JP2015147837A - Pressure-sensitive adhesive sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a pressure-sensitive adhesive sheet having excellent adhesiveness to a tire without causing interlayer peeling in layers of the pressure-sensitive adhesive sheet even after the sheet is subjected to a vulcanization process.SOLUTION: The pressure-sensitive adhesive sheet includes a print layer 1, a plastic film 2, a primer layer 3, and a rubber-based pressure-sensitive adhesive layer formed of a rubber-based pressure-sensitive adhesive composition 4. The print layer is formed on one surface side of the plastic film; and the rubber-based pressure-sensitive adhesive layer is disposed on the other surface of the plastic film via the primer layer. The pressure-sensitive adhesive sheet shows a peeling force of 5.5 N/10 mm or more in a peeling test to measure a peeling force of the pressure-sensitive adhesive sheet with respect to a raw rubber of a tire after heat treatment by peeling the sheet at a drawing speed of 300 mm/min at 23°C in a 180° direction.

Description

  The present invention relates to an adhesive sheet.

  Tire management labels with information such as serial numbers are affixed to tires for the purpose of managing tire products in tire manufacturing plants, such as record management of inspection results for each tire and prevention of mixing of different types of tires. There is a case.

  As such a label, a pressure-sensitive adhesive sheet having a rubber-based pressure-sensitive adhesive layer on a polyester film via a primer layer is known (see Patent Documents 1 and 2).

JP-A-7-306642 JP 2002-244561 A

  In general, tires are made from different materials such as carcass, belt, tread, bead, etc., and each part is assembled with a molding machine to form a single raw tire (green tire), and the raw tire is vulcanized. It is manufactured through a process (a vulcanization process, a process of increasing the elasticity of rubber by adding heat, etc.). In tire management in a tire manufacturing factory, an adhesive sheet (a tire management label) is often attached to a raw tire. Therefore, the vulcanization process is often performed in a state where an adhesive sheet is attached.

  The pressure-sensitive adhesive sheet is a pressure-sensitive adhesive sheet that is excellent in adhesion to a tire. However, these pressure-sensitive adhesive sheets may be peeled off (delaminated) between layers of the pressure-sensitive adhesive sheet (for example, a base material and a primer layer, a primer layer and a rubber pressure-sensitive adhesive layer, etc.) after undergoing a vulcanization process. In some cases, the efficiency of the vulcanization process may be reduced.

  That is, the present situation is that there is no known pressure-sensitive adhesive sheet that does not peel off between the layers of the pressure-sensitive adhesive sheet after passing through the vulcanization step and has excellent adhesion to the tire.

  Accordingly, an object of the present invention is to provide a pressure-sensitive adhesive sheet that does not peel off between layers of the pressure-sensitive adhesive sheet and has excellent adhesion to a tire even after the vulcanization step.

  Therefore, as a result of intensive studies by the present inventors, the peeling force on the tire after the vulcanization process is set to a specific value or more so that each layer does not peel between the layers of the adhesive sheet even after the vulcanization process. And it discovered that the adhesive sheet excellent in the adhesiveness with respect to a tire was obtained, and completed this invention.

That is, the present invention is a pressure-sensitive adhesive sheet having a rubber-based pressure-sensitive adhesive layer formed from a printing layer, a plastic film, a primer layer, and a rubber-based pressure-sensitive adhesive composition, wherein the printing is performed on one surface side of the plastic film. The rubber-based pressure-sensitive adhesive layer is provided on the other surface of the plastic film via the primer layer, and the peel force in the following peel test is 5.5 N / 10 mm or more. A pressure-sensitive adhesive sheet is provided.
(Peel test)
Rubber-based pressure-sensitive adhesive layer surface of pressure-sensitive adhesive sheet (width 10 mm, length 150 mm) and tire raw rubber (butadiene rubber (trade name “BR01”, manufactured by JSR Corporation): natural rubber (polyisoprene natural product): fine powder sulfur ( Hosoi Chemical Co., Ltd.): rubber compounding oil (trade name “Diana Process Oil (PW380)”, manufactured by Idemitsu Kosan Co., Ltd.) = 30: 70: 3: 9) Affixing is performed under conditions, and left to stand at a temperature of 23 ° C. for 1 hour, followed by heat treatment at a temperature of 170 ° C. for 10 minutes.
Then, after leaving the pressure-sensitive adhesive sheet to stand at a temperature of 23 ° C. for 1 hour, using a tensile tester (trade name “Tensile Tester”, manufactured by Shimadzu Corporation), a tensile speed of 300 mm / min and a temperature of 23 ° C. It peels in the direction of 180 degree | times and measures the peeling force of the adhesive sheet with respect to the raw rubber of the tire after heat processing.

