearance due to the peeling of the marking film from the adherend or the peeling of the interlayer in the marking film.

None of the above publications teaches an improvement of a vehicle marking film which is used by adhering it to a vehicle body surface using a petroleum-based fuel such as light oil. That is, it teaches that a specific resin should be selected and used effectively to effectively enhance the property (petroleum resistance) that does not cause a poor appearance due to swelling by petroleum-based fuel such as light oil as described above. Absent. For example, the above-mentioned poor appearance due to swelling is remarkable when the receptor layer contains a polyolefin. Further, such a swelling is less likely to occur in the receptor layer containing polyurethane, but ordinary polyurethane has low moisture resistance, and the marking film is exposed to the wind and rain for a relatively long period of time (for example, 6 months).
When used, the edge of the marking film peeled off from the adherend, and the edge of the marking film sometimes turned up.
An object of the present invention is to provide a marking film which is excellent in petroleum resistance and moisture resistance and which is particularly suitable for a vehicle that moves using a petroleum-based fuel such as light oil.

[0011]

The present invention comprises: (a) a receptor film having a surface which is a colorant receiving surface and a back surface facing the surface; and (b) coloring received on the surface of the receptor film. And (c) an adhesive layer fixedly disposed on the back surface of the receptor film and containing an adhesive for adhering the receptor film to an adherend, the adhesive layer being adhered to the adherend A convex portion containing the adhesive formed on the adhesive surface, and a concave portion surrounding the convex portion, and the surface of the adherend and the adhesive layer in a state of being adhered to the adherend. In a marking film in which a communication path communicating with the outside is formed between the adhesive surface and the concave portion, the receptor film comprises a thermoplastic resin film having a surface serving as the colorant receiving surface. The thermoplastic resin film comprises a polyurethane layer having a polyol unit derived from a polycarbonate polyol in the molecule, a polyurethane having a polyol unit derived from a polycaprolactone polyol in the molecule, and a phenoxy resin. A resin component containing at least one petroleum-resistant resin selected, or the receptor film contains at least one alkyl acrylate having 1 to 8 carbon atoms in the alkyl group and methyl methacrylate. A marking film, which is a petroleum-resistant resin film containing a copolymer containing the marking film, is provided to solve the above problems.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION [Function] In the marking film of the present invention, the receptor layer contains at least one petroleum-resistant resin selected from the aforementioned group. Therefore, it is possible to effectively prevent petroleum-based fuels such as light oil and gasoline from penetrating into the receptor layer through the adhesive layer and swelling, and when used by adhering to a moving vehicle body surface using petroleum-based fuel, It is possible to effectively prevent appearance defects due to fuel penetration. In addition, since the above petroleum-resistant resin has high hydrolysis resistance, it also has excellent moisture resistance. Therefore, even when the marking film is used outdoors exposed to the weather, it is possible to effectively prevent the marking film from being turned over.

When the surface of the receptor film is likely to be wet with light oil, it is preferable to protect the image forming surface (the surface receiving the coloring material) of the receptor film with a protective film containing a fluororesin. It is also effective to use a protective film formed from a resin composition containing at least one petroleum-resistant resin selected from the above group.

The receptor film may have a base layer disposed between the receptor layer and the adhesive layer, but preferably the receptor film consists essentially of the receptor layer. As a result, the thickness of the marking film can be reduced, and the flexibility of the entire marking film can be easily increased. Therefore, it is possible to effectively enhance the ease of construction on an adherend having an adherend including a curved surface. You can When the receptor film comprises a base layer, the base layer preferably comprises at least one petroleum-resistant resin selected from the aforementioned group. As a result, the base layer functions as a barrier layer, and it is possible to more effectively prevent fuel such as light oil from penetrating into the receptor layer.

Further, according to the present invention, the film layer containing the petroleum-resistant resin can be made substantially free of polyvinyl chloride. In recent years, there is a strong demand in the market for so-called non-vinyl chloride type marking films that are substantially free of polyvinyl chloride. Therefore, according to the present invention, it is also possible to manufacture a non-vinyl chloride type marking film having excellent petroleum resistance and capable of meeting such requirements.

(Marking Film) A preferred example of the marking film of the present invention will be described with reference to FIG. FIG. 1 schematically shows an example of the marking film of the present invention. The receptor film (1) of the marking film (100) is formed of a single layer of a receptor layer which is a thermoplastic resin film. The thermoplastic resin film contains the petroleum-resistant resin as described above. The receptor film (1) has a front surface (11) and a back surface (1).
2), and the surface (11) receives a colorant, that is, the toner (2). The toner (2) passes through the protective film (3) and passes through the outermost surface (31) of the protective film (3).
An image that can be viewed from is formed.

The back surface (12) of the receptor film (1)
An adhesive layer (4) is fixedly arranged on the. Although not shown, the adhesive surface (41) of the adhesive layer (4) is
A convex portion (not shown) containing an adhesive and a concave portion (not shown) surrounding the convex portion are formed, and the surface of the adherend and the adhesive surface (41) are adhered to the adherend. ), A communication path (not shown) communicating with the outside defined by the recess is formed.

The adhesive of the adhesive layer (4) is not particularly limited, but is usually a pressure sensitive adhesive containing a tacky polymer. Examples of such pressure-sensitive adhesive layer include:
A pressure sensitive adhesive film in the form of a single layer containing a tacky polymer or a double-sided adhesive sheet having two pressure sensitive adhesive layers is preferably used.

