JPH1049051A - Film for label sheet and label sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a film for a label sheet which allows bright printing and has an excellent stainproof property, chemical resistance, etc., by fonning a thin film consisting of specific metal oxide atop a fluorine-contained film. SOLUTION: The film for the label sheet is formed by forming the thin film consisting of the oxide of at least >=1 kinds of metals selected from a group consisting of Si, Ti, Ta, Hf, Mo, W, Nb, Sn, Cr and Zn, etc., is formed by a dry process method atop at least the fluorine-contained film. The oxide thin film 6 consisting of Si and Sn is formed by a sputtering method on the surface of the fluorine-contained film 4 prepd. as the surface base material of the label, by which the film for the label sheet is obtd. The rear surface of the resin layer 3 with the oxide layer obtd. in such a manner is subjected to a corona discharge treatment and, thereafter, a vapor deposited Cr layer 8 is formed by a vacuum vapor deposition method on its surface. Further, a tacky adhesive layer 10 is applied on the surface of this vapor deposited Cr layer 8 and release paper 1 is stuck, by which the label sheet 2 is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a label sheet film and a label sheet used for labels on which characters and patterns are printed which are attached to various articles such as motorcycles.

[0002]

2. Description of the Related Art A resin sheet such as a vinyl chloride sheet is generally used as a base material for a label or a sticker attached to a motorcycle, an automobile, a signboard, an electric appliance, etc. Is provided with release paper via an adhesive, while the surface of the sheet is printed. However, when a vinyl chloride sheet is used as a base material, particularly in applications such as motorcycles,
Since it is used outdoors, dirt easily adheres, and gasoline or the like may adhere to the label, which may cause deterioration.

[0003] In response to such problems, in recent years, fluororesin films have been used as a base material from the viewpoints of, for example, excellent antifouling properties such that dirt hardly adheres and chemical resistance such that they are not deteriorated by gasoline or the like. It has become.
However, on the other hand, there is a problem that the adhesion and the adhesion (so-called ink paste) with the ink when printing are reduced, and it is difficult to print clearly.

[0004]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above circumstances, and enables clear printing and
It is an object of the present invention to provide a label sheet film and a label sheet having excellent antifouling properties and chemical resistance.

[0005]

Means for Solving the Problems To achieve the above object, the present invention provides a method for manufacturing a semiconductor device comprising the steps of:
Zr, Ti, Ta, Hf, Mo, W, Nb, Sn, I
Provided is a printable label sheet film, characterized in that a thin film made of an oxide of one or more metals selected from the group consisting of n, Al, Cr and Zn is formed by a dry method.

Further, the present invention relates to a release paper, an adhesive layer,
Deposition layer, Fluorine-containing resin film, Si, Zr, Ti, T
a, Hf, Mo, W, Nb, Sn, In, Al, Cr, and a label sheet in which thin films made of at least one metal oxide selected from the group consisting of Zn are sequentially laminated, wherein the thin film is A printable label sheet formed on the fluororesin film by a dry method is provided.

Here, the dry method is preferably a sputtering method.

Hereinafter, the present invention will be described in detail. The label sheet film of the present invention comprises at least the upper surface (the surface on the side to be printed) of the fluororesin film (resin layer)
, Si, Zr, Ti, Ta, Hf, Mo, W, Nb,
Thin film (oxide layer) made of oxide of one or more metals selected from the group consisting of Sn, In, Al, Cr and Zn
Is formed by a dry method (hereinafter referred to as a resin layer with an oxide layer).

(A) Resin Layer with Oxide Layer The fluorine-containing resin film used as the base material (resin layer) of the label sheet film of the present invention has antifouling properties, chemical resistance, transparency, durability, and weather resistance. It is excellent in properties and the like, and has a property that it is not denatured even in film formation in an oxygen-containing atmosphere.
The fluorine-containing resin film is not particularly limited as long as it is a thermoplastic resin containing fluorine in the molecular structural formula of the resin,
Conventionally known various fluorine-containing resins can be used. Specific examples include a tetrafluoroethylene resin, a chlorotrifluoroethylene resin, a vinylidene fluoride resin, a vinyl fluoride resin, and a composite of these resins. Particularly, a tetrafluoroethylene-based resin is preferable from the viewpoint of hydrophobicity.