  The plastic film is preferably a plastic film having a melting point of 170 ° C. or higher, and the other surface of the plastic film is preferably corona-treated.

  The wetting tension of the plastic film measured by a wetting tension test according to JIS K6768: 1999 is preferably 45 dyne / cm or more.

  The rubber-based pressure-sensitive adhesive composition preferably contains a vulcanization accelerator.

  The rubber-based pressure-sensitive adhesive composition preferably contains a natural rubber pressure-sensitive adhesive.

  The rubber-based pressure-sensitive adhesive composition preferably contains a natural rubber-modified pressure-sensitive adhesive having a structural unit derived from methyl methacrylate.

  The printing layer is preferably a barcode.

  The pressure-sensitive adhesive sheet of the present invention is preferably a pressure-sensitive adhesive sheet for tires.

  Moreover, this invention provides the tire which has the said adhesive sheet.

  Since the pressure-sensitive adhesive sheet for tires of the present invention has the above configuration, each layer does not peel between the layers of the pressure-sensitive adhesive sheet and is excellent in adhesion to the tire even after the vulcanization step.

FIG. 1 is a schematic view (cross-sectional view) showing an example of the pressure-sensitive adhesive sheet of the present invention.

[Adhesive sheet]
The pressure-sensitive adhesive sheet of the present invention has at least a printing layer, a plastic film, a primer layer, and a rubber-based pressure-sensitive adhesive layer.

(Print layer)
The printed layer is provided on one surface side of the plastic film. The printed layer may be provided on one surface of the plastic film (may be in contact with one surface of the plastic film) or on the other surface of the plastic film. It may be provided via a layer. Especially, it is preferable that the said printing layer is provided on one surface of the said plastic film.

  Although the said printing layer is not specifically limited, For example, it is preferable to form from the ink containing resin and a coloring agent.

The resin contained in the ink is not particularly limited, and examples thereof include a polyester resin, a polyamide resin, an acrylic resin, a polycarbonate resin, and a phenol resin. Among these, polyester resins are preferable.
The resins contained in the ink can be used alone or in combination of two or more.

  When the material (resin) constituting the plastic film and the resin contained in the ink forming the print layer are the same type, when forming the print layer by thermal transfer or during the vulcanization process In some cases, the resins are melted and pressure-bonded (melt pressure-bonded), and the plastic film and the printed layer are more firmly bonded. Therefore, the material (resin) constituting the plastic film and the resin contained in the ink forming the printing layer are the same type of resin (for example, resins having the same type of main skeleton such as polyester resin and polyester resin). It is preferable that

The colorant contained in the ink is not particularly limited, and examples thereof include organic or inorganic pigments, carbon, and metal powder. The organic pigment is not particularly limited, and examples thereof include azo pigments, phthalocyanine pigments, triphenylmethane pigments, metal complex pigments, vat dye pigments, quinacridone pigments, and isoindolinone pigments. . Although it does not specifically limit as said inorganic pigment, For example, black things, such as chromium oxide, cobalt oxide, iron oxide, manganese oxide, chromate, permanganate; Manganese oxide, alumina, chromium oxide, tin oxide, Red materials such as iron oxide, cadmium sulfide, selenium sulfide; blue materials such as cobalt oxide, zirconia, vanadium oxide, chromium oxide, divanadium pentoxide; zirconium, silicon, praseodymium, vanadium, tin, chromium, titanium, antimony, etc. Yellow matter; Green color such as chromium oxide, cobalt / chromium, alumina / chromium; Pink color such as aluminum / manganese, iron / silicon / zirconium; White color such as silica, titania, alumina, zinc white, zirconia, calcium oxide, mica Thing, etc. Among these, a black colorant is preferable from the viewpoint of excellent visibility of the printed layer.
The colorants contained in the ink can be used alone or in combination of two or more.