To adhere the protective film (3) to the receptor film (1), the protective film adhesive layer (30) is usually used. The adhesive of the protective film adhesive layer (30) is not particularly limited, but is usually a pressure-sensitive adhesive containing a tacky polymer. The unevenness formed by the toner (2) on the surface of the receptor film (11) can be closely followed, and the protective film (3) and the receptor film (1) can be adhered to each other so that no bubbles remain. Because. Bubbles reduce the visibility of the image, so it is better not to leave bubbles.

(Receptor Sheet) The receptor sheet of the present invention is a receptor film with an adhesive layer, which comprises a receptor film to which a coloring material such as toner is applied and an adhesive layer for adhering the receptor film to an adherend. .
The receptor film usually comprises (i) a single-layer film comprising a thermoplastic resin film containing a petroleum-resistant resin, or (ii) disposed between the receptor layer and the receptor layer and the adhesive layer. And a laminated base film provided with the base layer. In the case of (ii) above, the base layer is also preferably a resin film formed of a petroleum-resistant resin.

The oil resistance of the resin film can usually be evaluated as follows. First, a sample of a predetermined size made of a resin film is prepared. Drop a drop of light oil (about 0.01-0.02g) on the surface of this sample and
Leave for 0 minutes. When the sample left to stand is visually observed and wrinkles do not occur, the petroleum resistance is judged to be good. In addition, such light oil resistance (petroleum resistance to light oil)
If the resin film has a high degree, the sheet swelling due to other petroleum fuels such as gasoline can be effectively prevented.

The petroleum resistance in the state of the receptor sheet (with an adhesive layer) can usually be evaluated as follows.
A sample having a predetermined size prepared in the same manner as above is adhered to a test adherend (for example, a melamine baking plate or the like). At this time, a communication path communicating with the outside is formed between the adhered surface of the adherend and the adhesive layer. A part of the sample adhered to the adherend is immersed in light oil at room temperature for 8 hours, then taken out from the light oil and dried in the shade at room temperature for 16 hours. When the shaded product is visually observed and wrinkles, peeling from the adherend and delamination (such as peeling between the receptor film and the adhesive layer) do not occur, the petroleum resistance is judged to be good. The petroleum resistance in the state of the marking film can be evaluated in the same manner as above.

On the other hand, the moisture resistance of the resin film is usually evaluated as follows. First, a resin film is attached to a melamine coated plate with an adhesive to prepare a sample. After leaving this sample for 1 week in an oven conditioned at 65 ° C. and 95% RH, it is observed whether or not the edge of the film is turned up. If no edge flipping occurs under these conditions, the moisture resistance is judged to be good. An acrylic pressure-sensitive adhesive is usually used as the adhesive for attaching the resin film to the melamine coated plate. Further, an adhesive used for actually adhering the marking film to the adherend may be used. Moisture resistance when used as a marking film is also evaluated by the same method.

Polyurethane used as a petroleum-resistant resin is a polymer obtained by polymerizing a raw material containing the above-mentioned polyol (polycarbonate polyol and / or polycaprolactone polyol) and diisocyanate. A short chain diol such as neopentyl glycol, ethylene glycol or propylene glycol may be added to the raw material as a chain extender. Diisocyanate is
For example, isophorone diisocyanate (IPDI),
Diphenylmethane diisocyanate (MDI), hydrogenated M
DI, 1,6-hexanediol diisocyanate, tolylene diisocyanate (TDI), tetramethylxylylene diisocyanate (TMXDI) and the like can be used. The raw material may contain one or more polyols and may also contain one or more diisocyanates.

The type (chemical structure) of the diisocyanate contained in the raw material and the ratio of the short chain diol and the polyol in the case of containing the short chain diol are appropriately determined, and the physical properties of the thermoplastic resin film containing polyurethane (glass transition point, It is preferable that the complex dynamic viscosity and the Vicat softening point) be in the optimum range. The glass transition point of the thermoplastic resin film of the receptor layer is usually in the range of 0 to 100 ° C. If the glass transition point of the receptor layer is too high, the toner transfer performance may be deteriorated and a clear image may not be obtained. Furthermore, if the glass transition point of the receptor layer is too high, the flexibility of the marking film as a whole may decrease. On the other hand, if the glass transition point is lower than 0 ° C, the petroleum resistance may decrease. Further, in order to effectively lower the room temperature tack of the colorant receiving surface, the glass transition point of the receptor layer is set to 0.
It is better to keep it above ℃. By doing so, it is possible to effectively prevent the marking film precursors before they are covered with the protective film and the receptor sheets from sticking to each other. Therefore, after these are stored in a roll shape, the roll can be easily unwound and used.

In order to enhance the above-mentioned effects, namely, improvement of petroleum resistance, improvement of toner transfer performance, reduction of room temperature tack and improvement of film flexibility, in a more effective manner, the glass transition point of the receptor layer is , 10 to 90 ° C is preferable, and 20 to 80 ° C is particularly preferable. The glass transition point (Tg) of the thermoplastic resin film such as the receptor layer has a thickness of about 10 μm (usually 8 to 2).
0 μm) film is prepared as a sample, and this sample is D
Set it in SC (Differential Scanning Calorimeter) and measure. During the measurement, the temperature is raised from -50 to 120 ° C. (first scan), and Tg is determined from the inflection point corresponding to the second-order transition point during the first scan.

