JP2001072950A - Adhesive sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive sheet having good printability by forming an easily printable layer on a face of a transparent polyolefin film base, the face having no lamination of a metallic deposited layer, an adhesive layer and a peeling sheet thereon. SOLUTION: An adhesive sheet is produced by either coating a resin for an easily printable layer on a longitudinally orientated to form the easily printable layer and then transversely orientating the resulting film, or coating the resin for the easily printable layer on a film biaxially orientated to form the easily printable layer. As the coating resin in the former method is preferable a resin comprising an ionomer as a principal component. As the coating resin in the latter method is preferable particularly a polymer or copolymer of acrylic acid, methacrylic acid, an acrylate and a methacrylate, a polyester resin, an ethylene-vinyl acetate copolymer, a vinyl chloride-vinyl acetate copolymer or the like. In addition to these, adhesion of a metallic deposited layer is improved by forming an adhesiveness between the film and the metallic deposited layer. The adhesiveness may be formed by coating it and the easily printable layer at the same time.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pressure-sensitive adhesive sheet for use as a display label or the like using a polyolefin film in which a surface substrate is metal-deposited (for example, aluminum-deposited).

[0002]

2. Description of the Related Art Conventionally, a pressure-sensitive adhesive sheet has a structure in which a surface base material, a pressure-sensitive adhesive layer, and a release sheet are laminated, and is commercially available.
It is used in a wide variety of forms such as labels, stickers, stickers, patches, delivery slips, etc. for office use, process control, logistics control, home use, etc.

[0003] As one application of the pressure-sensitive adhesive sheet, aluminum is deposited on a film such as a polyethylene terephthalate film or a polyolefin-based film as a surface base material, and is further printed to provide an aluminum-deposited label having excellent design properties (hereinafter referred to as an aluminum-deposited label). ). Above all, a vapor-deposited label using a polyolefin-based film has the properties of flexibility, smoothness,
Due to its transparency and the like, the metallic luster is good and the design is excellent as a display label. Further, due to its design and flexibility, demand is expected as a label for displaying containers such as bottles and bottles.

[0004]

When such an adhesive sheet (vapor-deposited label) is used as a display label, printing such as display of contents is performed. However, in a container such as a bottle or a bottle, it is used during use or transportation. In many cases, the label is deformed or rubbed, so that printing is peeled off or the aluminum vapor-deposited layer is peeled off. Moreover, since these containers are often used with the label attached,
It is required to improve the adhesion of the printed matter and the adhesion of the aluminum deposition layer.

[0005]

Means for Solving the Problems The present inventors have intensively studied to solve this problem. First, in order to eliminate defects due to rubbing of the aluminum vapor deposition layer, a vapor deposition process was performed on the side of the film substrate on which the pressure-sensitive adhesive layer was provided. However, polyolefin-based films have poor ink adhesion, and have insufficient ink adhesion even after corona treatment, so that when used as a display label, they cannot be printed or read. Therefore, it has been found that the adhesion of printed matter is improved by coating the printing surface with an easy-to-print layer.

(1) That is, according to the present invention, in a pressure-sensitive adhesive sheet obtained by laminating a film substrate, a metal vapor-deposited layer, a pressure-sensitive adhesive layer, and a release sheet, the film substrate is a transparent polyolefin film, and the metal vapor-deposited layer is formed. The pressure-sensitive adhesive sheet has good printability, characterized by having an easy-to-print layer on the surface not to be treated.

Further, when a polyolefin film having excellent transparency, particularly a polypropylene film, is used as the film substrate, the adhesion is weak when directly vapor-deposited on the film, and delamination occurs between the metal-deposited layer and the film layer. Cheap. In particular, when used after being immersed in water or soapy water, the delamination thereof is remarkable. It was found that by providing an adhesive layer containing a resin as a main component between the film and the metal deposition layer, the adhesion of the metal deposition layer was improved. (2) That is, the pressure-sensitive adhesive sheet according to (1), further including an adhesive layer on a surface of the film substrate on which the metal deposition layer is formed.

[0008] As a result of further study on the adhesion of the metal deposition layer, acrylic polyol and vinyl chloride-
It has been found that when a vinyl acetate copolymer resin is used, the adhesion of the metal deposition layer is extremely excellent. (3) That is, the present invention is the pressure-sensitive adhesive sheet according to the above (2), wherein the adhesive layer is a layer to which a coating liquid containing an acrylic polyol and a vinyl chloride-vinyl acetate copolymer resin is applied. In particular, a layer in which the adhesive layer is coated with a coating solution containing an acrylic polyol, a vinyl chloride-vinyl acetate copolymer resin, and an isocyanate compound is preferable.