  Although content of the said coloring agent is not specifically limited, For example, 1-90 weight% is preferable with respect to ink whole quantity (100 weight%), More preferably, it is 5-90 weight%. When the ink and the colorant are contained in the ink, the content of the colorant is not particularly limited, but is preferably 50 to 500 parts by weight with respect to 100 parts by weight of the resin, for example.

  The ink may further contain a solvent such as an organic solvent or alcohol as necessary.

  The shape (pattern, pattern) in plan view of the printing layer is not particularly limited, and examples thereof include shapes such as printing, a pattern, and a barcode (for example, a one-dimensional barcode, a two-dimensional barcode). Among these, a barcode is preferable from the viewpoint of a large amount of information and ease of information management.

  Although the thickness of the said printing layer is not specifically limited, From a viewpoint of adhesiveness with the said plastic film, 0.5-20 micrometers is preferable, for example, More preferably, it is 0.5-10 micrometers.

The printed layer may be provided on the entire surface of the plastic film, or may be provided on at least a part of the surface of the plastic film.
Although the said printing layer is not specifically limited, For example, it is preferable to be provided in 1 to 100% of the total surface area (100%) of one surface of the said plastic film, More preferably, it is 1 to 95%, More preferably Is 1 to 90%, particularly preferably 1 to 85%.
The ratio of the portion where the printed layer is provided to the total surface area of one surface of the plastic film is not particularly limited. For example, the ratio is 1 to the total surface area (100%) of one surface of the plastic film. -95% is preferable, More preferably, it is 1-80%, More preferably, it is 1-70%, Most preferably, it is 1-40%. When the ratio is 1% or more, it is easy to read information displayed on the print layer.

(Plastic film)
The said plastic film is a base material (reinforcing layer) in the adhesive sheet of this invention, and is a layer which does not peel from an adhesive sheet. That is, the pressure-sensitive adhesive sheet of the present invention has a plastic film as a substrate.
From the viewpoint that the plastic film can withstand a vulcanization process (for example, a vulcanization process at a temperature of 100 to 200 ° C., a time of 5 to 200 minutes) and is not easily deformed in the vulcanization process. A film that does not melt is preferred.

Although it does not specifically limit as said plastic film, For example, polyamide-type resin (polyamide etc.), polycarbonate-type resin (polycarbonate etc.), polyester-type resin (polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate etc.), polyolefin resin ( Polyethylene, polypropylene, etc.), polyphenylene ether, polyphenylene sulfide, polyarylate, polymethylpentene, polyamideimide, or a plastic film made of a combination thereof. Among these, from the viewpoint of cost and handling properties, a plastic film composed of a polyester resin is preferable, and a polyethylene terephthalate film is more preferable.
The plastic film may be a single layer or a multilayer.

  Although the melting point of the said plastic film is not specifically limited, From a heat resistant viewpoint at the time of vulcanization, 170 degreeC or more is preferable, for example, More preferably, it is 175 degreeC or more, More preferably, it is 180 degreeC or more. That is, the plastic film is preferably, for example, a plastic film having a melting point of 170 ° C. or higher. The melting point can be measured by DSC (differential scanning calorimetry).

  Although the said plastic film is not specifically limited, For example, you may be colored. Although it does not specifically limit as a color of the said plastic film, From the viewpoint that the visibility of a printing layer improves, the plastic film colored white is mentioned, for example.

The present inventor has found a problem that the pressure-sensitive adhesive sheet attached to the green tire is easily peeled between the plastic film and the primer layer after the vulcanization step.
The pressure-sensitive adhesive sheet for tire has properties different from those of a normal pressure-sensitive adhesive sheet in the following points. For example, in the pressure-sensitive adhesive sheet for tires, during the vulcanization step after being attached to the raw tire, the vulcanization accelerator contained in the pressure-sensitive adhesive layer absorbs the vulcanizing agent (sulfur compound) in the raw tire, The vulcanizing agent moves to the adhesive layer. And it cures and cures through the vulcanization accelerator in an adhesive layer, and an adhesive sheet and a tire adhere firmly (a tire and an adhesive sheet are integrated through a vulcanization process).
Further, although the cause is unknown, it is considered that the vulcanizing agent in the green tire also moves to the primer layer during the vulcanization process, and the composition of the primer layer changes.
Furthermore, it is conceivable that the primer layer softens after the vulcanization step, the interaction between the plastic film and the primer layer changes, and the adhesive force decreases.
From the peculiarity of such pressure-sensitive adhesive sheets for tires, based on conventional knowledge, it is possible to elucidate the cause of the problem that specific two layers, a plastic film and a primer layer, easily peel off after the vulcanization process, It was very difficult to find a solution.