The physical properties other than the glass transition point of the thermoplastic resin film include, for example, the Vicat softening point of the thermoplastic resin film measured at 25 ° C. using a viscoelasticity spectrometer. The Vicat softening point of the thermoplastic resin film is usually 30 to 95 ° C., preferably 40 to 93.
℃. If the Vicat softening point is too high, thermal transfer of toner may be difficult. On the other hand, if the Vicat softening point is too low, the mechanical strength will decrease, and the durability of the marking film may decrease. The Vicat softening point is a softening temperature measured by a method in accordance with Japanese Industrial Standard JIS-K7206, and a test is performed while applying a predetermined load to a needle-shaped indenter standing vertically on a test piece (thermoplastic resin film). It is the temperature when the temperature of the piece is raised at a constant rate and the indenter penetrates the test piece by 1 mm.

A particularly preferred polyurethane is a polyurethane having a polyol unit derived from a polycarbonate polyol in the molecule (polycarbonate polyurethane). The polycarbonate-based polyurethane has excellent weather resistance as well as moisture resistance, and can effectively prevent the film containing it from being deteriorated or colored. Coloring of the protective film or the receptor film causes discoloration of the image. Therefore, a receptor film or a protective film that is difficult to be colored is advantageous as a constituent material of a marking film used outdoors, particularly a marking film for vehicles.

The number of carbon atoms of alkylene of the polyol main chain molecule is preferably 5 to 7. If the carbon number is 8 or more,
Petroleum resistance of the thermoplastic resin film tends to decrease, and conversely, when the carbon number is 4 or less, the thermal transfer property of the toner may decrease. The molecular weight of polyurethane is not particularly limited, but it is usually 20,000 to 1,000,
It has a weight average molecular weight of 000.

The phenoxy resin is also highly resistant to petroleum and moisture. This is mainly due to having a repeating unit derived from bisphenol in the molecule. As the phenoxy resin, those usually used for paints can be used. As a commercially available specific example, "Product number: YP50" manufactured by Tohto Kasei Co., Ltd.
S "," Trademark: Paphen PKHH "of Phenoxy Specialties
Etc. can be mentioned. The molecular weight of phenoxy resin is
It is not particularly limited as long as it has sufficient toughness, but usually 2
It has a weight average molecular weight of from 0,000 to 1,000,000. Further, the phenoxy resin has higher breaking strength than polyurethane, and is therefore advantageous in increasing the toughness of the receptor film. By increasing the toughness of the receptor film, it is possible to prevent the marking film from breaking when the marking film adhered to the adherend is peeled for replacement, and the peeling work can be effectively reduced.

When a phenoxy resin is used, it is preferably combined with polyurethane. This is because it is particularly easy to balance and enhance the flexibility and toughness of the receptor film. In such a case, the mass ratio of polyurethane in the polyurethane / phenoxy resin mixture is usually 60% or more, preferably 65% or more, and particularly preferably 70%.
That is all. The polyurethane used in combination with the phenoxy resin is usually a polycarbonate-based polyurethane or a polycaprolactone-based polyurethane, but when the mass ratio of the polyurethane is 70% or less,
Polyurethane other than the above may be used.

As the petroleum-resistant resin, it is also possible to use a copolymer containing at least one alkyl acrylate having 1 to 8 carbon atoms in the alkyl group, which is a soft component, and methyl methacrylate, which is a hard component. The alkyl acrylate lowers the glass transition point of the copolymer. This copolymer has at least 1
It may further include three other comonomers, such as methacrylate (excluding methylmethacrylate), styrene, and the like. The glass transition point of this copolymer is generally 0 to 100 ° C, preferably 20 to 90 ° C, more preferably 30 to 80 ° C. The proportion of the alkyl acrylate in the copolymer is preferably 10% by mass or more, but is not limited thereto. Among the copolymers, a copolymer containing butyl acrylate and methyl methacrylate is particularly preferable. When the above acrylic copolymer is used as the petroleum-resistant resin, the receptor film is a monolayer film.

The resin component constituting the receptor layer (and the base layer) may contain other resins as long as the effects of the present invention are not impaired. Examples of other resins are
It is an acrylic resin. The acrylic resin is a polymer formed by polymerizing a (meth) acrylic monomer mixture. The (meth) acrylic monomer mixture is usually a mixture of (meth) acrylate having an alkyl group having 1 to 10 carbon atoms and other copolymerizable monomers. The other copolymerizable monomer is preferably a hydrophilic monomer such as hydroxy (meth) acrylate, alkylene glycol diacrylate, acrylic acid or methacrylic acid in order to enhance petroleum resistance. The acrylic resin can be formed from such a monomer mixture by a usual polymerization method, for example, solution polymerization. The mixing ratio of each monomer is appropriately determined so that the glass transition point of the thermoplastic resin film and other physical properties are in the optimum range. Although the molecular weight of the acrylic resin is not particularly limited, it usually has a weight average molecular weight of 20,000 to 1,000,000.

The ratio of the petroleum-resistant resin to the entire resin components contained in the thermoplastic resin film which becomes the receptor layer or the base layer is usually 70% by mass or more. In order to enhance the oil resistance of the film more effectively, the ratio of the oil resistant resin to the entire resin components is preferably 80% by mass or more, particularly preferably 90% by mass or more.

