JP2002244561A - Label for management of tire - Google Patents

Abstract

PROBLEM TO BE SOLVED: To develop a label for the management of tires which can be printed as required on the job site by adding information with ink by a thermal transfer method without requiring an overcoat or the like, which hardly causes dropout of the ink even when the label is adhered to a green tire and subjected to vulcanization, which hardly causes contamination in the vulcanization dies or failure in the appearance of the tire due to transfer of the ink to the dies, which distinctly maintains the added ink information and which firmly adheres to the produced tire through the vulcanization process of the green tire. SOLUTION: The label base material consists of a heat-resistant resin film (2) containing a white filler the one surface of which is matted, a primer layer (3) formed on the other surface of the film, and a rubber adhesive layer (4) containing a vulcanization accelerator but no vulcanizing agent on the primer layer, and the label for the management of tires has information (1) by thermal transfer ink on the matted surface of the label base material. The information by the thermal transfer ink has at least a two-layer structure of a lower layer (12) made of heat-resistant resin ink and a surface layer (11) of polymethyl methacrylate and is in an exposed state on the label surface.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention can be issued on an occasional basis for each tire, and can be adhered firmly while maintaining the clearness of display by temporarily attaching to a green tire and vulcanizing the same, for automobiles and aircrafts. The present invention relates to a tire management label suitable for managing various rubber tires.

[0002]

BACKGROUND OF THE INVENTION Various rubber tires for automobiles, aircraft, etc. are sometimes provided with bar code labels for the purpose of controlling production and the like. In that case, in order to be able to manage tires of high-mix low-volume production in the distribution process in addition to the production process,
Information such as the type of tire and production lot can be entered on the bar code label at any time at the production site, and can be issued on the spot.In addition, it is adhered to the green tire and misaligned, wrinkled, and ink dropped through the vulcanization process. It is required that the tire can be firmly adhered and fixed to the tire after vulcanization without accompanying the above.

For this reason, a conventional bar code label of a type which can be issued at a manufacturing site or the like by forming a pattern by a thermal transfer method using a general-purpose ink ribbon such as a wax-based or resin-based ink ribbon has a poor ink rubbing property. Problems such as transfer to the vulcanization mold by the heat of vulcanization and contamination of the mold, and the ink pattern after vulcanization being damaged by friction with the vulcanization mold and causing defects in the appearance of the tire. This was liable to occur and practical use was difficult. Also, conventional labels in which a transparent overcoat of a transparent resin or an overlamination of a transparent film are provided on a barcode for the purpose of preventing mold contamination and the like cannot be issued on a production site or the like, so that practical use is difficult.

Further, conventional labels using a heat-resistant resin film which maintains an initial shape without being thermally deformed at the vulcanization temperature of a green tire as a label substrate also have poor adhesion to rubber. Thus, it has only an adhesive strength enough to be easily peeled off with a fingertip from a vulcanized tire, and is easily detached during operation of an automobile or the like, so that tire management in a distribution process cannot be realized and practical use is difficult.

[0005]

The present invention does not require an overcoat or the like, and can provide ink information by a thermal transfer method and can be issued on site on an occasional basis. The ink retains its initial shape without thermal deformation, and it is difficult for ink to fall off, and the transfer of ink to the vulcanization mold is unlikely to cause mold contamination and tire appearance defects. It is an object of the present invention to develop a tire management label that is maintained and firmly adhered to a formed tire through a green tire vulcanization process.

[0006]

According to the present invention, a rubber-based pressure-sensitive adhesive layer containing a vulcanization accelerator and containing no vulcanizing agent is provided on the other surface of a heat-resistant resin film containing a white filler, one surface of which is matted, via a primer layer. The mat transfer surface of the label substrate has thermal transfer ink information, and the thermal transfer ink information has at least a two-layer structure of a lower layer made of a heat-resistant resin-based ink and a surface layer made of polymethyl methacrylate. The present invention provides a tire management label characterized by being exposed on the label surface.