Further, as a result of repeated studies on the adhesion of the metal deposition layer, it was found that the adhesion of the metal deposition layer was extremely excellent when an ethyleneimine-based polymer or a methacrylate containing polyethyleneimine was used for the adhesive layer. I found it. (4) The present invention is the pressure-sensitive adhesive sheet according to (2), wherein the adhesive layer is a layer to which a coating liquid containing a methacrylate ester containing an ethyleneimine-based polymer or polyethyleneimine is applied. In particular, a layer in which the adhesive layer is coated with a coating liquid containing a methacrylic acid ester containing polyethyleneimine and a bisphenol-type epoxy resin is preferable.

Further, as a result of repeated studies on the adhesion and the metallic glossiness of the metal-deposited layer, it was found that an adhesive layer using a specific resin was excellent. (5) In the present invention, the adhesive layer is a layer coated with an aqueous dispersion solution of an ionomer-based polyolefin copolymer, and the coating layer is formed by longitudinally stretching at the time of film forming, coating, drying, and transversely stretching. The pressure-sensitive adhesive sheet according to (2).

Further, by using a compound having a glass transition point of 20 ° C. or more for the adhesive layer, blocking between the adhesive layer and the easily printable layer is less likely to occur, and workability is further improved. (6) The present invention is the pressure-sensitive adhesive sheet according to any one of (2) to (5), wherein the adhesive layer is a layer containing a compound having a glass transition point of 20 ° C or higher.

In order to obtain good surface properties with a metallic luster,
It has been found that the base film has a certain arithmetic surface roughness. (7) The above-mentioned (1) to (1) to which the arithmetic average roughness (Ra) according to JIS B 0601 of the easily printable layer is 3.5 μm or less.
The pressure-sensitive adhesive sheet according to any one of (6).

Further, as a result of repeated studies on the suitability of printing the pressure-sensitive adhesive sheet on the surface substrate, it was found that an easily printable layer using a specific resin was excellent. (8) In the present invention, the easily printable layer is a layer coated with an aqueous dispersion solution of an ionomer-based polyolefin copolymer, and the coating layer is formed by longitudinally stretching at the time of film forming, coating, drying, and transversely stretching. (1) to
The pressure-sensitive adhesive sheet according to any one of (7).

(9) In the present invention, the easily printable layer is formed of at least one polymer or copolymer selected from acrylic acid, methacrylic acid, acrylic acid ester and methacrylic acid ester, polyester resin, ethylene-vinyl acetate. The pressure-sensitive adhesive sheet according to any one of (1) to (7), wherein the pressure-sensitive adhesive sheet is a layer coated with a coating liquid containing at least one selected from a copolymer and a vinyl chloride-vinyl acetate copolymer.

(10) The pressure-sensitive adhesive sheet according to (9), wherein the surface substrate has an anchor layer containing an adhesive resin formed between the substrate film and the easily printed layer.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION As a surface substrate constituting a pressure-sensitive adhesive sheet, an easy-printing layer is provided on one side of a transparent polyolefin-based film, and an adhesive layer is provided on the other side, either directly or for enhancing adhesion between the film and a metal deposition layer. This is a configuration having a metal deposition layer through the intermediary.

The polyolefin resin used for the base film used in the present invention includes polypropylene, low density polyethylene, medium density polyethylene, high density polyethylene, ethylene-α olefin copolymer, propylene-α olefin copolymer, Examples include an ethylene-ethyl acrylate copolymer, an ethylene-vinyl acetate copolymer, an ethylene-methyl methacrylate copolymer, and an ethylene-n-butyl acrylate copolymer. Further, these may be used alone, and a mixture in any combination can be suitably used. Further, it may have a single-layer or multi-layer structure. Further, a light stabilizer, an ultraviolet absorber, an antioxidant, a filler, and the like can be added to these polyolefin-based resins as needed.

A further example of a film mainly composed of polypropylene is a polypropylene composition mainly composed of polypropylene, a polypropylene copolymer, or a mixture thereof. Not only a homopolymer of polypropylene, but also ethylene, butene, -A copolymer of propylene with a monomer copolymerizable with propylene such as α-olefins represented by methylpentene, aromatic olefins represented by styrene, dienes represented by butadiene, or polypropylene And polypropylene copolymers, known blends of these, such as polyethylene, poly-α such as various ethylene copolymers
・ Blends with olefins, polystyrene, synthetic rubbers, terpene resins, polyamides, polyesters, polyethers, etc., or mixtures thereof, etc. as main components, and copolymer components of polypropylene copolymers or blend compositions Is not particularly limited as long as the characteristics of the polypropylene film are not lost. Further, an auxiliary agent such as an ultraviolet absorber may be included. In the case of a film made of polypropylene alone, the adhesion of the metal vapor-deposited layer was low, so that a copolymer mainly composed of polypropylene was mixed in an amount of 70 to 95% by weight and a resin mainly composed of polyethylene in an amount of 5 to 30% by weight. Use of a film or a layer in which only polypropylene is laminated on one side of a film in which 5 to 30% by weight of polyethylene is blended with 70 to 95% by weight of polypropylene, or an adhesive layer for improving the adhesion of a metal deposition layer is formed. Is preferred.