As the tetrafluoroethylene resin,
Specifically, tetrafluoroethylene resin (PTF
E), tetrafluoroethylene / perfluoro (alkoxyethylene) copolymer (PFA), tetrafluoroethylene / hexafluoropropylene / perfluoro (alkoxyethylene) copolymer (EPE), tetrafluoroethylene / hexafluoropropylene copolymer Merging (FE
P), tetrafluoroethylene / ethylene copolymer (ETFE), ethylene / trichlorofluoroethylene copolymer (ETCFE), and the like. Among them, PFA, FEP, ETFE, and ETCFE are preferable from the viewpoint of chemical resistance, antifouling property, and the like, and ETFE is particularly preferable from the viewpoint of cost, mechanical strength, sputter film forming property, and the like.
ETFE is mainly composed of ethylene and tetrafluoroethylene, and may be one obtained by copolymerizing a small amount of a comonomer component, if necessary.

As the comonomer component, tetrafluoro
Ethylene and monomers copolymerizable with ethylene, such as
For example, the following compounds may be mentioned. CF_Two= CFCl, C
F_Two= CH_TwoFluorinated ethylenes such as CF_Two= CF
CF_Three, CF_Two= CHCF_ThreeSuch as fluorinated propylene
Kind, CH_Two= CHC_TwoF_Five, CH_Two= CHC_FourF₉, C
H_Two= CFC_FourF₉, CH _Two= CF (CF_Two)_ThreeH etc.
A fluoroalkyl group having 2 to 10 carbon atoms
Alkyl ethylenes, CF_Two= CFO (CF_TwoCFXO)
_mR_f(Where R_fIs a perfluoroalkyl having 1 to 6 carbon atoms
X is a fluorine atom or a trifluoromethyl group, m
Represents an integer of 1 to 5) and the like.
Vinyl ethers), CF_Two= CFOCF_TwoCF_TwoCF
_TwoCOOCH_ThreeAnd CF_Two= CFOCF_TwoCF (CF_Three)
OCF_TwoCF_TwoSO_TwoF and other carboxylic acid groups
Vinyl ethers having a group that can be converted to a sulfonic acid group
And so on. Ethylene / tetrafluoro in ETFE
The molar ratio of polyethylene is 40 / 60-70 / 30, especially
40/60 to 60/40 is preferred. In addition,
-The content of the component is 0.3 to 10
%, Especially 0.3 to 5 mol% is preferred. Chlorotri
As the fluoroethylene resin, specifically, for example,
Chlorotrifluoroethylene homopolymer (CTF
E) or ethylene / chlorotrifluoroethylene
Polymer (ECTFE) and the like.

In the base material of the label sheet film of the present invention, a mixed resin containing the above-mentioned fluorine-containing resin as a main component and other thermoplastic resin is also preferably used. As the thermosetting synthetic resin, for example, melamine resin, phenol resin, urea resin, furan resin, alkyd resin, unsaturated polyester resin, diallyl phthalate resin, epoxy resin, silicon resin, polyurethane resin, polyimide resin, or polyparabanic acid resin And the like.

The thickness of the fluorine-containing resin film used in the present invention is preferably as small as possible from the viewpoints of aesthetics and difficulty in peeling, while it is preferable to increase the thickness from the viewpoints of strength and ease of handling. The thickness is preferably from 200 to 200 μm, particularly preferably from 20 to 100 μm.

