JP4592973B2 - Tire management label - Google Patents

Description

【図面の簡単な説明】
【図１】ラベル例の断面図
【図２】ラベル基材例の断面図
【符号の説明】
１：熱転写インク情報
１１：ＰＭＭＡよりなる表層
１２：樹脂系インクよりなる下層
２：白色フィラー含有の耐熱性樹脂フィルム
２１：マット処理面
３：プライマー層
４：ゴム系粘着層
５：タイヤ
６：セパレータ[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention can be issued on a case-by-tire basis, and can be firmly bonded while maintaining the sharpness of display by temporarily attaching to a green tire and vulcanizing, and is suitable for management of various rubber tires for automobiles, aircrafts, etc. The present invention relates to a tire management label.
[0002]
BACKGROUND OF THE INVENTION
Barcode labels may be attached to various types of rubber tires for automobiles and aircrafts for the purpose of production control. In that case, in order to be able to manage the tires of high-mix low-volume production in the distribution process in addition to the production process, information such as the tire type and production lot is entered on the barcode label as needed at the manufacturing site. It is required to be able to be issued on-site, and to be firmly bonded and fixed to a vulcanized tire without positional displacement, wrinkles, ink drop, etc. through the vulcanization process by bonding it to a green tire.
[0003]
For this reason, conventional barcode labels that can be issued on the spot at the manufacturing site by forming a pattern using a general-purpose ink ribbon such as a wax or resin system by a thermal transfer method, etc. are poor in ink scratching and are vulcanized. This causes problems such as transfer to the vulcanization mold due to heat and contamination of the mold, or damage to the tire pattern by rubbing the ink pattern after vulcanization with friction with the vulcanization mold. It was easy and practical to use. In addition, conventional labels in which a transparent resin overcoat or a transparent film overlaminate is provided on a bar code for the purpose of preventing mold contamination are difficult to put into practical use because they cannot be issued on the spot at the manufacturing site.
[0004]
Furthermore, conventional labels using heat-resistant resin films that maintain the initial shape without thermal deformation at the vulcanization temperature of green tires are also vulcanized because the heat-resistant resin films have poor adhesion to rubber. Only an adhesive strength that can be easily peeled off with a fingertip from the treated tire is exhibited, and it is easily detached during operation of an automobile or the like, and the tire management in the distribution process cannot be realized, so that it is difficult to practically use.
[0005]
[Technical Problem of the Invention]
The present invention does not require an overcoat, etc., can be issued on the spot by providing ink information by a thermal transfer method, and does not cause thermal deformation such as misalignment and wrinkles even if it is bonded to a green tire and subjected to vulcanization treatment It retains the initial shape and does not easily drop off ink, and transfer of ink to the vulcanization mold does not easily cause mold contamination or tire appearance failure. The challenge is to develop a label for tire management that adheres firmly to the formed tire through the sulfurization process.
[0006]
[Means for solving problems]
The present invention relates to a label group comprising a rubber-based adhesive layer containing a vulcanization accelerator and containing no vulcanizing agent via a primer layer on the other side of a heat-resistant resin film containing a white filler that is matted on one side. The mat-treated surface of the 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. The present invention provides a tire management label characterized by being in a state.
[0007]
【The invention's effect】
According to the present invention, a label for tire management can be issued at any time at a production site by providing ink information such as a barcode by a thermal transfer method, and temporarily attached to a green tire without providing an overcoat or the like. The vulcanization process prevents the contamination of the mold due to ink dropping and unsharpness of the added ink information without causing thermal deformation such as misalignment or wrinkles, and with sufficient strength to withstand peeling by the fingertips. A label can be formed that adheres firmly to the subsequent tire. Therefore, a label that enables individual management for each tire in the production process and distribution process can be issued on the spot at the production site.
[0008]
Therefore, distribution of automobile tires and the like can be managed throughout the industry by the label according to the present invention. In other words, conventional printed labels that cannot be issued on-site use serial numbers that have no meaning as individual tire back numbers, so individual information such as tire part numbers must be managed by the host computer. Although it is possible to manage production in Japan, distribution management throughout the industry with different tire manufacturers is very difficult. However, with the tire management label according to the present invention, individual information can be recorded for each tire in the field, and the tire can be screened only by reading the ink information such as the barcode of the label fixed to each tire. Accordingly, distribution management over the entire industry can be easily performed.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
The label for tire management according to the present invention has a rubber-based adhesive layer containing a vulcanization accelerator and no vulcanizing agent on the other side of a heat-resistant resin film containing a white filler matted on one side via a primer layer. The mat base 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 heat-resistant resin-based ink and a surface layer made of polymethyl methacrylate. It consists of what is exposed on the label surface.