Incidentally, the polyolefin-based film needs to be transparent to such a degree that it can be seen from the opposite side when the metal deposition layer is formed on one side. Therefore, it is not preferable to add a material that forms a void to the film. The thickness of the polyolefin-based film is not particularly limited, but is about 25 to 200 μm for a label and about 25 to 80 μm for a display label for a plastic container.

The easily printable layer formed on one side of the polyolefin-based film can be roughly divided into a film obtained by applying a resin for an easily printable layer after stretching the film in a longitudinal direction, and a film stretched in a lateral direction and a film stretched biaxially. There are two types, one in which a layer coated with a printing resin is applied, and both methods are possible in the present invention. Also, an easily printable layer is formed using the method described above,
It is also possible to form a plurality of easy-to-print layers by forming an easy-to-print layer using the method of forming an easy-to-print layer by a further method, and forming an easy-to-print layer by a further method.

The former method using polypropylene as a main component will be described. The polypropylene composition is melt-extruded according to a conventional method, and is first stretched in the machine direction to obtain a machine direction uniaxially stretched film. A desired one side or both sides of the obtained longitudinally uniaxially stretched film may be subjected to a flame treatment and / or a corona discharge treatment in order to increase the wetting tension of the surface. Thereafter, an easy print layer is applied to the surface.

The resin to be applied is an acrylic resin,
Polyester resin, ionomer resin, SBR resin,
There are vinyl acetate resins and the like, and among them, a resin containing an ionomer as a main component (particularly, a polyolefin copolymer containing an ionomer as a main component) is preferable because of excellent adhesion.
As a method for applying these resins, a known method, for example, a method such as a metaling bar method, a gravure roll method, an air knife method, a spray method, and a reverse roll method can be used. After coating, the applied layer is sufficiently dried and stretched in the transverse direction before stretching in the transverse direction. The corona discharge treatment can be further applied to the resin film surface of the film after the transverse stretching. Thus, a polypropylene film having an easily printed layer is obtained. In this case, the coating amount is about 0.001 to 0.4 g / m ² , preferably 0.1 to 0.4 g / m ² .
005 to 0.2 g / m ² . The easily printed layer formed in this manner is preferable because of its excellent transparency.

The latter method will be described. A polypropylene film is obtained by biaxially stretching the polypropylene composition according to a conventional method. A resin such as an acrylic resin, a polyester resin, an ionomer resin, an SBR resin, or a vinyl acetate resin is applied to the surface. In particular, one or more polymers and copolymers of acrylic acid, methacrylic acid, acrylic esters and methacrylic esters containing ester bonds, polyester resins, ethylene-vinyl acetate copolymers, and vinyl chloride-vinyl acetate copolymers It is preferable to select one or more from polymers and the like.

Examples of the acrylic resin include acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, sec-butyl acrylate, and tert-acrylate.
Butyl, pentyl acrylate, heptyl acrylate, hexyl acrylate, octyl acrylate, hexadecyl acrylate, dimethylpropyl acrylate, ethyl propyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, 2-t-acrylate
tert-butylphenyl, naphthol acrylate, chlorophenyl acrylate, cyanobenzyl acrylate, cyanophenyl acrylate, thiabutyl acrylate, isobornyl acrylate, methacrylic acid, methyl methacrylate, homopolymers of butyl methacrylate and the like.
Copolymers of at least one kind, and copolymers of at least one of these with styrene can be mentioned.

Examples of the polyester resin include poly-2-hydroxyacetic acid, polyhydroxypropionic acid, polyethylene oxalate, polymethylene azelate, polyethylene terephthalate and the like. Further, the above-mentioned polyester resin may be modified with hydroxyl or carboxyl.

The ethylene-vinyl acetate copolymer-based resin and the vinyl chloride-vinyl acetate copolymer-based resin include those modified with hydroxy or carboxyl.