In the label sheet film of the present invention, Si, Zr, Ti, Ta, Hf, Mo, W, N
A thin film made of an oxide of one or more metals selected from the group consisting of b, Sn, In, Al, Cr and Zn is formed by a dry method. The thickness of the oxide thin film in the present invention, from the viewpoint of ensuring adhesion to the ink when printed,
It is preferably 0.5 nm or more. Further, from the viewpoint of maintaining transparency, maintaining the flexibility of the synthetic resin substrate, and adhesion to the fluorine-containing resin film, 30 nm or less, particularly,
Preferably it is 10 nm or less.

The oxide thin film used is Si, Zr, Ti,
Ta, Hf, Mo, W, Nb, Sn, In, Al, Cr
And any one of at least one metal oxide selected from the group consisting of Zn and Zn.

It is preferable that the thin film is made of a metal oxide containing at least Si, since the adhesion is further improved. Specific examples of the metal oxide containing at least Si include SiO ₂ , an oxide of Si and Zr, an oxide of Si and Ti, an oxide of Si and Ta, an oxide of Si and Nb, and an oxide of Si and Nb. And oxide of Sn, oxide of Si and Zn or oxide of Si, Sn and Ti as a main component.

From the viewpoint of the adhesion of the printing layer to the ink and the productivity, an oxide containing Si and Sn, an oxide of Si and Zr, and an oxide of Si and Ti as main components Is particularly preferable, and an oxide containing an oxide of Si and Sn as a main component is particularly preferable.

In the present invention, the content of Si in the oxide thin film is preferably 20 to 80 atomic%, and more preferably 30 to 70 atomic%, based on all metals. By setting the content of Si in such a range, 1) the coverage of the fluorine-containing resin film is improved by the action of a metal component other than Si. 2) When DC sputtering is used as the film forming method, arcing is prevented by using an alloy target having the same composition range as the oxide film. The effect is obtained. On the other hand, when an alloy target is used, S
When the content ratio of i increases, the film forming rate tends to decrease. Therefore, from the viewpoint of productivity, it is preferable that Si is 70 atomic% or less.

In the present invention, the method for obtaining the oxide thin film is not particularly limited as long as it is a dry method. The dry method is
Compared with the wet method, the film can be made uniform, and the formed film has high adhesion to the fluorine-containing resin film, which is one of the important components for achieving the object of the present invention. Examples of the dry method include a vacuum deposition method, a sputtering method, and a CVD method.
And an ion plating method. Especially,
The sputtering method is preferable because it has excellent productivity, is widely used industrially, and can obtain a very dense film having high adhesion to the fluorine-containing resin film in a uniform film thickness.

As the sputtering method, any of a direct current sputtering method and a high frequency sputtering method can be used. The DC sputtering method is preferable because a film can be efficiently formed on a large-area substrate at a high film forming rate.

As an example of an oxide film containing an oxide of Si and Sn as a main component, there is a thin film made of an oxide of Si and Sn. A thin film composed of an oxide of Si and Sn is obtained by forming a film by a reactive sputtering method in an oxygen-containing atmosphere using a mixture target of Si and Sn. When a mixture target of Si and Sn is used, unlike a Si target, a normal DC sputtering method can be used for reasons such as improvement in the conductivity of the target, and the film formation rate can be increased.
At this time, by applying an intermittent negative DC voltage to the target, it is possible to effectively suppress the occurrence of arcing during film formation, increase input power, and maintain a higher film formation rate for a long time. It is. In addition, as a result of an increase in the coverage on the resin layer surface, a reduction in the minimum film thickness for exhibiting printability is also advantageous in terms of productivity and economy. The power density on the target during sputtering is 0.5
It is used at about 10 to 10 W / cm ² , and the gas pressure is 1 to 1
0 mTorr, preferably about 2 to 6 mTorr.

Other than Sn, Zr, Ti, Ta, Hf,
Although the same effect as that of the Si—Sn system can be obtained by using a target composed of Si and one or more metals selected from the group consisting of Mo, W, Nb, In, Al, Cr, and Zn, Si—Sn When a metallic target is used, the deposition rate is the highest and the productivity is the highest.