[0010]
An example of the above-described tire management label is shown in FIG. Moreover, the example of the label base material of the state before providing thermal transfer ink information and making it the said label was shown in FIG. 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 mat processing surface for applying ink information, and 6 denotes a separator. The separator is for protecting the rubber adhesive layer from being contaminated with dust or the like until it is temporarily attached to the green tire, and is provided as necessary.
[0011]
As the heat-resistant resin film for forming the label base material, any suitable heat-resistant resin film that does not undergo thermal deformation due to vulcanization treatment of a green tire can be used. In general, since the vulcanization treatment is usually performed under heating conditions of 160 to 180 ° C. for 10 to 60 minutes, those made of a resin having a melting point of 200 ° C. or more are preferably used. From this point, a thermoplastic resin is preferable. Examples thereof include polyamide, polycarbonate, polybutylene terephthalate, polyethylene terephthalate, polyphenylene ether, polyphenylene sulfide, polyarylate, polymethylpentene, and a film made of one or more of polyamideimide.
[0012]
The thickness of the heat-resistant resin film can be appropriately determined, but is generally preferably 100 to 150 μm, and more preferably 120 to 130 μm. If the thickness is less than 100 μm, it may be deformed by heat during vulcanization of the green tire, and if it exceeds 150 μm, if the label is adhered to the bead portion of the tire and it wears away, it will cause tire air leakage There is.
[0013]
Examples of the white filler to be included for whitening the heat-resistant resin film include silica, titania (titanium white), alumina, zinc white, oxide type ceramics such as calcium oxide and mica, and ceramics obtained by oxidation. Examples include carbonates, nitrates and sulfates. The content of the white filler is generally 90% by weight or less, especially 50% by weight or less, particularly 1 to 30% by weight, and the visible light reflectance is 75% or more, especially 80% or more, particularly 90% or more. What was made into this film is preferable.
[0014]
By using a heat-resistant heat-resistant resin film containing a white filler as described above, thermal adhesion such as misalignment and wrinkles occurs while achieving strong adhesion to the rubber tire through the vulcanization process of the green tire. Therefore, it is possible to obtain a label that favorably holds the initial shape. A white polyethylene terephthalate film containing titanium white is particularly preferable from the viewpoint of firmly bonding to a rubber tire.
[0015]
The primer layer is provided for the purpose of improving the adhesive strength between the heat-resistant resin film and the rubber-based adhesive layer, particularly for improving the adhesive strength after vulcanization. As the primer, for example, phenol, resorcinol, pyrogallol, 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.
[0016]
In particular, a chlorophenol primer mixed with RFL (resorcinol, formaldehyde, latex) is preferable. 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, especially 5 to 80 parts by weight, especially 10 to 50 parts per 100 parts by weight of chlorophenol. Part by weight is used. The composition of RFL is generally a weight ratio of 1 / 0.5 to 2/2 to 10 based on R / F / L.
[0017]
The primer layer can be attached to the heat resistant resin film by applying an appropriate method such as a known coating method or impregnation method using a kiss coater or a doctor blade. The thickness of the primer layer is generally 1 to 50 μm, in particular 2 to 30 μm, in particular 5 to 20 μm. By attaching the rubber-based adhesive layer via the primer layer, it is possible to achieve strong adhesion without temporary displacement to the green tire or positional displacement with respect to the formed tire through the vulcanization process.
[0018]
The rubber-based adhesive layer is formed of a rubber-based composition that contains a vulcanization accelerator and does not contain a vulcanizing agent from the viewpoints of adhesion to the tire and storage stability until practical use. The composition is, for example, a mixture of 100 parts by weight of a rubber-based polymer such as natural rubber, isoprene rubber, butadiene rubber, styrene-butadiene rubber, butyl rubber, 20-50 parts by weight of tackifier, 1-5 parts by weight of a vulcanization accelerator, and the like. Prepared. When a vulcanizing agent is included, vulcanization proceeds during storage at room temperature or during distribution, resulting in a decrease in tack and a drop in the label from the separator and temporary attachment to the green tire, resulting in poor practicality. Become.