The present inventor has studied means for solving the above problems from various viewpoints such as the composition of the plastic film and the primer layer, the post-treatment of each layer, and combinations thereof. As a result, it was surprisingly found that delamination between the plastic film and the primer layer can be prevented by strengthening the interaction between the plastic film and the primer layer.
After further investigation on an appropriate method for preventing delamination between the plastic film and the primer layer after the vulcanization process, unexpectedly, in particular, the other surface of the plastic film ( It has been found that it is very effective to perform surface treatment on the interface between the plastic film and the primer layer.

  The surface treatment applied to the other surface of the plastic film is not particularly limited. For example, corona discharge treatment, plasma treatment, sand mat processing treatment, ozone exposure, flame exposure, high piezoelectric impact exposure, ionizing radiation treatment, etc. Examples include physical treatment, chemical treatment such as chromic acid treatment, and easy adhesion treatment (coating treatment) with a coating agent (primer). Of these, corona discharge treatment and coating treatment with a coating agent are preferable from the viewpoint of excellent adhesion and retention between the adjacent plastic film and the primer layer. Among these, a corona discharge treatment is particularly preferable from the viewpoint of production stability.

  Although it does not specifically limit as a corona output in the said corona discharge process, For example, 0.5-8.0 kW is preferable, More preferably, it is 0.5-7.0 kW, Most preferably, it is 0.5-6.0 kW. .

  The treatment speed in the corona discharge treatment is preferably 5 to 100 m / min, more preferably 5 to 90 m / min, and particularly preferably 5 to 80 m / min.

The discharge amount in the corona discharge treatment is not particularly limited, for example, preferably 1～100W · min / m ^2, more preferably 1～90W · min / m ^2, more preferably 1～80W · min / m ² .

  By the corona discharge treatment, an organic functional group (polar functional group) such as a carboxyl group, a hydroxyl group, a ketone group, an aldehyde group, or a carbonyl group is introduced on the surface of the plastic film, and the hydrophilicity is considered to increase. For this reason, the affinity between the plastic film and the primer agent is improved, and the wettability of the primer agent with respect to the plastic film is improved. Moreover, it is thought that the adhesiveness of a plastic film and a primer layer also improves.

  Although it does not specifically limit as a coating agent in the said coating process, For example, polyester resins, such as polyester, polyester polyether, polyester polyurethane, polyester vinyl, acrylic resin, acrylic-urethane resin, acrylic-silicone resin, urethane-type resin , Vinyl chloride resin, vinyl chloride-vinyl acetate resin, phenol resin, epoxy resin, or a combination thereof. Of these, ester resins are preferred from the viewpoint of adhesion to the rubber adhesive layer and the plastic film. Examples of ester resins used as a coating agent include “Byron” series (Toyobo Co., Ltd.) (for example, Byron 29SS), “Polyester” series (Nippon Synthetic Chemical Co., Ltd.) (for example, Polyester LP050). Etc.), “Esper” series (manufactured by Hitachi Chemical Co., Ltd.) (for example, Esper 9940A), “Rigo rack” (manufactured by Showa Denko), “Arachid” series (manufactured by Arakawa Chemical Industries, Ltd.) (for example, 7063, etc.) ) And unsaturated ester resins such as “Sandoma” and “Exdoma” (manufactured by DIC Corporation).

  From the viewpoint of coatability, the coating agent may be used after diluted with a solvent (for example, toluene, MEK, ethyl acetate, etc.).

  The above-mentioned coating treatment is not particularly limited, but for example, a plastic film is coated by an appropriate method according to the material, such as a method of coating with a bar coater, a gravure roll or the like, or a method of hot-melting and hot-melt coating. be able to.

  Although it does not specifically limit as thickness of the layer which consists of a coating agent formed by the said coating process, For example, 0.1-30 micrometers is preferable, More preferably, it is 0.1-20 micrometers.