The receptor sheet can be manufactured, for example, as follows. The thermoplastic resin film to be the receptor layer can be formed by a usual film forming method. For example, it can be formed by applying a coating material containing a resin component on the release surface of the liner and solidifying it. A usual coater, for example, a bar coater, a knife coater, a roll coater, a die coater or the like can be used for the coating device. The solidifying operation is a drying operation in the case of a coating material containing a volatile solvent or an operation of cooling the molten resin component. Further, it can be formed by a melt extrusion molding method.

When the receptor sheet comprises a base layer and a receptor layer, it can be produced, for example, as follows, although not particularly limited thereto. First, a receptor layer is formed on a liner, and on this liner-bearing receptor layer,
A paint containing a resin component for the base layer is applied and solidified.
This makes it possible to form a receptor film composed of a laminate film. Further, another layer such as a primer layer or an adhesive layer may be disposed between the receptor layer and the base layer as long as the effects of the present invention are not impaired.

An adhesive layer is adhered to the back surface of the receptor film completed as described above. The adhesive layer is formed by applying a coating solution containing an adhesive to the release surface of the liner and drying it to form an adhesive layer with a liner, and then laminating the adhesive layer with a liner to a receptor film to bring them into close contact. Thereby, the receptor sheet of the present invention can be completed.

The total thickness of the receptor film is usually 2
It is 0 to 150 μm, preferably 30 to 100 μm. If the thickness is too thin, the mechanical strength will decrease, and the receptor sheet may be damaged when the marking film is adhered to an adherend and then peeled off. On the other hand, if it is too thick, the flexibility of the marking film including the receptor sheet may decrease.

(Adhesive Layer) On the adhesive layer for adhering the marking film (receptor film) to the adherend, the uneven adhesive surface as described above is formed. As the method for forming the uneven adhesion surface, the method disclosed in the above-mentioned prior art document can be used, and one example thereof will be described here. First, a liner having a release surface having a predetermined uneven structure is prepared. A coating material containing an adhesive polymer (adhesive coating material for forming an adhesive layer of an adhesive sheet) is applied to the release surface of the liner and dried to form an adhesive layer. As a result, the surface of the adhesive layer that contacts the liner (this becomes the adhesive surface of the adhesive sheet),
The concavo-convex structure (negative structure) of the liner is transferred to form a concavo-convex adhesive surface having a predetermined structure (positive structure) on the adhesive surface.
As described above, the unevenness of the bonding surface is designed in advance so as to include a groove capable of forming a communication path when the convex portion is bonded to the adherend.

Such grooves of the adhesive layer may be of a certain shape arranged on the adhesive surface along a regular pattern, as long as bubbles can be prevented from remaining when the marking film is applied. The ones may be arranged irregularly. When a plurality of grooves are formed so as to be arranged substantially parallel to each other, the arrangement interval of the grooves is preferably 10 to 2,000 μm. The groove depth (the distance from the adhesive surface to the bottom of the groove measured in the direction of the receptor film) is usually 1
It is 0 to 100 μm. The shape of the groove is not particularly limited as long as the effect of the present invention is not impaired. For example, in the cross section of the groove in the direction perpendicular to the bonding surface, a substantially rectangular shape (including a trapezoid),
It has a substantially semi-circular shape and a substantially semi-elliptical shape.

The liner is usually formed from paper or plastic film. The paper liner is usually formed by laminating a release coat (release layer) such as polyethylene coat or silicone coat on the surface of paper. When laminating a silicone release coat, usually, an undercoat such as a clay coat or a polyethylene coat is laminated on paper, and then the release coat is laminated. The concavo-convex structure of the liner can be formed, for example, by laminating a release coat and then bringing the concavo-convex transfer tool into pressure contact with the release surface.

The adhesive layer can be formed from, for example, a coating film of an adhesive containing a tacky polymer. A preferred adhesive contains a tacky polymer and a crosslinking agent that crosslinks the tacky polymer. In this specification, the adhesive polymer (self
-Adherent polymer) is a polymer that exhibits adhesiveness at room temperature (about 25 ° C). As the adhesive polymer, acrylic polymer, polyurethane, polyolefin, polyester and the like can be used.

An example of synthesizing the tacky polymer will be described by taking an acrylic polymer as an example. First, as the first monomer, a polar (meth) acrylic monomer such as an acrylic unsaturated acid (for example, acrylic acid, methacrylic acid, itaconic acid, maleic acid, etc.) or acrylonitrile is prepared. The first monomer and the acrylic monomer as the second monomer are mixed to prepare a monomer mixture.
As the second monomer, an alkyl acrylate, for example, isooctyl acrylate, butyl acrylate,
2-Methylbutyl acrylate, 2-ethylhexyl acrylate, isononyl acrylate, etc. can be used.
The monomer mixture thus prepared is used to synthesize an adhesive polymer having a predetermined molecular weight by using a usual polymerization method such as solution polymerization, emulsion polymerization or bulk polymerization.

When a cross-linking agent is used to cross-link the tacky polymer, the addition amount of the cross-linking agent depends on the kind of the cross-linking agent, but is usually 0.0 per 100 parts by mass of the tacky polymer.
It is 2 to 2 parts by mass, preferably 0.03 to 1 part by mass. The crosslinking agent is an isocyanate compound, a melamine compound, a poly (meth) acrylate compound, an epoxy compound, an amide compound, a bisamide compound [isophthaloylbis (2-
Bisaziridine derivative of dibasic acid such as methylaziridine) and the like can be used.