[0019]
Graft rubber is preferably used from the standpoint of strong adhesion to the vulcanized tire, and natural rubber is preferably used from the standpoint of temporary attachment to the green tire. Accordingly, a rubber-based polymer in which 5 to 30% by weight of natural rubber is used in combination with graft rubber is particularly preferable. In addition, 1-5 weight part of anti-aging agents, such as a phenol type | system | group, can also be mix | blended per 100 weight part of rubber-type polymers as needed for the purpose of a label preservability improvement.
[0020]
For example, terpene resins, rosin resins, hydrogenated rosin resins and their glycerin esters, coumarone indene resins, terpene phenol resins, alkylphenol resins, aliphatic resins can be used as tackifiers for the purpose of controlling adhesive force. One or two or more appropriate ones such as known materials such as aromatic petroleum resins can be used. As the vulcanization accelerator used for the purpose of improving the curability of the pressure-sensitive adhesive layer itself, one or more appropriate ones such as known substances can be used. In particular, as a tackifier, a petroleum resin type is preferable from the viewpoint of temporary attachment to a green tire. Further, as a vulcanization accelerator, a churam-based one is preferable from the viewpoints of curability and improvement of adhesive strength by vulcanization treatment.
[0021]
The rubber-based adhesive layer can be formed by diluting the rubber-based composition with an organic solvent as necessary, and using a fountain method, comma roll method, doctor blade method, calendar roll method, gravure roll coater method, etc. An appropriate method such as a method of coating on the primer layer or a method of transferring a rubber-based adhesive layer coated on the separator can be used. The thickness of the rubber-based adhesive layer to be formed is preferably 10 to 50 μm, especially 15 to 30 μm.
[0022]
If the thickness of the rubber-based adhesive layer is less than 10 μm, the temporary adhesion to the green tire may be poor, and if it exceeds 50 μm, the amount of sticking of the paste may increase during processing of the label. Adhesion of 3 kg / cm or more (180 degree peel) is usually developed by temporarily attaching to a green tire through such a rubber-based adhesive layer and vulcanizing, which is resistant to peeling by the fingertips Adhesive strength that does not disengage even under various usage conditions.
[0023]
As shown in the example of FIG. 2, at least the mat treatment applied to the surface side 21 of the heat-resistant resin film 2 that does not have the rubber-based adhesive layer 4 causes the surface to function as an ink receiving layer and the ink information applied by the thermal transfer method is green. The purpose is to withstand the vulcanization of tires. In other words, when the applied thermal transfer ink information is temporarily attached to a green tire as a label and exposed without being provided with an overcoat, the ink is allowed to flow into the recesses of the mat processing surface. An object of the present invention is to firmly fix the surface of a label base material so that ink transfer (ink dropping) does not occur even at the vulcanization temperature.
[0024]
As a result of the above, vulcanization while preventing contamination of the vulcanization mold due to transfer of ink, poor appearance of the tire due to ink transfer, and blurring of ink information such as applied barcodes, etc., can be easily performed by simple processing operations. Can be processed. In the ink information on the non-matted surface, the ink is transferred by heat during vulcanization, and the vulcanization mold is contaminated, the tire appearance is poor, and the ink information provided is unclear.
[0025]
The degree of the mat treatment is preferably 0.1 to 1.0 μm, particularly preferably 0.15 to 0.6 μm, based on the surface roughness Ra. If the Ra is less than 0.1 μm, the depth of ink flow into the recess may be insufficient, and the vulcanization mold may be significantly contaminated. If the Ra exceeds 1.0 μm, the surface unevenness may cause sharpness due to thermal transfer. It may be difficult to provide ink information. The surface irregularity based on Rmax is preferably 1 to 4 μm, and more preferably 1.5 to 3 μm. The mat treatment can be performed by an appropriate roughening treatment method such as a blasting method using a sand mat, a matting agent coating method, or a kneading matting method.
[0026]
As shown in the figure, the label is formed on the mat-treated surface 21 of the heat-resistant resin film 2 on the label base material by at least two layers of a lower layer 12 made of heat-resistant resin-based ink and a surface layer 11 made of polymethyl methacrylate (PMMA). This can be done by applying thermal transfer ink information having a structure. By adopting such multi-layered ink information, the ink information is provided by a thermal transfer method using a thermal transfer printer and an ink ribbon, and the label is left exposed without providing an overcoat or the like on the ink. It can be temporarily attached to a green tire and used for vulcanization.