Known methods for applying these easy-to-print layers can be used, for example, methods such as a metering bar method, a gravure roll method, an air knife method, a spray method, and a reverse roll method. Incidentally, it is preferable that the thickness of the easy printing layer is 5 g / m ² or less, printability, and more preferably 3 g / m ² or less from the haze. If it exceeds 5 g / m ² , transparency may decrease, or drying may be insufficient in a coating process, resulting in blocking.

The resin applied as the easy print layer is -20 to 20.
It is selected from a mixture of at least one ester bond-containing polymer (a) having a glass transition temperature of 20 ° C and at least one ester bond-containing polymer (b) having a glass transition temperature of 40 to 80 ° C. Is preferred.

In the easily printable layer, an organic and / or inorganic pigment may be contained in the binder resin as a blocking measure. At this time, the arithmetic average roughness (Ra) is 3.
The average particle size and content of the pigment are not particularly limited as long as they do not exceed 5 μm. By the way, when the arithmetic average roughness (Ra) exceeds 3.5 μm, the transparency is reduced, the surface is roughened, and the appearance may be impaired.

In the present invention, the kind of the easy-to-print layer is not particularly limited, but it is necessary that the metal deposition layer formed on the opposite surface is transparent enough to be seen through the easy-to-print layer. In addition, a recording layer such as an ink jet recording layer, a thermal transfer image receiving layer, and a thermosensitive coloring layer may be formed on the entire surface or a part of the easy printing layer. In addition, ink jet recording suitability and thermal transfer image receiving suitability can be imparted to the easy print layer itself.

When the easy-printing resin is applied to the biaxially stretched film, an adhesive resin is contained between the polyolefin-based film and the easy-printing layer in order to improve the adhesion between the easy-printing layer and the polyolefin-based film. An anchor layer can be provided. Alternatively, to provide a layer coated with a resin for an easy-to-print layer after longitudinal stretching of the film, and to further apply an easy-to-print layer to the horizontally stretched film, in order to improve the adhesion of the easy-to-print layer formed by coating. , An anchor layer can be formed.

Examples of the adhesive resin for the anchor layer include, but are not limited to, isocyanate compounds, resins having an oxozaline group, and resins having an ethyleneimine group. The isocyanate-based compounds may be used alone or as a mixture of two or more. In addition, the resin having an oxazoline group and the resin having an ethyleneimine group may be used alone, and may be used in combination with an epoxy compound for improving water resistance.

As a method for applying the anchor layer, a known method, for example, a metaling bar method, a gravure roll method, an air knife method, a spray method, a reverse roll method, or the like can be used. Further, the coating amount of the anchor layer is about 0.01 to 1 g / m ² , preferably 0.03 to 1 g / m ^2.
It is in the range of 0.3 g / m ² .

An adhesive layer can be formed to increase the adhesion between the film and the metal deposition layer. The composition of the adhesive layer is a resin (compound) that improves the adhesion of the metal deposition layer.
Any layer may be used as long as it is a layer coated with. Specifically, acrylic polyol and vinyl chloride-vinyl acetate copolymer, methacrylic acid ester compound containing ethyleneimine-based polymer or polyethyleneimine, and nitrocellulose and acrylic polyol resin have excellent adhesion, and It is preferable because it has excellent water resistance. In addition, an auxiliary agent such as a curing agent or an ultraviolet absorber may be added to the adhesive layer. In particular, it is preferable to add an isocyanate compound to the acrylic polyol and the vinyl chloride-vinyl acetate copolymer to promote crosslinking, since the adhesion is further improved. In particular, an adhesive layer containing a methacrylic acid ester compound containing polyethyleneimine and a bisphenol-type epoxy resin is preferable because the adhesion to polypropylene is good and the water resistance is improved. In particular, it is preferable to use a resin (compound) having a glass transition point of 20 ° C. or higher because blocking with the easily printable layer can be prevented.

As a method of forming the adhesive layer, the above-mentioned coating components are diluted with a solvent such as toluene, ethyl acetate, IPA or MEK to such an extent that they can be coated, for example, a metaling bar system, a gravure roll system, or an air knife. It can be formed by a known coating method such as a method, a spray method, and a reverse roll method.

The thickness of the adhesive layer is not problematic and is not particularly limited as long as the adhesion with the metal deposition layer is good, but excessive coating increases the cost and may cause blocking. Therefore, it is preferable to form the film in a range of about 3.0 μm or less, preferably about 1.5 μm or less. The easy print layer and the adhesive layer may be simultaneously applied to form the easy print layer and the adhesive layer.