The glass transition point (Tg) of the adhesive layer is preferably -50 to 0 ° C, particularly preferably -45 to -5 ° C.
If the Tg of the adhesive layer is too high, the adhesion between the adherend and the marking film may be reduced. On the other hand, if the Tg is too low, when the marking film is rolled and stored, the adhesive may It may not be possible to prevent sticking of the marking films that are exuded from the side portions (side surface portions) of the roll and overlap each other. The Tg of the adhesive layer is tan δ measured using a dynamic viscoelasticity measuring device.
It is the value obtained from. The measurement conditions are a twist mode with a share rate of 1 radian / second and a temperature rise range of -60 to 100.
The temperature rise rate is 5 ° C / sec. Sample thickness is usually 1 ~
It is 2 mm.

The thickness of the adhesive layer is usually 20 to 100 μm,
It is preferably 25 to 80 μm. Also, the pressure sensitive adhesive layer is
Additives such as tackifiers, elastic microspheres, adhesive polymer microspheres, crystalline polymers, inorganic powders, and ultraviolet absorbers may be contained as long as the effects of the present invention are not impaired.

(Protective Film) The protective film as a whole has a light transmitting property. The light transmittance is usually 60% or more,
It is preferably 70% or more, and particularly preferably 80% or more.
In the present specification, "light transmittance" means a spectrophotometer or
550 using a color meter that also has the function of a photometer
Mean total light transmittance measured using nm light.
The protective film is preferably a resin film containing a highly transparent resin. The resin of the resin film is, for example, a fluorine resin, a phthalate polyester (PET, PEN, etc.), an acrylic resin, or the petroleum-resistant resin described above. The fluororesin is a polymer obtained by polymerizing a fluoromonomer.
The fluorine-based monomer is, for example, vinylidene fluoride, 6
It is a fluorine-based ethylene monomer such as propylene fluoride, ethylene tetrafluoride, and ethylene chloride trifluoride. In addition to fluorine-based monomers, one of the copolymerizable monomers such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate and other methacrylates, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate and other acrylates.
You may mix 1 type (s) or 2 or more types. Moreover, you may form a protective film from the resin composition which blended the fluororesin and acrylic resin.

When the marking film of the present invention is used as a marking film for vehicles that move using light oil as an energy source, the resin of the protective film is preferably a fluorine resin or a petroleum resistant resin. In this case, the proportion of the fluorine-based resin or the petroleum-resistant resin with respect to the entire resin components constituting the protective film is usually 70% by mass or more, preferably 80% by mass or more, and particularly preferably 90% by mass or more. When the protective film contains both the fluororesin and the petroleum-resistant resin, it is preferable that the total amount of these is within the above range. The thickness of the protective film is usually 5 to 120.
μm, particularly preferably 10 to 100 μm. When an adhesive layer is used to adhere the protective film to the receptor film, the thickness of the adhesive layer is usually 20-100 μm.
m, particularly preferably 25 to 80 μm.

(Image forming) Colorant is usually toner or ink. For example, when the toner is transferred to the receptor layer to form an image, the toner is transferred to the back surface of the protective film by using a normal printing method such as an electrostatic printing method. In the electrostatic printing method, an image is directly printed on the back surface of the protective film, and a transfer method in which the image is temporarily printed on the temporary carrier and then the image is transferred to the protective film. There is. In the latter transfer method,
An image is formed on a temporary carrier called a transfer medium, and the image is transferred onto the back surface of the protective film by heating and pressing to complete the image-recorded protective film.

The toner forming an image contains a binder resin and a pigment dispersed in the binder resin. The binder resin is formed, for example, of one type selected from the group consisting of vinyl chloride-acetate-based copolymers, acrylic resins and polyester resins, or a mixture containing two or more types. Details of such an electrostatic printing method are disclosed in, for example, Japanese Patent Application Laid-Open No. 4-216562 and Japanese Patent Publication No. 11-513818.

[0051]

EXAMPLES Example 1 A receptor sheet of this example was prepared as follows. First, a polycarbonate polyurethane and a phenoxy resin were mixed in a ratio of 70:30 (mass ratio) and dissolved in toluene to prepare a coating material for a receptor layer. Polyurethane was obtained by polymerizing a raw material containing 1,6-hexanediol carbonate polyol and hexamethylene diisocyanate. The phenoxy resin was "Trademark: Paphen PKHH" from Phenoxy Specialties. This paint is applied on a polyester carrier (a liner made of a polyester film having a release treatment layer and having a thickness of 50 μm) so that the thickness after drying becomes 10 μm, and dried to give a transparent thermoplastic resin film. A receptor layer consisting of The Tg of the receptor layer (thermoplastic resin film) was 24 ° C. The Tg of the polyurethane was 34 ° C and the Tg of the phenoxy resin was 72 ° C.