[0027]
In other words, the thermal transfer ink information has robustness based on the multilayer structure, and resists the temperature and friction applied from the mold during the vulcanization process to prevent contamination of the vulcanization mold and poor appearance of the tire, and vulcanization. After that, clear ink information is maintained. As a result, labels that can be practically used by providing ink information such as barcodes necessary for individual management for each tire in the production process and distribution process at the production site can be issued at any time. In the above, when the ink information is applied by the wax-based ink, the ink is transferred by heat at the time of vulcanization, resulting in contamination of the vulcanization mold, poor appearance of the tire, and blurring of the applied ink information.
[0028]
The thermal transfer ink information can be formed using an ink ribbon and an appropriate commercially available thermal transfer printer. In this case, at least two layers of a lower layer made of heat-resistant resin-based ink and a surface layer made of polymethyl methacrylate are used as the ink ribbon. It can be performed by using a material capable of forming thermal transfer ink information having a layer structure. For example, such an ink ribbon is provided with a PMMA layer on a support substrate made of a film, cloth, or the like by an appropriate method such as a coating method or an impregnation method, and then the adhesion is improved on the PMMA layer as necessary. It can be obtained by a method of providing a heat-resistant resin-based ink layer through an appropriate intermediate layer such as a layer.
[0029]
When thermal transfer is performed through a thermal transfer printer by using an ink ribbon having a multilayer structure as described above, the upper and lower sides of the ink layer are reversed, and the PMMA layer is positioned as a surface layer on the upper side of the resin-based ink layer, so Thermal transfer ink information having excellent durability such as friction can be formed. In addition, as said support base material, the cloth which consists of heat resistant resin films, such as a polyethylene terephthalate, a polyimide, a fluororesin, a fiber, such as polyamide and polyester, is used normally, for example.
[0030]
On the other hand, as heat-resistant resin-based inks, for example, polyester-based, polyamide-based, acrylic-based, polycarbonate-based, phenol-based resins, among others, thermoplastic polyimide, polyetheretherketone, polyethersulfone, polyetherimide, Roll mill or polysulfone, polyphenylene sulfide, polyamide imide, polyester imide, aromatic polyamide, polyparabanic acid, one or more heat resistant resins such as fluororesin and epoxy resin, and one or more colorants Examples thereof include those prepared by mixing in a suitable kneader such as a pot mill using a solvent as necessary to prepare a fluid such as a paste.
[0031]
As the colorant, for example, an appropriate one such as an organic or inorganic pigment, carbon, metal powder or the like 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 inorganic pigments include black oxides such as chromium oxide, cobalt oxide, iron oxide, manganese oxide, chromate and permanganate, manganese oxide / alumina, chromium oxide / tin oxide, iron oxide, cadmium sulfide, Red materials such as selenium sulfide, blue materials such as cobalt oxide, zirconia and vanadium oxide, chromium oxide and divanadium pentoxide, yellow materials such as zirconium, silicon and praseodymium, vanadium and tin, chromium, titanium and antimony, chromium oxide, Typical examples include green materials such as cobalt / chromium and alumina / chromium, and pink materials such as aluminum / manganese and iron / silicon / zirconium.
[0032]
The resin-based ink generally contains 50 to 500 parts by weight of a colorant per 100 parts by weight of the resin component, but is not limited thereto. For the formation of ink information, particularly barcodes, those using black resin-based inks such as carbon and black pigment are particularly preferable from the viewpoint of contrast.
[0033]
Ink ribbons that can be preferably used have a resin-based ink layer thickness of 1 to 3 μm, especially about 2 μm. If the thickness is less than 1 μm, the ink density may be insufficient and the background color hiding power may be poor. If the thickness exceeds 3 μm, the ink layer may be sheared and thermal transfer cannot be performed well, and good ink information may not be formed. is there. Although it may contain a colorant, the thickness of the PMMA layer as a transparent layer is usually 3 μm or less, preferably 0.1 to 2 μm, and particularly preferably 0.5 to 1 μm from the viewpoint of thermal transferability. The thickness of all layers to be thermally transferred 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.
[0034]
The application of the tire management label is, for example, a process of vulcanizing a green tire for forming rubber tires for various uses such as for automobiles and aircrafts, etc. A method of forming a label by applying thermal transfer ink information to a label substrate, temporarily attaching the label to an appropriate position such as a bead portion of a green tire, and heating at 160 to 180 ° C. for 10 to 60 minutes for vulcanization treatment Etc.