The target composed of Si and Sn is as follows:
It may be in the form of a mixture or in the form of an alloy. For example, a mixture target of Si and Sn is obtained by molding a mixture of Si and Sn by a CIP method (cold isostatic pressing method) or a warm press (a mold forming press at a temperature just below the melting point of Sn). Can be.

(B) Cr Vapor Deposition Layer In the label sheet film of the present invention, in addition to the resin layer with an oxide layer (A), a Cr vapor deposition layer (B) can be formed as a lower layer on the resin surface side. By forming the Cr vapor-deposited layer, it is possible to obtain an effect of imparting a metal color to the label to improve the appearance and texture, and to enhance the color of the printed layer when printing is performed. In this case, if the surface of the fluororesin film (the surface on which Cr is deposited) is subjected to corona discharge treatment, the adhesion between the fluororesin film and the Cr deposition layer is ensured. Further, as another aspect, in order to increase the adhesion with the Cr deposited layer also on the surface on which Cr is deposited,
The above-mentioned oxide thin film may be formed instead of the corona discharge treatment. Cr deposition may be performed by a vacuum deposition method, a sputtering method, an ion plating method, or the like. Cr
The deposition layer is not particularly limited as long as it is a thin film of metal Cr or a Cr-based alloy.

(C) Adhesive Layer, Release Paper The label sheet film of the present invention may be further provided with a release paper (C) below the Cr-deposited layer (B) via an adhesive to form a label sheet. Good. The pressure-sensitive adhesive is not particularly limited, and natural rubber to which a tackifier such as rosin is added, synthetic rubber (styrene-butadiene-based, styrene-isoprene-based), acrylic acid higher ester-based vinyl copolymer, or the like is used as an organic solvent. A conventionally known adhesive such as a dissolved one or an aqueous emulsion-based adhesive obtained by emulsion copolymerization of an acrylic monomer such as butyl acrylate or 2-ethylhexyl acrylate with another vinyl monomer may be used. Further, these adhesives may be subjected to a crosslinking treatment, if necessary, and other components such as a coagulant, a plasticizer, and a release agent may be added.

The release paper is not particularly limited, and any conventionally known release paper may be used. For example, a cross-linked polydimethylsiloxane (PD) may be used for release base paper such as glassine paper or woodfree paper.
(MSiO) or the like as a release layer, or a plastic film. With such a configuration,
Since the release paper can be peeled off at the work site and attached to a desired article, the workability is excellent.

(D) Print Layer, Protective Film Layer The label sheet of the present invention may further have a print layer on the surface of the resin layer with an oxide layer (A), ie, the surface of the metal oxide thin film. As described above, since such a metal oxide thin film is formed on the surface of the fluorine-containing resin film by a dry method, the adhesion between the printing layer and the ink is excellent, and therefore, without any special pretreatment. Printing can be performed sharply, and the printing clarity is maintained for a long time.
The ink used for the printing layer is not particularly limited, and a known ink is used. Further, a protective film may be provided on the upper surface of the printing layer to protect the printing layer thus formed. This protective film is mainly for protecting the printed layer of the label before use, and is often peeled off after the label is attached to the article. Therefore, the protective film is preferably configured to be releasable. The material of the protective film is not particularly limited, and a conventionally known film material such as vinyl chloride can be used.

The label sheet film and label sheet of the present invention are constituted as described above. In the case of a label sheet film consisting of only the resin layer (A) with an oxide layer, It is only necessary to adhere to the target adherend by a known method such as application of an adhesive, and the adhesion method is not particularly limited. In the case of a label sheet provided with release paper (C), printing is performed, a protective film is attached as necessary, and then the release paper is peeled off at the time of use.
The adhesive layer may be exposed and attached to the adherend. In addition, you can print, paint,
By sticking to a place where writing or the like is desired, printing, painting, writing, or the like can be performed even on a material that is originally difficult to print.