A polyester-based polyurethane resin solution ("(trademark) Rezamin (product number) NE310" manufactured by Dainichiseika Co., Ltd. is formed on the back surface of the receptor layer (the surface in contact with the carrier serves as the colorant receiving surface). )) Was applied and dried so that the thickness after drying was 33 μm to form a base layer. Thereby, a receptor film composed of a laminate of the receptor layer and the base layer was obtained. On the other hand, a coating for the adhesive layer was applied to the release surface of the liner having a regular unevenness on the release surface by knife coating so that the thickness after drying was 40μ.
It was applied so as to have a thickness of m and dried at 90 ° C. for 5 minutes. This paint was prepared by mixing an acrylic adhesive polymer, a crystalline polyurethane, and a bisamide crosslinking agent in an ethyl acetate / toluene mixed solvent. The mixing ratio (mass ratio) of adhesive polymer / crystalline polyurethane / crosslinking agent was 90: 10: 0.2 (nonvolatile content ratio).

The above-mentioned acrylic adhesive polymer is a butyl acrylate / acrylonitrile / acrylic acid
It was a copolymer obtained by solution polymerization of a monomer mixture contained in a ratio of 3: 3: 4 (mass ratio). The adhesive polymer had a weight average molecular weight of 460,000 and Tg of -21 ° C. The crystalline polyurethane is polycaprolactone (trademark: Praxel 220, manufactured by Daicel Chemical Industries, Ltd., weight average molecular weight = 6,000, weight average molecular weight / number average molecular weight = 1.
8) was polymerized with isophorone diisocyanate (IPDI) in toluene to give a polyurethane.
The molar ratio of polycaprolactone to IPDI was 2: 1. The weight average molecular weight of this polyurethane is 13,0.
00, weight average molecular weight / number average molecular weight = 2.2.

On the release surface of the liner, convex portions composed of a plurality of ridges corresponding to the grooves to be transferred to the adhesive layer are arranged continuously along the grid line so as to intersect each other. It had been. The height of the ridge was 19.5 μm (the maximum depth of the groove on the adhesive surface was 19.5 μm). The maximum distance between adjacent ridges (distance between bottoms of ridges) is 1.
The width of the ridge was 2 mm and the width of the ridge was 55 μm. Further, the vertical cross-sectional shape of the ridge was substantially trapezoidal, and correspondingly, the groove of the adhesive layer had a substantially trapezoidal vertical cross-sectional shape.

The adhesive layer with a liner thus produced was dry laminated on the back surface of the base layer of the receptor sheet obtained as described above, and the polyester carrier was removed from the surface of the receptor layer to obtain the receptor sheet of this example. It was

Using the receptor sheet thus obtained, the marking film of this example was prepared as follows. First, an electrostatic printing system manufactured by 3M Co., Ltd., and a trademark Scotchprint product number 9512 were used to form a transfer digital image on a transfer medium manufactured by 3M Co., Ltd. and trademark Trident by using a special toner. This image-recorded transfer medium was wound into a roll to prepare a media roll.

Next, the receptor sheet and the media roll were attached to a laminator manufactured by 3M Co., Ltd., trade name Orca III, and the toner image was transferred to the receptor sheet by operating the laminator under the following conditions. A roll of marking film was obtained. Image transfer conditions; -Upper roll temperature = 130 ° C-Lower roll temperature = 50 ° C-Web transport speed = 70 cm / min-Pressure = about 410 kPa (60 psi) With the marking film of this example, the image observed through the protective film is clear. Met.

The toner adhesion test was conducted as follows. A grid pattern on the toner image (the size of one square is about 1 mm
After making 100 cuts in (about 1 mm), an adhesive tape (product number # 610) manufactured by 3M was attached to the toner image. When the attached tape was quickly peeled off, no toner transfer was observed on the adhesive tape side, and it was confirmed that the adhesion between the toner and the receptor layer was good.

On the other hand, a transparent protective film was adhered to the toner image (colorant receiving surface) of the marking film with an adhesive to prepare a marking film with a protective film. This protective film was a fluororesin-containing protective film with an adhesive layer (overlaminated film part number SP4114 manufactured by Sumitomo 3M Ltd.).

The petroleum resistance of this marking film with a protective film was evaluated as follows. First, two marking films prepared by cutting into a substantially rectangular shape having a length of about 50 mm and a width of about 30 mm are prepared. One marking film is attached to a melamine baking coated plate manufactured by Paltec Co., Ltd. through an adhesive layer having an uneven adhesive surface provided on the marking film, and the other marking film is partially attached to one marking film. In the same manner, it was attached to the above-mentioned coated plate via the adhesive layer so as to overlap with the above, to prepare a sample. At this time, the width-direction end portions of each of them overlap each other with a length of about 10 mm. By doing so, the petroleum-based fuel easily permeates from the edge of the film between the adhesive layer and the coated plate, and the test can be performed under relatively severe conditions. The thus-prepared sample was fixed by immersing a portion having a width of about 10 mm from two end portions in the length direction of the marking film in light oil (manufactured by Mobile Oil Co., Ltd.), and left standing for 8 hours. After standing, the appearance of the sample dried in the shade at room temperature for 16 hours was visually confirmed. No peeling was observed at the adhesive interface, delamination of the receptor layer or the like, and wrinkles were observed at any of the two marking films, and the marking films had a good appearance.

On the other hand, when the moisture resistance of the marking film was evaluated as described above, no flipping from the adherend (the above-mentioned melamine baking coated plate) occurred at the end of the marking film, and the moisture resistance was good. Was judged.