Further, as the adhesive layer, a layer in which a resin for improving the adhesive property is applied after the film is stretched in the longitudinal direction and the film is stretched in the transverse direction can be used. This method is preferable because an adhesive layer having high transparency can be obtained. Specifically, the polyolefin composition is melt-extruded according to a conventional method, and is first stretched in the longitudinal direction to obtain a longitudinally uniaxially stretched film. A desired one side or both sides of the obtained longitudinally uniaxially stretched film may be subjected to a flame treatment and / or a corona discharge treatment in order to increase the wetting tension of the surface. Thereafter, an adhesion improving layer is applied to the surface. Prior to the stretching in the transverse direction, the applied layer is sufficiently dried and stretched in the transverse direction. The corona discharge treatment can be further applied to the resin film surface of the film after the transverse stretching. In this way, a film having an adhesive layer can be formed. The resin to be applied is preferably an aqueous dispersion of an ionomer-based polyolefin copolymer. Also, after longitudinal stretching, apply a coating liquid on both sides and dry,
By stretching in the transverse direction, the resin film surface can be applied to both surfaces, and the easy print layer can be used on one surface and the adhesive layer for metal deposition can be used on the other surface. This configuration is preferable because it becomes a film substrate having excellent transparency and the number of manufacturing steps is reduced.

The haze value of the film before metal deposition is 5
% Or less, and more preferably 3% or less. If the haze value of the film before metal deposition exceeds 5%, the luster state is reduced when the metal is deposited, resulting in impaired appearance. At least one of the layers such as the film base material, the adhesive layer, and the easily printable layer contains a coloring agent (dye or the like), so that a color tone that cannot be obtained by simple vapor deposition can be obtained.

As a method of vacuum-depositing a metal on the adhesive layer, a vacuum deposition method usually used can be used as it is.
Aluminum (aluminum) is the most common metal that can be used, and gold, silver, copper, chromium, tin, indium, antimony, nickel and the like can be used in addition to aluminum. For example, a metal may be heated and vapor-deposited on one surface of a base film in a container under a high vacuum, and may be suitably used from a small batch type to a continuous type in which vapor deposition is continuously performed on a film wound in a roll. The thickness of aluminum to be deposited is 20
行 う to 1000Å, preferably 500Å
The following is preferred.

In the present invention, the pressure-sensitive adhesive layer and the release sheet are laminated on the metal-deposited layer side of the thus-deposited vapor-deposited film. Note that an adhesive layer may be laminated after forming a resin layer for protecting the deposited layer on the surface of the metal deposited layer.

The constituents of the pressure-sensitive adhesive used in the present invention are not particularly limited, and include rubber-based, acrylic-based, vinyl ether-based, urethane-based and silicone-based adhesives. In particular, an acrylic premonomer or an acrylic resin containing an acrylic monomer as a main component is preferable from the viewpoint of transparency and weather resistance.

The acrylic resin is not particularly limited.
Vinyl monomer having an acrylic group, vinyl monomer having an epoxy group, vinyl monomer having an alkoxyl group, vinyl monomer having an ethylene oxide group,
Vinyl monomer having an amino group, vinyl monomer having an amide group, vinyl monomer having a halogen atom,
A vinyl monomer having a phosphate group, a vinyl monomer having a sulfonic acid group, a vinyl monomer having a silane group,
Examples include those containing a vinyl monomer having a phenyl group, a vinyl monomer having a benzyl group, a vinyl monomer having a tetrahydrofurfuryl group, and other copolymerizable monomers.

Examples of the form of the pressure-sensitive adhesive include a solvent type, an emulsion type and a hot melt type. In the case of the emulsion type, care must be taken because the existing emulsifier may cause discoloration of the metal deposition layer. Various additives such as natural resins such as rosin, modified rosin, rosin and modified rosin derivatives, polyterpene resins, modified terpene, aliphatic hydrocarbon resins, and cyclopentadiene resins for improving the adhesive properties of these acrylic resins , Aromatic petroleum resins, phenolic resins, alkyl-phenol-acetylene resins, cumarone-indene resins, tackifiers including vinyltoluene-α-methylstyrene copolymers, antioxidants, stabilizers, Softeners such as oils, fillers, stabilizers, pigments, colorants, and the like can be added as needed. These may be used in combination of two or more as necessary. The acrylic resin is a bulk polymerization method, a solution polymerization method, a suspension polymerization method, and an emulsion polymerization method in which a monomer insoluble or hardly soluble in water is dispersed together with an emulsifier and polymerization is performed using a water-soluble polymerization initiator. And the like. The mixing ratio of the tackifier is 1 to 50 parts by weight based on 100 parts by weight of the acrylate polymer. Incidentally, if the amount is less than 1 part by weight, the effect of improving the adhesive strength is poor, and if it exceeds 50 parts by weight, the adhesive strength tends to decrease.