The details of the reason why delamination between the plastic film and the primer layer after the vulcanization process is suppressed by applying the above corona discharge treatment or coating treatment to the surface of the plastic film is unknown. Can be considered.
By corona discharge treatment or coating treatment, an organic functional group (polar functional group) such as a carboxyl group, a hydroxyl group, a ketone group, an aldehyde group, and a carbonyl group is introduced on the surface of the plastic film, and the hydrophilicity is considered to increase. For this reason, the organic functional group on the surface of the plastic film and the organic functional group in the primer agent attract each other by intermolecular force, and the affinity is improved. In addition, in the vulcanization process, it is considered that the organic functional group on the surface of the plastic film and the organic functional group in the primer layer promote a chemical reaction (for example, a dehydration reaction) to generate a covalent bond. As a result, even after the vulcanization process, the adhesiveness between the plastic film and the primer layer is strong, and it seems that delamination can be prevented.

  Although the thickness of the said plastic film is not specifically limited, For example, 25-1000 micrometers is preferable, More preferably, it is 38-500 micrometers, More preferably, it is 50-250 micrometers. If the plastic film is too thin, when the pressure-sensitive adhesive sheet of the present invention is affixed to a tire (particularly a raw tire), wrinkles may occur, resulting in poor adhesion. If the plastic film is too thick, the followability to the surface of the tire (particularly the raw tire) may be inferior, resulting in poor adhesion. Moreover, punching may be difficult.

  The present inventors have repeatedly studied the effect of preventing the delamination between the plastic film after the vulcanization step and the primer layer by the surface treatment of the plastic film. As a result, surprisingly, there is a correlation between the wettability (wetting tension) of the plastic film surface before applying the primer agent and the effect of preventing delamination between the plastic film and the primer layer after the vulcanization process. I found.

The wetting tension of the plastic film (wetting tension before applying the primer on the surface of the plastic film) is not particularly limited. For example, it is preferably 45 dyne / cm or more (for example, 45 to 60 dyne / cm), more preferably. Is 47 dyne or more, more preferably 49 dyne / cm or more, and particularly preferably 50 dyne / cm or more. When the wetting tension on the surface of the plastic film when applying the primer agent is 45 dyne / cm or more, the adhesion between the plastic film after the vulcanization step and the primer layer is improved. In particular, when it is 50 dyne / cm or more, the adhesion between the plastic film after the vulcanization step and the primer layer is remarkably improved. Therefore, delamination between the plastic film and the primer layer after the vulcanization process can be further suppressed.
The wetting tension refers to a wetting tension measured by a wetting tension test according to JIS K6768: 1999. The wetting tension can be adjusted by, for example, surface treatment of a plastic film.

(Primer layer)
The primer layer is a layer provided between the other surface of the plastic film and the rubber-based pressure-sensitive adhesive layer. That is, the primer layer is a layer provided on the surface of the plastic film different from the surface provided with the printing layer.
The primer layer is provided for the purpose of improving the adhesive strength between the plastic film and the rubber-based pressure-sensitive adhesive layer (particularly improving the adhesive strength after the vulcanization step). Even if a rubber-based pressure-sensitive adhesive layer is provided on a plastic film without providing a primer layer, the adhesion between the plastic film and the rubber-based pressure-sensitive adhesive layer may be insufficient and may be easily peeled off.

  The primer layer is preferably formed from a primer agent.

  The primer agent preferably contains a phenolic resin. Although it does not specifically limit as said phenol-type resin, For example, resin which has a structural unit derived from phenol, resorcinol, chlorophenol, pyroganol, etc. is mentioned.

  As the primer agent, for example, a mixture of resorcinol and formaldehyde is preferably used. Of these, a chlorophenol-based primer mixed with RFL (resorcinol, formaldehyde, latex) is preferable. In that 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, more preferably 5 to 80 parts by weight, More preferably, it is 10-67 weight part, Most preferably, it is 10-50 weight part. The composition of RFL includes a weight ratio of 1 / 0.5 to 2/2 to 10 based on R / F / L.

The viscosity of the primer agent is not particularly limited, but is preferably 1 mPa · s to 80 Pa · s, more preferably, from the viewpoint that the primer agent can be uniformly applied and the adhesion between the primer layer and the plastic film is further excellent. Is 5 mPa · s to 60 Pa · s.
In addition, the viscosity of the said primer agent shall say the viscosity measured using the BH type | mold viscosity meter.

  Although the thickness of the said primer layer is not specifically limited, For example, 1-50 micrometers is preferable, More preferably, it is 2-30 micrometers, More preferably, it is 5-20 micrometers.