[0007]

According to the present invention, a label for tire management can be issued at any time at a production site or the like by providing ink information such as a bar code by the thermal transfer method, and the label can be green without providing an overcoat or the like. By temporarily attaching to the tire and vulcanizing, it is possible to prevent mold contamination due to ink dropping and blurring of the applied ink information, without thermal deformation such as misalignment and wrinkles, and sufficient for peeling off with a fingertip It is possible to form a label that can be firmly adhered to a tire after vulcanization with a strength that can be endured. Therefore, a label that enables individual management for each tire in a production process or a distribution process can be issued on a production site or the like on an occasional basis.

[0008] Therefore, the label according to the present invention can be used to distribute and manage automobile tires and the like throughout the industry. In other words, in the case of conventional printed labels that cannot be issued on site, serial numbers that have no meaning are used as the individual tires' serial numbers, so it is necessary to manage individual information, such as tire part numbers, with a host computer. Can control production, but it is very difficult to manage distribution throughout the industry with different tire manufacturers. However, in the tire management label according to the present invention, individual information can be recorded for each tire on site, and the tire can be sieved only by reading ink information such as a bar code of a label fixed to each tire. Therefore, distribution management throughout the industry can be easily performed.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The tire management label according to the present invention comprises a vulcanizing accelerator-containing vulcanizing agent-free and a primer-free layer on the other surface of a white filler-containing heat-resistant resin film matted on one side. The mat transfer surface of a label substrate having a rubber-based adhesive layer has thermal transfer ink information, and the thermal transfer ink information is at least two of a lower layer made of a heat-resistant resin-based ink and a surface layer made of polymethyl methacrylate. It has a layer structure and is exposed on the label surface.

FIG. 1 shows an example of the tire management label described above. FIG. 2 shows an example of the label base material in a state before the thermal transfer ink information is added to the label. 1 is thermal transfer ink information, 2 is a heat-resistant resin film containing a white filler, 3 is a primer layer, and 4 is a rubber-based adhesive layer.
Reference numeral 5 denotes a rubber tire as an adherend. In FIG. 2, reference numeral 21 denotes a matte processing surface for giving ink information, and reference numeral 6 denotes a separator. The separator is provided for protecting the rubber-based adhesive layer from contamination by dust and the like until the rubber-based adhesive layer is temporarily attached to the green tire, and is provided as necessary.

As the heat-resistant resin film forming the label substrate, any suitable heat-resistant resin film that does not thermally deform in the vulcanization of a green tire can be used. Generally, since the vulcanization treatment is usually performed under heating conditions at a temperature of 160 to 180 ° C. for 10 to 60 minutes, a resin having a melting point of 200 ° C. or more is preferably used, and handleability due to flexibility and the like is used. In view of the above, a resin made of a thermoplastic resin is preferable. Examples are polyamides and polycarbonates,
Examples include films made of one or more of polybutylene terephthalate, polyethylene terephthalate, polyphenylene ether, polyphenylene sulfide, polyarylate, polymethylpentene, and polyamideimide.

The thickness of the heat resistant resin film can be determined as appropriate, but is generally 100 to 150 μm, preferably 120 to 150 μm.
It is preferable to set it to 130 μm. Its thickness is 100
If the thickness is less than μm, the green tire may be deformed by heat during vulcanization, and if it exceeds 150 μm, when the label is adhered to the bead portion of the tire, if it is worn, air leakage of the tire may be induced.

The white filler to be contained in the heat-resistant resin film for whitening is, for example, an oxide ceramic such as silica, titania (titanium white), alumina, zinc white, calcium oxide or mica, or oxidized. Carbonates, nitrates, sulfates, and the like that become ceramics can be given. The content of the white filler is generally 90% by weight or less, preferably 50% by weight or less, particularly 1 to 30% by weight,
The reflectance of visible light is 75% or more, especially 80% or more, especially 9
Films of 0% or more are preferred.

By using a heat-resistant heat-resistant resin film containing a white filler as described above, strong adhesion to a rubber tire can be achieved through a vulcanization treatment step of a green tire, and heat such as positional deviation and wrinkles can be obtained. It is possible to obtain a label that satisfactorily retains its initial shape without deformation.
Particularly preferred from the viewpoint of firmly adhering to a rubber tire is a white polyethylene terephthalate film containing titanium white.