Further, in order to improve weather resistance, an organic UV absorber such as benzophenone or benzotriazole may be added to the pressure-sensitive adhesive layer. To form the pressure-sensitive adhesive layer, the pressure-sensitive adhesive as described above is applied to a release sheet, dried if necessary to form a pressure-sensitive adhesive layer, and bonded to a surface substrate, or the pressure-sensitive adhesive is applied to the surface substrate. After application, the adhesive sheet of the present invention is obtained by laminating with a release sheet. The former method is preferred from the viewpoint of work efficiency and the like.

As a device for applying the pressure-sensitive adhesive, a reverse roll coater, knife coater, bar coater, slot die coater, air knife coater, reverse gravure coater, vario gravure coater, or the like is used. in the range of 50 g / m ^2, and more preferably is adjusted from 10 to 30 g / m ^2.
If the amount is less than 5 g / m ² , the adhesive strength to the adherend will be insufficient. On the other hand, if it exceeds 50 g / m ² , the adhesive may protrude, cause cohesive failure at the time of peeling, or cause rise at the time of punching. is there.

The release sheet that covers the pressure-sensitive adhesive layer is not particularly limited, and paper such as high-density base paper such as glassine paper, clay-coated paper, kraft paper, or high-quality paper laminated with a film such as polyethylene, or high-quality paper A dry weight of a fluororesin or silicone resin is applied to a paper coated with polyvinyl alcohol or acrylate copolymer resin or a plastic film such as polyethylene terephthalate or polypropylene to a weight of about 0.1 to 3 g / m ^2. What has been applied and provided with a release agent layer by thermal curing, ionizing radiation curing, or the like is appropriately used.

As a coating device in this case, a bar coater, an air knife coater, a direct gravure coater, an offset gravure coater, a multi-stage roll coater and the like are appropriately used.

[0048]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should be understood that the present invention is by no means restricted thereto.

Example 1 (Production of surface substrate) A biaxially stretched polypropylene film (trade name "PY-101", manufactured by Oji Paper Co., Ltd.) (thickness: 50 μm) was formed of an acrylic ester copolymer as an easy print layer. After applying a coating agent (trade name “X-590-354W”, manufactured by Seiden Chemical Co., Ltd.) so as to have a thickness of 1.0 μm, a copolymer of acrylic polyol and vinyl chloride is coated on the surface opposite to the easy print layer. (Two-component reaction type ink VM
-D medium, glass transition temperature of 50 ° C. or higher, manufactured by Dainichi Seika Co., Ltd.) and an isocyanate compound (VM-D curing agent,
(Nippon Seika Chemical Co., Ltd.) diluted with toluene to a thickness of 0.7
It was applied to a thickness of μm to form an adhesive layer. This sheet did not cause blocking even when held in a rolled state. Next, aluminum is coated on the surface of the adhesive layer by 200 to 40.
Vapor deposition was performed to a thickness of 0 mm.

(Production of pressure-sensitive adhesive sheet) Acrylic pressure-sensitive adhesive
(Product name "OPT-1", manufactured by Seiden Chemical Co., Ltd.)
Metal chelate crosslinking agent (trade name "M-2"
Was added and mixed to obtain an adhesive coating liquid. Commercially available
Polyethylene terephthalate separator (trade name)
"Therapeutic BK # 25", Toyo Metallizing Co., Ltd.
20g / m in dry weight ^TwoWill be
And dried at 90 ° C for 1 minute.
After that, the adhesive sheet is adhered to the surface
Obtained.

Example 2 (Production of surface substrate) After a polypropylene film was uniaxially stretched, a solution composed of an ionomer-based polyolefin copolymer was applied on one surface as an easily printable layer, and further stretched to form a printable polypropylene film (50 μm thick). )
(Coat amount 0.03μm) on the opposite side to the printable side,
Acrylic polyol, vinyl chloride-vinyl acetate copolymer (two-part reaction type ink VM-D medium, manufactured by Dainichi Seika Co., Ltd.) and isocyanate compound (VM-D curing agent,
(Nippon Seika Chemical Co., Ltd.) diluted with toluene to a thickness of 0.7
It was applied to a thickness of μm to form an adhesive layer. This sheet did not cause blocking even when held in a rolled state. Next, aluminum is coated on the surface of the adhesive layer by 200 to 40.
Vapor deposition was performed to a thickness of 0 mm. (Production of pressure-sensitive adhesive sheet) A pressure-sensitive adhesive sheet of the present invention was obtained in the same manner as in Example 1 except that the above-mentioned surface substrate was used.