(Rubber adhesive layer)
The rubber-based pressure-sensitive adhesive layer is a layer provided on the other surface of the plastic film via the primer layer. That is, the rubber-based pressure-sensitive adhesive layer is a layer provided on the surface of the primer layer opposite to the surface in contact with the plastic film.

  The rubber-based pressure-sensitive adhesive layer is a layer formed from a rubber-based pressure-sensitive adhesive composition. The rubber-based pressure-sensitive adhesive composition is not particularly limited, but from the viewpoint of adhesion to a tire, storage stability until practical use, and the like, for example, a rubber-based pressure-sensitive adhesive composition containing a pressure-sensitive adhesive and a vulcanization accelerator is used. preferable. The pressure-sensitive adhesive composition may further contain a tackifier resin, a crosslinking agent, an anti-aging agent, a plasticizer, an oil and the like.

  The pressure-sensitive adhesive contained in the rubber-based pressure-sensitive adhesive composition is not particularly limited, and examples thereof include rubber-based pressure-sensitive adhesives (synthetic rubber pressure-sensitive adhesives, natural rubber pressure-sensitive adhesives, natural rubber-modified pressure-sensitive adhesives, etc.), acrylic pressure-sensitive adhesives. And pressure sensitive adhesives such as urethane pressure sensitive adhesives and silicone pressure sensitive adhesives. Among these, a rubber-based pressure-sensitive adhesive is preferable from the viewpoint of adhesion to a tire. That is, the rubber-based pressure-sensitive adhesive composition preferably contains a rubber-based pressure-sensitive adhesive.

The rubber-based pressure-sensitive adhesive is not particularly limited. For example, diene-based synthetic rubber (for example, isoprene rubber, butadiene rubber, styrene-butadiene rubber, chloroprene rubber) or non-diene-based synthetic rubber (for example, butyl rubber, ethylene propylene). Synthetic rubber adhesives such as rubber, urethane rubber and silicone rubber), natural rubber adhesives such as natural rubber, and rubbers modified with natural rubber (for example, rubber obtained by addition polymerization of monomer components and oligomer components to natural rubber) And natural rubber-modified pressure-sensitive adhesives. Examples of the synthetic rubber pressure-sensitive adhesive include, from the viewpoint of firmly bonding the tire and the pressure-sensitive adhesive layer, for example, a graft rubber that is a graft copolymer (for example, a graft formed by graft polymerization of a rubber sol and a monomer). System rubber).
The rubber-based pressure-sensitive adhesives can be used alone or in combination of two or more.

  The rubber-based pressure-sensitive adhesive is not particularly limited, but is temporarily attached to a green tire (adhesion between the green tire and the pressure-sensitive adhesive sheet before the vulcanization process, difficulty in peeling off the pressure-sensitive adhesive sheet before the vulcanization process), a vulcanization process From the viewpoint of adhesion to the later tire, it is preferable to include a natural rubber pressure-sensitive adhesive. That is, the rubber-based pressure-sensitive adhesive composition preferably contains a natural rubber pressure-sensitive adhesive.

  The rubber-based pressure-sensitive adhesive has a reduced cohesive force after the vulcanization step, and in some cases, the rubber-based pressure-sensitive adhesive layer may be broken (disintegrated into tatters). Therefore, the rubber-based pressure-sensitive adhesive preferably has heat resistance. Examples of the heat-resistant rubber-based pressure-sensitive adhesive include rubber-based pressure-sensitive adhesives obtained by addition polymerization of monomer components and oligomer components. Among these, a rubber-based pressure-sensitive adhesive obtained by addition polymerization (graft polymerization) of (meth) acrylic acid ester or (meth) acrylic acid ester oligomer is preferable.

Although it does not specifically limit as said (meth) acrylic acid ester (or (meth) acrylic acid ester oligomer) which carries out addition polymerization to rubber adhesive, For example, (meth) acrylic acid methyl, (meth) acrylic acid ethyl, (Meth) acrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms such as (meth) butyl acrylate (an oligomer of (meth) acrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms) Is mentioned. Among these, from the viewpoint that the cohesiveness of the rubber-based pressure-sensitive adhesive is remarkably improved, (meth) acrylic acid alkyl ester having an alkyl group having 1 to 2 carbon atoms (having an alkyl group having 1 to 2 carbon atoms ( (Meth) acrylic acid alkyl ester oligomer) is preferred, more preferably methacrylic acid alkyl ester having an alkyl group having 1 to 2 carbon atoms (methacrylic acid alkyl ester having an alkyl group having 1 to 2 carbon atoms) Oligomer, and particularly preferably methyl methacrylate (an oligomer of methyl methacrylate).
The said (meth) acrylic acid ester can be used individually or in combination of 2 or more types.