The primer layer is provided for the purpose of improving the adhesive strength between the heat-resistant resin film and the rubber-based pressure-sensitive adhesive layer, particularly for improving the adhesive strength after vulcanization. Examples of primers include phenol, resorcinol, pyrogallol and p
-Toluenesulfonic acid, a mixture of resorcinol and formaldehyde, a mixture of chlorophenol, resorcinol, formaldehyde, and a latex of an organic compound such as vinylpyridine or SBR are preferably used.

Of these, chlorophenol-based primers mixed with RFL (resorcinol, formaldehyde, latex) are preferred. In this case, the amount of RFL used is appropriately determined according to the effect of improving the adhesive strength, etc., but generally 100 parts by weight or less per 100 parts by weight of chlorophenol,
In particular, 5 to 80 parts by weight, especially 10 to 50 parts by weight, are used. The composition of RFL is 1 / 0.0 based on R / F / L.
Weight ratios of 5/2/2 to 10 are common.

The attachment of the primer layer to the heat-resistant resin film can be carried out by applying an appropriate method such as a known coating method using a kiss coater or a doctor blade or an impregnation method. The thickness of the primer layer is 1 to 50 μm, especially 2
-30 μm, especially 5-20 μm is common. By providing the rubber-based pressure-sensitive adhesive layer via the primer layer, it is possible to achieve a strong adhesion without a temporary attachment to a green tire or a positional deviation to a formed tire through a vulcanization process.

The rubber-based pressure-sensitive adhesive layer is formed of a rubber-based composition containing a vulcanization accelerator and containing no vulcanizing agent from the viewpoint of adhesive strength to a tire and storage stability until practical use. The composition is, for example, a mixture of 100 parts by weight of a rubber polymer such as natural rubber, isoprene rubber, butadiene rubber, styrene-butadiene rubber, and butyl rubber, 20 to 50 parts by weight of tackifier, and 1 to 5 parts by weight of a vulcanization accelerator. Prepared.
When a vulcanizing agent is included, vulcanization proceeds during storage or distribution at room temperature, etc., and the tack decreases, the label falls off the separator and the temporary adhesion to the green tire decreases, and the utility is poor. Become.

Graft rubber is preferably used from the viewpoint of strong adhesion to a tire after vulcanization, and natural rubber is preferably used from the viewpoint of temporary adhesion to a green tire. Accordingly, a rubber-based polymer in which 5 to 30% by weight of a natural rubber is used in combination with a graft-based rubber is particularly preferable. If necessary, an antioxidant such as a phenolic compound may be added to the rubber-based polymer 10 for the purpose of improving the storage stability of the label.
1 to 5 parts by weight per 0 parts by weight can be added.

Examples of tackifiers used for the purpose of controlling adhesive strength include terpene resins, rosin resins, hydrogenated rosin resins and glycerin esters thereof, coumarone indene resins, terpene phenol resins, alkylphenol resins, One or more suitable materials such as known materials such as aliphatic and aromatic petroleum resins can be used. Also, as the vulcanization accelerator used for the purpose of improving the curability of the pressure-sensitive adhesive layer itself, one or more kinds of appropriate ones such as known substances can be used. Among them, the tackifier is preferably a petroleum resin-based one from the viewpoint of temporary adhesion to a green tire. As the vulcanization accelerator, a turum-based vulcanizing agent is preferred from the viewpoints of curability and improvement in adhesive strength by vulcanization.

The rubber-based pressure-sensitive adhesive layer is formed by diluting the rubber-based composition with an organic solvent, if necessary, and using a fountain method, a comma roll method, a doctor blade method, a calendar roll method, a gravure roll coater method, or the like. It can be carried out by an appropriate method such as a method of coating on a primer layer of a resin film or a method of transferring a rubber-based adhesive layer coated and formed on a separator. The thickness of the rubber-based pressure-sensitive adhesive layer to be formed is preferably 10 to 50 μm, more preferably 15 to 30 μm.