Example 3 (Production of Surface Substrate) In Example 2, the surface substrate was a printable polypropylene film (thickness: 5) coated with a solution comprising an ionomer-based polyolefin copolymer on the surface.
0 μm) (coat amount 0.03 μm) and an olefin-based coating agent (trade name “PE-1035”, manufactured by Toho Chemical Co., Ltd.) so as to have a thickness of 1.0 μm to form an easily printable layer. On the surface, a graft compound of acrylic acid ester and polyethyleneimine (Polyment NK-35)
0, a glass transition temperature of 40 ° C., manufactured by Nippon Shokubai Co., Ltd.) and a bisphenol-type epoxy resin (Epicoat 828, manufactured by Yuka Shell Epoxy Co., Ltd.) diluted with toluene and applied to a thickness of 0.7 μm to form an adhesive layer. Was formed. This sheet hardly caused blocking even when held in a rolled state. Next, aluminum was vapor-deposited on the surface of the adhesive layer to a thickness of 200 to 400 °. (Production of pressure-sensitive adhesive sheet) A pressure-sensitive adhesive sheet of the present invention was obtained in the same manner as in Example 1 except that the above-mentioned surface substrate was used.

Example 4 (Production of surface base material) A biaxially stretched polypropylene film (trade name "PY-101", manufactured by Oji Paper Co., Ltd.) (thickness: 50 μm) was formed of an acrylic ester copolymer as an easy print layer. After applying a coating agent (trade name “X-590-354W”, manufactured by Seiden Chemical Co., Ltd.) to a thickness of 1.0 μm, an amino group-pending acrylic polymer (emulsion type coating) Agent Polyment S
K-1000, glass transition temperature 20 ° C., manufactured by Nippon Shokubai Co., Ltd.) and trimethylolpropane polyglycidyl ether (Denacol EX-321, manufactured by Nagase Kasei Kogyo Co., Ltd.) are diluted with toluene to have a thickness of 0.7 μm. It was applied to form an adhesive layer. This sheet showed little blocking even when held in a rolled state. Next, aluminum was vapor-deposited on the surface of the adhesive layer to a thickness of 200 to 400 °. (Production of pressure-sensitive adhesive sheet) A pressure-sensitive adhesive sheet of the present invention was obtained in the same manner as in Example 1 except that the above-mentioned surface substrate was used.

Example 5 (Production of surface substrate) In Example 2, a printable polypropylene film (thickness: 5) was prepared by coating a surface substrate with a solution comprising an ionomer-based polyolefin copolymer.
0 μm) (coating amount: 0.03 μm) and polyethyleneimine (P-1000, manufactured by Nippon Shokubai Co., Ltd.) as an anchor layer for easy printing to a thickness of 0.01 μm.
Further, an acrylic resin (Acrydick A-157, manufactured by Dainippon Ink and Chemicals, Inc .: 50 parts and Acrydick A-166, manufactured by Dainippon Ink and Chemicals, Inc .: 50 parts) is mixed as an easily printable layer. An organic pigment (Eposter MA1006, manufactured by Nippon Shokubai Co., Ltd .: 1 part) was applied to a thickness of 2.0 μm to form a print layer.
On the opposite side of the easy print layer, a copolymer of acrylic polyol and vinyl chloride (VM-D medium of two-part reaction type, manufactured by Dainichi Seika Co., Ltd.) and an isocyanate compound (V
An MD hardener, manufactured by Dainichi Seika Co., Ltd.) was diluted with toluene and applied to a thickness of 0.7 μm to form an adhesive layer. This sheet did not cause blocking even when held in a rolled state. Next, aluminum was vapor-deposited on the surface of the adhesive layer to a thickness of 200 to 400 °. (Production of pressure-sensitive adhesive sheet) A pressure-sensitive adhesive sheet of the present invention was obtained in the same manner as in Example 1 except that the above-mentioned surface substrate was used.

Example 6 A pressure-sensitive adhesive sheet of the present invention was obtained in the same manner as in Example 1, except that an emulsion-type acrylic pressure-sensitive adhesive (L-145A, manufactured by Nippon Carbide Industry Co., Ltd.) was used. In addition, even if stored for a long period of time, there was almost no discoloration of the metal deposition layer.

Comparative Example 1 An adhesive sheet was obtained in the same manner as in Example 1 except that the adhesive layer was not provided.

Comparative Example 2 (Production of Surface Substrate) A pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1 except that the easy-to-print layer was not provided.

Comparative Example 3 In Example 5, an organic pigment (Eposter MA100) was used.
6, manufactured by Nippon Shokubai Co., Ltd.) to obtain a pressure-sensitive adhesive sheet in the same manner as in Example 5.