(Example 2) A receptor sheet of this example was obtained in the same manner as in Example 1 except that the receptor layer was prepared only from the above-mentioned polycarbonate polyurethane and the receptor film consisting of this receptor layer alone was used. . The thickness of the receptor layer was 33 μm. With the marking film of this example, the image observed through the protective film was clear. Further, the toner adhesion was good, and no toner transfer was observed on the adhesive tape side. The petroleum resistance was evaluated in the same manner as in Example 1. As a result, no peeling of the marking film from the adherend, delamination of the receptor layer or the like, and wrinkles were observed at all, and it had a good appearance. Further, when the moisture resistance was evaluated in the same manner as in Example 1, no edge swelling occurred.

(Example 3) A receptor sheet of this example was obtained in the same manner as in Example 2 except that the polyurethane was changed to a polycaprolactone type polyurethane. The polyurethane used in this example was obtained by polymerizing polycaprolactone, MDI, and neopentyl glycol as raw materials. Also, receptor layer (thermoplastic resin film)
Had a Tg of 0 ° C. With the marking film of this example, the image observed through the protective film was clear. Further, the toner adhesion was good, and no toner transfer was observed on the adhesive tape side. The petroleum resistance was evaluated in the same manner as in Example 1. As a result, no peeling of the marking film from the adherend, delamination of the receptor layer or the like, and wrinkles were observed at all, and it had a good appearance. Further, when the moisture resistance was evaluated in the same manner as in Example 1, no edge swelling occurred.

Example 4 A receptor sheet of this example was obtained in the same manner as in Example 2 except that the receptor layer was made of only the above-mentioned phenoxy resin. Using the receptor sheet of this Example, a marking film roll was obtained in the same manner as in Example 1. With the marking film of this example, the image observed through the protective film was clear. Further, the toner adhesion was good, and no toner transfer was observed on the adhesive tape side. The petroleum resistance was evaluated in the same manner as in Example 1. As a result, no peeling of the marking film from the adherend, delamination of the receptor layer or the like, and wrinkles were observed at all, and it had a good appearance. Moreover, when the moisture resistance was evaluated in the same manner as in Example 1, no edge swelling occurred.

Comparative Example 1 A receptor layer having a thickness of 5
A marking film of this example was obtained in the same manner as in Example 2 except that a 0 μm ionomer resin film (Mitsui DuPont Chemical Co., Ltd., trade name Himilan 1601) was used. With the marking film of this example, the image observed through the protective film was clear. Further, the toner adhesion was good, and no toner transfer was observed on the adhesive tape side. As a result of evaluating the petroleum resistance in the same manner as in Example 1, swelling of the receptor layer occurred and peeling of the marking film from the adherend was observed.

(Comparative Example 2) A receptor sheet of this example was obtained in the same manner as in Example 2 except that the receptor layer was made only from the polyester polyurethane described below. The polyurethane used in this example is 1,6-hexanediol, 1,4-butanediol, adipic acid, IPD.
It was obtained by polymerizing a raw material containing I and hydrogenated MDI. In the marking film of this example, the transferability of toner was relatively low, and the sharpness of the image was worse than in Examples 1 to 4. Further, when the moisture resistance was evaluated in the same manner as in Example 1, the film was turned over at the edges, and the moisture resistance was obviously inferior to those in Examples 1 to 4.

(Example 5) Methyl methacrylate (MM
A) -butyl acrylate (BA) -methyl acrylate (MA) -styrene (St) copolymer (MMA: BA: MA: St
= 69: 23: 3: 5 (mass ratio)), a single-layer white film having a thickness of 80 μm was formed from a composition containing titanium oxide to obtain a receptor layer. The Tg of this receptor layer was 56 ° C. This film is cut into a width of 25 mm, and the gripping interval is 100 at 20 ° C using a Tensilon tester.
mm, elongation rate was measured at a tensile speed of 300 mm / min,
It was 55%.

On the other hand, in the same manner as in Example 1, a coating material for an adhesive layer was applied to the release surface of the liner and dried to produce an adhesive layer with a liner, and the adhesive layer was coated with the receptor layer produced above. The film was dry laminated to obtain a receptor sheet of this example.

A digital image for transfer was formed in the same manner as in Example 1. Next, the toner image was transferred to the receptor sheet under the same conditions as in Example 1 except that the upper roll temperature was set to 135 ° C. to obtain the marking film of this example. The paper carrier of Trident was peeled off, and it was visually confirmed that the toner image was completely transferred.

The adhesion of the toner was tested in the same manner as in Example 1. No toner transfer was observed on the adhesive tape side,
It was confirmed that the adhesion between the toner and the receptor layer was good.

On the other hand, the same transparent protective film as used in Example 1 was adhered to the toner image (colorant receiving surface) of the marking film via an adhesive to prepare a marking film with a protective film. The petroleum resistance of this marking film with a protective film was evaluated as follows. First, the marking film was cut into 50 mm square and was attached to a melamine baking coated plate manufactured by Paltec Co., Ltd. via an adhesive layer provided on the marking film to prepare a sample. About 10m from the lower end of the marking film
The m-width portion was fixed so as to be immersed in light oil (manufactured by Mobile Oil Co., Ltd.) and left for 8 hours. After leaving it at room temperature for 1
The appearance of the sample dried in the shade for 6 hours was visually confirmed. No swelling or peeling of the film was observed in any part of the marking film, and the film had a good appearance.