If the thickness of the rubber-based adhesive layer is less than 10 μm, the temporary adhesion to the green tire may be poor,
Exceeding the limit may result in a large amount of glue overflow during label processing. By temporarily attaching to a green tire via such a rubber-based adhesive layer and vulcanizing, an adhesive force of usually 3 kg / cm or more (180 degree peel) is developed, which is resistant to peeling by a fingertip and severe of tires. Adhesive force that does not come off even under normal use conditions.

As shown in the example of FIG. 2, the matting treatment to be performed at least on the surface 21 of the heat-resistant resin film 2 which does not have the rubber-based adhesive layer 4 is performed by using the ink transferred by the thermal transfer method with the surface functioning as an ink receiving layer. The purpose is to make the information resistant to vulcanization of green tires. That is, when the applied thermal transfer ink information is temporarily attached to a green tire as a label and vulcanized in a state where it is exposed without providing an overcoat or the like, the ink is allowed to flow into the recesses of the matte processing surface. It is an object of the present invention to firmly fix the ink on the surface of a label substrate so that transfer of ink (ink drop) does not occur even at the vulcanization temperature.

As a result, contamination of a vulcanization mold due to transfer of ink, poor appearance of tires, and unclear ink information such as a bar code applied can be prevented by mat processing which can be easily performed by a simple processing operation. It can be vulcanized while being cured. In the above, regarding the ink information on the non-matte-treated surface, the ink is transferred by the heat at the time of vulcanization, and contamination of the vulcanization mold, poor appearance of the tire, and blurring of the applied ink information are remarkable.

The degree of the mat treatment is 0.1 to 1.0 μm, preferably 0.15 to 0.6 μm, based on the surface roughness Ra.
Is preferable. If the Ra is smaller than 0.1 μm, the depth of the ink flowing into the recesses may be insufficient and the vulcanization mold may be significantly contaminated. It may be difficult to provide ink information. The surface unevenness based on Rmax is preferably 1 to 4 μm, particularly preferably 1.5 to 3 μm.
The mat treatment can be performed by an appropriate roughening treatment method such as a blast method using a sand mat, a method for applying a matting agent, and a kneading mat method.

The label is formed by forming a lower layer 12 made of a heat-resistant resin-based ink and a surface layer 11 made of polymethyl methacrylate (PMMA) on a mat-treated surface 21 of the heat-resistant resin film 2 on the label substrate as shown in the figure. This can be performed by providing thermal transfer ink information having at least a two-layer structure. By using such multi-layered ink information, a label in a state in which ink information is provided by a thermal transfer method using a thermal transfer printer and an ink ribbon and exposed without providing an overcoat or the like on the ink. It can be temporarily attached to a green tire and subjected to a vulcanization treatment.

That is, the thermal transfer ink information has robustness based on the multi-layer structure, resists the temperature and friction applied from the mold during the vulcanization treatment, and prevents contamination of the vulcanization mold and poor tire appearance. And maintain clear ink information even after vulcanization. As a result, a label which can be used practically by giving ink information such as a barcode necessary for individual management of each tire in a production process or a distribution process at a production site or the like can be issued at any time. In the above-described application of the ink information using the wax-based ink, the ink is transferred by heat at the time of vulcanization, causing contamination of the vulcanization mold, poor appearance of the tire, and blurring of the applied ink information.

The formation of the thermal transfer ink information can be performed using an ink ribbon and an appropriate thermal transfer printer such as a commercially available one. In this case, the ink ribbon has a lower layer made of a heat-resistant resin-based ink and a surface layer made of polymethyl methacrylate. This can be performed by using a material capable of forming thermal transfer ink information having at least a two-layer structure. Such an ink ribbon is, for example, PM on a supporting substrate made of a film or cloth by an appropriate method such as an application method or an impregnation method.
After the MA layer is provided, it can be obtained by a method in which a layer of a heat-resistant resin-based ink is provided on the PMMA layer via an appropriate intermediate layer such as an adhesion improving layer as needed.

When the thermal transfer is performed through a thermal transfer printer by using the ink ribbon having a multilayer structure as described above, the ink layer is turned upside down, and the PMMA layer is positioned as a surface layer above the resin-based ink layer and is robust. It is possible to form thermal transfer ink information that is excellent in durability such as durability and friction resistance. As the support substrate, for example, a heat-resistant resin film such as polyethylene terephthalate, polyimide, or fluororesin, or a cloth made of fibers such as polyamide or polyester is generally used.