As the rubber-based pressure-sensitive adhesive obtained by addition polymerization (graft polymerization) of (meth) acrylic acid ester or (meth) acrylic acid ester oligomer, for example, from the viewpoint of significantly increasing heat resistance, (meth) acrylic acid ester, Or, a natural rubber-modified pressure-sensitive adhesive obtained by addition polymerization (graft polymerization) of an oligomer of (meth) acrylate ester, more preferably a natural rubber-modified pressure-sensitive adhesive obtained by addition polymerization of methyl methacrylate (or an oligomer of methyl methacrylate). It is.
That is, the rubber-based pressure-sensitive adhesive preferably includes a rubber-based pressure-sensitive adhesive having a structural unit derived from (meth) acrylic acid ester, and a natural rubber-modified pressure-sensitive adhesive having a structural unit derived from (meth) acrylic acid ester. It is more preferable that a natural rubber-modified pressure-sensitive adhesive having a structural unit derived from methyl methacrylate is included.

  When the rubber-based pressure-sensitive adhesive is a rubber-based pressure-sensitive adhesive obtained by graft polymerization of (meth) acrylic acid ester (or (meth) acrylic acid ester oligomer), a branched (meth) acrylic acid ester terminal and a primer When the polar group-containing component (for example, phenol resin) in the layer is bonded, the adhesive layer between the primer layer and the rubber-based pressure-sensitive adhesive layer is further improved. This effect is particularly great when the (meth) acrylic acid ester is methyl methacrylate.

  The rubber-based pressure-sensitive adhesive is not particularly limited, but is more excellent in heat resistance, further excellent in adhesion to the tire after the vulcanization process, and further improves the adhesion between the primer layer and the rubber-based pressure-sensitive adhesive layer. From the viewpoint, for example, it is preferable to include a natural rubber pressure-sensitive adhesive and a natural rubber-modified pressure-sensitive adhesive (particularly a natural rubber pressure-sensitive adhesive and a natural rubber-modified pressure-sensitive adhesive having a structural unit derived from methyl methacrylate).

  Although it does not specifically limit as a compounding ratio in the case of addition-polymerizing (meth) acrylic acid ester (or (meth) acrylic acid ester oligomer) to a rubber-type adhesive, For example, with respect to 100 weight part of rubber-type adhesives The (meth) acrylic acid ester (or (meth) acrylic acid ester oligomer) is preferably 1 to 100 parts by weight, more preferably 5 to 100 parts by weight, and still more preferably 10 to 100 parts by weight. When the blending ratio of (meth) acrylic acid ester (or (meth) acrylic acid ester oligomer) is within the above range, the cohesiveness of the rubber-based pressure-sensitive adhesive is improved.

  The method for addition polymerization of (meth) acrylic acid ester (or (meth) acrylic acid ester oligomer) to the rubber-based pressure-sensitive adhesive is not particularly limited. For example, (meth) acrylic acid ester oligomer is added to the rubber-based pressure-sensitive adhesive. And (meth) acrylic acid ester are added to the rubber-based pressure-sensitive adhesive by polymerization.

  The ratio of the natural rubber pressure-sensitive adhesive in the rubber-based pressure-sensitive adhesive is not particularly limited. For example, it is preferably 1 to 99 parts by weight, more preferably 10 to 90 parts by weight based on the total amount of the rubber-based pressure-sensitive adhesive (100 parts by weight). Part by weight, more preferably 10 to 80 parts by weight. When the content of the natural rubber pressure-sensitive adhesive is in the above range, the adhesion between the tire after the vulcanization step and the pressure-sensitive adhesive sheet is further improved.