[0035]
As described above, the rubber-based adhesive layer absorbs the vulcanizing agent in the green tire and vulcanizes and cures through the vulcanization accelerator in the adhesive layer through the vulcanization process of the green tire, and the label cannot be peeled off with a fingertip. Adhesive strength, usually 3 kg / cm or more (180 degree peel), it adheres to the tire and withstands the harsh use conditions of the tire and does not leave. In addition, the resin-based ink layer of the ink information thermally transferred into the concave portion of the mat processing surface applied to the surface of the label base material in the initial stage of the vulcanization process flows and firmly fixed on the label surface, Since the surface of the ink information is coated with the PMMA layer, it has excellent scratch resistance, and the vulcanization mold is hardly contaminated with ink components. Therefore, it is possible to issue tire management labels during the tire production process, enter individual information for each tire, and filter the tires by vehicle type and manufacturer, etc. in the subsequent production and distribution processes. The management of each tire in the process from distribution to distribution can be performed by the entire industry including other manufacturers and dealers.
[0036]
As described above, the tire management label according to the present invention can be temporarily attached to a green tire without being provided with an overcoat or the like and can be used for vulcanization treatment. Depending on the solvent used, the PMMA layer or the like of the ink information may be lost by wiping. In such a case, an overcoat or the like can be provided, and an appropriate transparent material such as an acrylic UV curable resin can be used for the formation. In addition, the formation can be performed at an appropriate stage before and after the vulcanization treatment, but in general, it is over-treated as necessary after the vulcanization treatment from the viewpoint of taking advantage of the present invention such as the ability to issue labels. It is preferable to provide a coat or the like.
[0037]
【Example】
Example 1
A primer is applied to the other side of a white polyethylene terephthalate film containing titanium white having a thickness of 125 μm, one side of which is sandblasted, and dried at 160 ° C. for about 2 minutes to form a primer layer having a thickness of 10 μm. A graft rubber composition is applied on the top by a doctor blade method and dried at 120 ° C. for about 5 minutes to provide a rubber adhesive layer having a thickness of 20 μm. It was.
[0038]
The primer is 100 parts (parts by weight, the same applies hereinafter) of chlorophenol-based primer (CASABONDE, manufactured by ICI), 4.1 parts of resorcinol, 3.6 parts of formaldehyde, vinylpyridine latex (solid content 41% by weight) 47. 4 parts, 11.7 parts of SBR latex (solid content 40% by weight), and 6.4 parts of 5% by weight caustic soda solution were mixed uniformly with 26.8 parts of soft water. In addition, the above-mentioned graft rubber composition uniformly comprises 85 parts of graft rubber, 15 parts of natural rubber, 35 parts of petroleum resin, 4 parts of churam vulcanization accelerator, and 3 parts of phenolic anti-aging agent in 200 parts of toluene. It consists of a dissolved one.
[0039]
The label base material is cut into a size of 60 mm × 200 mm and a bar code is printed using an ink ribbon in which a black resin-based ink layer is provided on a transparent PMMA layer on the mat processing surface and a commercially available thermal transfer printer. Printing was performed, and this was further cut into a size of 12 mm × 45 mm to obtain a label for tire management.
[0040]
Comparative Example A ribbon for tire management was obtained in the same manner as in Example 1 except that an ink ribbon having no PMMA layer was used.
[0041]
The separator is peeled off from the tire management labels obtained in the evaluation test examples and comparative examples, and is temporarily attached to the bead portion of the green tire for automobiles through the rubber-based adhesive layer, which is vulcanized gold having a surface finish of 10 to 15S. After putting in a mold and vulcanizing at 175 ° C. for 15 minutes, the tire is taken out from the mold, and the degree of contamination of the mold due to ink drop is judged visually, and the PCS (print contrast signal) of the barcode pattern on the label is measured. Evaluation was performed based on ANSI standards. The PCS is calculated by the formula: (white background reflectance minus black reflectance) / white background reflectance, and the black portion of the tire management label becomes thinner and lowers as the ink is taken into the mold. The barcode standard requires PCS to be 0.75 or higher.
[0042]
The results are shown in the following table.

[Brief description of the drawings]
1 is a cross-sectional view of a label example. FIG. 2 is a cross-sectional view of a label base material.
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: Matt-treated surface 3: Primer layer 4: Rubber-based adhesive layer 5: Tire 6: Separator

Claims (1)

Matting treatment of a label base material comprising a rubber-based adhesive layer containing a vulcanization accelerator and containing no vulcanizing agent via a primer layer on the other side of a heat-resistant resin film containing a white filler matted on one side It has heat transfer ink information on its surface, and the heat transfer ink information has at least a two-layer structure of a lower layer made of heat-resistant resin-based ink and a surface layer made of polymethyl methacrylate and is exposed on the label surface. A label for tire management.

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