On the other hand, examples of heat-resistant resin-based inks include, for example, polyester-based, polyamide-based, acrylic-based, polycarbonate-based, and phenol-based resins, particularly, thermoplastic polyimide, polyetheretherketone, polyethersulfone, and polyether. One or two of heat-resistant resins such as ether imide, polysulfone, polyphenylene sulfide, polyamide imide, polyester imide, aromatic polyamide, polyparabanic acid, fluororesin and epoxy resin.
One or more kinds of colorants and one or two or more kinds of colorants are mixed with a suitable kneading machine such as a roll mill or a pot mill using a solvent as necessary to prepare a fluid such as a paste. .

As the colorant, for example, an appropriate one such as an organic or inorganic pigment, carbon or metal powder is used. Specific examples thereof include organic pigments such as azo pigments, phthalocyanine pigments, triphenylmethane pigments, metal complex pigments, vat dye pigments, quinacridone pigments, and isoindolinone pigments. Examples of the inorganic pigments include chromium oxide, cobalt oxide, iron oxide, manganese oxide, black matter such as chromate and permanganate, manganese oxide and alumina, chromium oxide and tin oxide, iron oxide, and cadmium sulfide. Red substance such as selenium sulfide, blue substance such as cobalt oxide, zirconia / vanadium oxide, chromium oxide / divanadium pentoxide, yellow substance such as zirconium / silicon / praseodymium, vanadium / tin, chromium / titanium / antimony, chromium oxide, Typical examples thereof include green materials such as cobalt chromium and alumina chromium, and pink materials such as aluminum manganese and iron silicon zirconia.

The resin-based ink generally contains 50 to 500 parts by weight of a coloring agent per 100 parts by weight of the resin component, but is not limited thereto. For formation of ink information, particularly barcodes, it is particularly preferable to use black resin-based ink such as carbon or black pigment from the viewpoint of contrast.

An ink ribbon which can be preferably used has a resin ink layer having a thickness of 1 to 3 μm, preferably about 2 μm. If the thickness is less than 1 μm, the ink density may be insufficient and the hiding power of the ground color may be poor. If the thickness exceeds 3 μm, the ink layer may be sheared and thermal transfer may not be performed well, and good ink information may not be formed. is there. Although a colorant may be contained, the thickness of the surface PMMA layer which is a transparent layer is usually 3 μm or less, preferably 0.1 to 2 μm, particularly preferably 0.5 to 1 μm from the viewpoint of thermal transferability and the like. The thickness of all layers subjected to thermal transfer is preferably 10 μm or less, more preferably 5 μm or less, and particularly preferably 2 to 3 μm from the viewpoint of thermal transferability and the like.

The label for tire management is applied, for example, in the step of vulcanizing green tires for forming rubber tires for various uses such as for automobiles and aircraft, and is used for barcodes and the like necessary for individual management of tires. The appropriate thermal transfer ink information is applied to a label base material to form a label, and the label is temporarily attached to an appropriate position such as a bead portion of a green tire and vulcanized by heating at 160 to 180 ° C. for 10 to 60 minutes. It can be performed by a processing method or the like.

As described above, during the vulcanization process of the green tire, the rubber-based adhesive layer absorbs the vulcanizing agent in the green tire, vulcanizes and cures via the vulcanization accelerator in the adhesive layer, and is cured with a fingertip. Strong adhesion that cannot be peeled off, usually 3 kg /
Adhesion force of 180 cm or more (180 degree peel) adheres to the tire,
The tire can withstand severe use conditions of tires and does not come off. In addition, the vulcanization process, particularly during the initial stage, the resin-based ink layer of the ink information thermally transferred into the concave portion of the matted surface applied to the surface of the label substrate flows in and firmly fixes to the label surface, Excellent scratch resistance because the surface of the ink information is covered with the PMMA layer,
The vulcanizing mold is hardly contaminated with the ink component. Therefore, it becomes possible to issue a tire management label in the tire production process, input individual information for each tire, and then sift the tires by vehicle type, manufacturer, etc. in the subsequent production process and distribution process. From tire to distribution can be managed for the entire industry including other manufacturers and dealers.