The adhesive sheet thus obtained was evaluated as follows, and the results are shown in Table 1.

<Evaluation Items> [Adhesion Strength] The obtained pressure-sensitive adhesive sheet was adhered to a heat-resistant glass having a thickness of 5 mm, immersed in warm water of 40 ° C. for 48 hours, taken out, and then a cellophane tape (Nichiban CT-18) was applied for about 1 hour.
After applying 50 mm and pressing it evenly with a finger, quickly peel it off and check whether the print or label has come off on the cellophane tape. In the pressure-sensitive adhesive sheet of Example 4, the adhesive layer was slightly clouded. ：: Label is not peeled at all △: Label is slightly peeled ×: Label is completely peeled

[Ink Adhesion] A sample printed with a seal printing machine of Onda Seisakusho was adhered with an adhesive tape (manufactured by Oji Chemical Co., Ltd.) in such a manner that air was not embraced. ,evaluated. ：: The ink is not peeled off at all △: The ink is peeled slightly ×: The ink is peeled a lot

[Surface Roughness] The arithmetic average roughness of the easily printable layer of the obtained pressure-sensitive adhesive sheet was measured according to JIS B 0601-1994.
It was measured according to.

[Surface gloss] ：: glossy, good Δ: slightly cloudy ×: cloudy

[Comprehensive evaluation] ：: Very good as a printable glossy pressure-sensitive adhesive sheet ○: A level that does not pose a practical problem as a printable glossy pressure-sensitive adhesive sheet X: A level that causes a practical problem as a printable glossy pressure-sensitive adhesive sheet

[0065]

[Table 1]

[0066]

As is clear from the results shown in Table 1, the pressure-sensitive adhesive sheet of the present invention has excellent adhesiveness for printing and metal deposition, so that printing or vapor deposition does not come off even when used for a display label or the like. It is a pressure-sensitive adhesive sheet which does not cause delamination even when it is immersed in water or the like.

Continued on the front page F-term (reference) 4F100 AB01B AK03 AK03A AK07 AK15D AK15G AK22D AK22G AK24D AK25D AK25G AK41D AK51G AK68D AK70G AL01 AL01D AL01G AT00A BA03 BA04 BA07 BA10E BAH EJB EH AA06 AA07 AA08 AA10 AA11 AA14 AB01 CA04 CA08 CC03 CC04 CC05 CD01 CD05 DB02 FA01

Claims (10)

[Claims] 1. A pressure-sensitive adhesive sheet comprising a film substrate, a metal vapor-deposited layer, a pressure-sensitive adhesive layer, and a release sheet laminated on each other, wherein the film substrate is a transparent polyolefin-based film and the surface on which no metal vapor-deposited layer is formed is easily printed. An adhesive sheet having good printability, characterized by having a layer. 2. The pressure-sensitive adhesive sheet according to claim 1, wherein an adhesive layer is provided on the surface of the film substrate on which the metal deposition layer is formed. 3. The pressure-sensitive adhesive sheet according to claim 2, wherein the adhesive layer is a layer containing an acrylic polyol and a vinyl chloride-vinyl acetate copolymer resin. 4. The pressure-sensitive adhesive sheet according to claim 2, wherein the adhesive layer is a layer containing a methacrylate ester containing an ethyleneimine-based polymer or polyethyleneimine. 5. The adhesive layer is a layer coated with an aqueous dispersion of an ionomer-based polyolefin copolymer, and is a layer formed by longitudinally stretching, applying, drying and then transversely stretching the film when forming the film. Item 3. The pressure-sensitive adhesive sheet according to Item 2. 6. The pressure-sensitive adhesive sheet according to claim 2, wherein the adhesive layer has a layer containing a compound having a glass transition point of 20 ° C. or higher. 7. The easy print layer has an arithmetic average roughness (Ra) according to JIS B 0601 of 3.5 μm or less.
7. The pressure-sensitive adhesive sheet according to any one of 6. 8. The easy-to-print layer is a layer coated with an aqueous dispersion of an ionomer-based polyolefin copolymer,
After coating the coating layer in the longitudinal direction during film formation,
The pressure-sensitive adhesive sheet according to any one of claims 1 to 7, which is a layer formed by drying and laterally stretching. 9. An easy print layer comprising acrylic acid, methacrylic acid,
Coating liquid containing at least one polymer or copolymer selected from acrylates and methacrylates, polyester resin, ethylene-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer The pressure-sensitive adhesive sheet according to any one of claims 1 to 7, which is a layer coated with: 10. The pressure-sensitive adhesive sheet according to claim 9, wherein an anchor layer containing an adhesive resin is formed between the film substrate and the easily printable layer.