The application of the label sheet film and label sheet of the present invention can be widely used as decorations and display materials, and is not particularly limited. Therefore, it can be suitably used for those used outdoors such as motorcycles, automobiles and other vehicles, signs and the like, or those used in places where dirt easily adheres such as kitchen appliances. In particular, it is preferable that the label sheet of the present invention can exert its function most, since it does not deteriorate even when gasoline adheres, when it is attached to a gasoline tank of a vehicle such as a motorcycle.
Further, it can be widely used in other applications, for example, in electric appliances and the like.

[0030]

EXAMPLE A label sheet 2 of the present invention was produced with the structure shown in FIG. 1, and a label 20 having a pattern 20 and a shape shown in FIG. 2 was produced. An ETFE film 4 (thickness: 60 μm) was prepared as a surface substrate of the label. In a direct-current sputtering device, a substrate having the above-mentioned film piece of 10 cm square fixed to a glass plate of 10 cm square was set on the anode side, and Si and Sn were placed.
(Atomic ratio 50:50) of the target (hereinafter, referred to as
Target A) was set on the cathode side. After evacuating the inside of the apparatus to the order of 10 ⁻⁵ Torr, argon and oxygen were introduced into the apparatus at a flow ratio of 1: 4, and the sputtering gas pressure was adjusted to 5 × 10 ⁻³ Torr. Sputtering was performed at a power density of 2.75 W / cm ² using a DC power supply, and an oxide thin film 6 of Si and Sn (thickness: about 6 n
m) was formed on the surface of the film 4 to obtain a film for a label sheet. After performing a corona discharge treatment on the back surface (the surface opposite to the treated surface) of the resin layer 3 with the oxide layer obtained in this way, a Cr vapor-deposited layer 8 was formed on this surface by a vacuum vapor deposition method. Further, an adhesive 10 was applied to the surface of the Cr vapor-deposited layer 8 and a release paper 12 was attached to obtain a label sheet.

A pattern was printed on the surface of the oxide film thin film 6 of the obtained label sheet to form a printed layer 14. The label sheet of the present invention had good print paste and was able to print a pattern very sharply. Further, a vinyl chloride film was formed as a protective film layer 16 on the surface of the print layer 14. The label sheet obtained as described above was cut into a desired shape to obtain a label.

[0032]

The film for label sheet and the label sheet of the present invention have excellent adhesiveness to ink, so that clear printing is possible, and the antifouling property and chemical resistance are also excellent. Therefore, the beauty of the label can be maintained over a long period of time. In addition, when an oxide thin film is formed by a sputtering method, a film can be efficiently formed on a large-area substrate at a high film formation rate, and thus productivity is high. Furthermore, the label sheet film and label sheet of the present invention are particularly excellent in gasoline resistance, and thus are suitable for use in sticking to gasoline tanks such as motorcycles.

[Brief description of the drawings]

FIG. 1 is a partial cross-sectional view of an example of a label sheet of the present invention.

[Explanation of symbols]

 2 Label sheet 3 Resin layer with oxide layer 4 Fluorine-containing resin film 6 Oxide thin film 8 Cr vapor deposition layer 10 Adhesive layer 12 Release paper 14 Printing layer 16 Protective film

Claims (4)

[Claims] 1. A method according to claim 1, wherein the fluorine-containing resin film has Si, Z
r, Ti, Ta, Hf, Mo, W, Nb, Sn, In,
A printable label sheet film, wherein a thin film made of one or more metal oxides selected from the group consisting of Al, Cr and Zn is formed by a dry method. 2. The label sheet film according to claim 1, wherein the dry method is a sputtering method. 3. Release paper, pressure-sensitive adhesive layer, Cr vapor deposited layer, fluororesin film, Si, Zr, Ti, Ta, Hf, Mo,
A label sheet in which thin films made of one or more metal oxides selected from the group consisting of W, Nb, Sn, In, Al, Cr, and Zn are sequentially laminated, wherein the thin film is formed by a dry method. A printable label sheet formed on a resin film. 4. The label sheet according to claim 3, wherein the dry method is a sputtering method.