Comparative Example 3 A receptor sheet of this example was prepared in the same manner as in Example 5 except that a polymethylmethacrylate film (thickness: 80 μm) was used instead of the MMA-BA-MA-St copolymer film. The elongation percentage of this polymethylmethacrylate film measured under the same conditions as in Example 5 was 5%. Therefore, there was almost no elongation, and the curved surface conformability as a marking film was insufficient.

A marking film was produced in the same manner as in Example 5 except that the receptor sheet obtained above was used. However, a part of the toner remained on the paper carrier side and the transferability of the toner was unsatisfactory. However, the toner once transferred does not move to the adhesive tape side in the toner adhesion test,
It had good adhesion.

In the same manner as in Example 5, the protective film was brought into close contact with the toner image of the marking film to prepare a marking film with a protective film, and the oil resistance was tested. No swelling or peeling of the film was observed. .

(Comparative Example 4) An acrylic resin film consisting of 90 parts by mass of BA and 10 parts by mass of acrylic acid was used in place of the MMA-BA-MA-St copolymer film (thickness: 5).
The receptor sheet of this example was prepared in the same manner as in Example 5 except that the thickness of the receptor sheet was 0 μm. The Tg of this film is-
It was 17 ° C. The surface of this film was tacky, making it unsuitable for use as a receptor layer in marking films.

[Brief description of drawings]

FIG. 1 is a cross-sectional view of an example of a marking film of the present invention.

[Explanation of symbols]

100: marking film, 1: receptor film, 11: front surface, 12: back surface, 2: toner, 3: protective film, 4: adhesive layer, 41: adhesive surface, 30: adhesive layer for protective film

   ─────────────────────────────────────────────────── ─── Continued front page    F term (reference) 4F100 AK01A AK01D AK17D AK25A                       AK51A AK54A AL05A AR00C                       BA03 BA04 BA10B BA10C                       CA13B CB00 EJ91D GB90                       JA05A JB06 JB16A JD04                       JD14B JL11C JN01D

Claims (8)

[Claims] 1. A receptor film having (a) a surface that is a colorant-receiving surface and a back surface facing the surface, (b) a colorant that is received on the surface of the receptor film, and (c) the receptor. An adhesive layer that is fixedly arranged on the back surface of the film and that contains an adhesive that adheres the receptor film to an adherend, wherein the adhesive layer is formed on an adhesive surface that is adhered to the adherend. A convex portion including an adhesive and a concave portion surrounding the convex portion, and the concave portion between the adherend surface and the adhesive surface of the adhesive layer in a state of being adhered to the adherend. The marking film, in which a communicating path communicating with the outside is formed, wherein the receptor film comprises a receptor layer made of a thermoplastic resin film having a surface to be the colorant receiving surface, The plastic resin film is at least one petroleum resistance selected from the group consisting of a polyurethane having a polyol unit derived from a polycarbonate polyol in the molecule, a polyurethane having a polyol unit derived from a polycaprolactone polyol in the molecule, and a phenoxy resin. A marking film comprising a resin component containing a resin. 2. The marking film according to claim 1, wherein the thermoplastic resin film contains polyurethane and a phenoxy resin. 3. The marking film according to claim 1, wherein the receptor film consists essentially of the receptor layer. 4. A receptor sheet used for producing the marking film according to claim 1 by using electrostatic toner printing, wherein the receptor film and the receptor film fixedly arranged on the back surface of the receptor film. An adhesive layer is provided, and the receptor film comprises a receptor layer made of a thermoplastic resin film having a surface serving as the colorant receiving surface onto which the toner is transferred, and the thermoplastic resin film is derived from a polycarbonate polyol. A resin component containing at least one petroleum-resistant resin selected from the group consisting of a polyurethane having a polyol unit in its molecule, a polyurethane having a polyol unit derived from a polycaprolactone polyol in its molecule, and a phenoxy resin. And the glass transition point of the receptor layer is 0. A receptor sheet in the range of -100 ° C. 5. A receptor film having (a) a surface which is a colorant receiving surface and a back surface facing the front surface, (b) a colorant received on the surface of the receptor film, and (c) the receptor. An adhesive layer that is fixedly arranged on the back surface of the film and that contains an adhesive that adheres the receptor film to an adherend, wherein the adhesive layer is formed on an adhesive surface that is adhered to the adherend. A convex portion including an adhesive and a concave portion surrounding the convex portion, and the concave portion between the adherend surface and the adhesive surface of the adhesive layer in a state of being adhered to the adherend. In the marking film described above, in which a communication path communicating with the outside is formed, the receptor film has at least one alkyl acrylate having 1 to 8 carbon atoms in the alkyl group.
A marking film, which is a petroleum-resistant resin film comprising a copolymer containing one and methyl methacrylate. 6. A receptor sheet used for producing the marking film according to claim 5 by using electrostatic toner printing, wherein the receptor film and the receptor film fixedly arranged on the back surface of the receptor film. An adhesive layer, the receptor film is a petroleum-resistant resin film comprising a copolymer containing at least one alkyl acrylate having 1 to 8 carbon atoms in the alkyl group and methyl methacrylate, and a glass transition. A receptor sheet having a point in the range of 0 to 100 ° C. 7. A light-transmitting protective film, which covers the surface of the receptor film that has received the coloring material, is further provided, and the protective film contains a fluororesin.
The marking film according to claim 1 or 5. 8. A marking film for a vehicle, comprising the marking film according to claim 1 or 5, which is used by adhering to the body surface of a vehicle that moves using petroleum-based fuel as an energy source.