As described above, the label for tire management according to the present invention can be temporarily attached to a green tire and provided for vulcanization without providing an overcoat or the like. When wiping with alcohol or the like, depending on the solvent used, the wiping may cause the PMMA layer or the like of the ink information to be lost. In such a case, an overcoat or the like can be provided, and an appropriate transparent material such as an ultraviolet curable resin such as an acrylic resin can be used for the formation. Further, the formation can be carried out at an appropriate stage before and after the vulcanization treatment. However, in general, the treatment is performed as necessary after the vulcanization treatment in order to take advantage of the advantages of the present invention such as the issuance of labels. It is preferable to provide a coat or the like.

[0037]

Example 1 A primer was applied by a doctor blade method to the other surface of a titanium white-containing white polyethylene terephthalate film having a thickness of 125 μm and having one surface sandblasted.
C. for about 2 minutes to form a primer layer having a thickness of 10 .mu.m, on which a graft rubber composition was applied by a doctor blade method and dried at 120.degree.
A rubber-based pressure-sensitive adhesive layer having a thickness of μm was provided, and was wound while being covered with a separator to obtain a label substrate.

The above-mentioned primer is a chlorophenol-based primer (CASABONDE, manufactured by ICI) 100
Parts (parts by weight, the same applies hereinafter), resorcinol 4.1 parts, formaldehyde 3.6 parts, vinylpyridine latex (solid content 41% by weight) 47.4 parts, SBR latex (solid content 40% by weight) 11.7 parts, And 6.4 parts of a 5% by weight sodium hydroxide solution were uniformly mixed with 26.8 parts of soft water. Further, the graft rubber composition,
Graft rubber 85 parts, natural rubber 15 parts, petroleum resin 35
Parts, 4 parts of a churam-based vulcanization accelerator and 3 parts of a phenolic antioxidant were uniformly dissolved in 200 parts of toluene.

The above-mentioned label base material is cut into a size of 60 mm × 200 mm, and a matted surface thereof is formed by using an ink ribbon having a black resin-based ink layer provided on a transparent PMMA layer and a commercially available thermal transfer printer. A bar code was printed, and the bar code was further cut into a size of 12 mm × 45 mm to obtain a tire management label.

Comparative Example A tire management label was obtained in the same manner as in Example 1 except that an ink ribbon having no PMMA layer was used.

Evaluation Test The separator was peeled off from the tire management labels obtained in the Examples and Comparative Examples, and the separator was temporarily attached to a bead portion of an automobile green tire via the rubber-based pressure-sensitive adhesive layer.
After placing in a 15S vulcanizing mold and vulcanizing at 175 ° C. for 15 minutes, the tire is taken out of the mold, and the degree of contamination of the mold due to ink drop is visually determined. Signal) was measured and evaluated based on the ANSI standard.
The PCS is calculated by the formula: (white background reflectance / black character reflectance) / white background reflectance. As ink is taken into the mold, the black portion of the tire management label becomes thinner and lower. The bar code standard requires that the PCS be 0.75 or more.

The results are shown in the following table.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of an example of a label.

FIG. 2 is a cross-sectional view of an example of a label base material.

[Explanation of symbols]

 1: Thermal transfer ink information 11: Surface layer made of PMMA 12: Lower layer made of resin-based ink 2: Heat-resistant resin film containing white filler 21: Matted surface 3: Primer layer 4: Rubber-based adhesive layer 5: Tire 6: Separator

Claims (1)

[Claims] 1. A label comprising a white filler-containing heat-resistant resin film having a matte treatment on one side and a vulcanization accelerator-containing and vulcanizing agent-free rubber-based adhesive layer via a primer layer on the other side. The matte-treated surface of the base material has thermal transfer ink information, and the thermal transfer ink information has at least a two-layer structure of a lower layer made of a heat-resistant resin-based ink and a surface layer made of polymethyl methacrylate, and is exposed on the label surface. A tire management label characterized in that it is in a state where it has been worn.