  The ratio of the rubber-based pressure-sensitive adhesive obtained by addition polymerization (graft polymerization) of (meth) acrylic acid ester or (meth) acrylic acid ester oligomer in the rubber-based pressure-sensitive adhesive is not particularly limited. 1-99 weight part is preferable with respect to the agent whole quantity (100 weight part), More preferably, it is 10-90 weight part, More preferably, it is 20-80 weight part.

  The rubber pressure-sensitive adhesive is not particularly limited, but is natural with respect to the total amount of rubber-based pressure-sensitive adhesive (100 parts by weight) from the viewpoint of further excellent heat resistance and further excellent adhesion to the tire after the vulcanization process. The ratio of the rubber adhesive is 10 to 90 parts by weight, and the ratio of the natural rubber modified adhesive (particularly, the natural rubber modified adhesive having a structural unit derived from methyl methacrylate) is 10 to 90 parts by weight. Preferably there is.

By including the vulcanization accelerator in the rubber-based pressure-sensitive adhesive composition, the vulcanizing agent (sulfur component, sulfur-based compound) contained in the tire moves to the rubber-based pressure-sensitive adhesive layer during the vulcanization process. This facilitates the adhesion between the rubber-based pressure-sensitive adhesive layer and the tire after the vulcanization process.
The vulcanization accelerator contained in the rubber-based pressure-sensitive adhesive composition is not particularly limited, and examples thereof include thiuram vulcanization accelerators (for example, tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetra Butyl thiuram disulfide, dipentamethylene thiuram tetrasulfide), dithiocarbamate vulcanization accelerator (eg zinc dimethyldithiocarbamate), thiazole vulcanization accelerator (eg 2-mercaptobenzothiazole, dibenzothiazyl disulfide) ), Sulfenamide vulcanization accelerators (for example, N-cyclohexyl-2-benzothiazole sulfenamide, Nt-butyl-2-benzothiazole sulfenamide, etc.), guanidine vulcanization accelerators (for example, Diphenylguanidine, etc.), aldehydes - ammonia-based vulcanization accelerator, aldehyde - amine-based vulcanization accelerator, thiourea based vulcanization accelerator, and the like xanthate based vulcanization accelerator. Of these, a thiuram vulcanization accelerator is preferred because it is more excellent in curability and adhesion after the vulcanization step.
The said vulcanization accelerator can be used individually or in combination of 2 or more types.

The tackifying resin contained in the rubber-based pressure-sensitive adhesive composition is not particularly limited, and examples thereof include terpene resins, rosin resins, hydrogenated rosin resins and glycerin esters thereof, coumarone indene resins, terpene phenols. Resin, alkylphenol resin, aliphatic and aromatic petroleum resin, and the like. Of these, petroleum resins are preferred from the viewpoint of temporary attachment to a raw tire.
The tackifier resins can be used alone or in combination of two or more.

Although it does not specifically limit as said crosslinking agent contained in the said rubber-type adhesive composition, For example, an isocyanate type crosslinking agent and a thiuram type crosslinking agent are mentioned.
The said crosslinking agent can be used individually or in combination of 2 or more types.

The anti-aging agent contained in the rubber-based pressure-sensitive adhesive composition is not particularly limited. For example, an amine ketone anti-aging agent, an aromatic secondary amine anti-aging agent, a phenol anti-aging agent, a benzimidazole type Examples thereof include an anti-aging agent, a dithiocarbamate anti-aging agent, a thiourea anti-aging agent, a phosphorous acid anti-aging agent, an organic thio acid anti-aging agent, and a special wax anti-aging agent. Among these, from the viewpoint of storage stability, a phenol-based antioxidant is preferable.
The above antioxidants can be used alone or in combination of two or more.

  The rubber-based pressure-sensitive adhesive composition is a vulcanizing agent (for example, sulfur, sulfur chloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, tetramethylthiuram, from the viewpoints of adhesion to tires and storage stability until practical use. Sulfur compounds such as disulfide and selenium dithiocarbamate) are preferably not included.

  The content of the pressure-sensitive adhesive (for example, rubber-based pressure-sensitive adhesive) in the rubber-based pressure-sensitive adhesive composition is not particularly limited, but for example, 1 to 1 with respect to the total amount of the rubber-based pressure-sensitive adhesive composition (100% by weight). 100 weight% is preferable, More preferably, it is 10-100 weight%, More preferably, it is 30-75 weight%.

  The content of the vulcanization accelerator in the rubber-based pressure-sensitive adhesive composition is not particularly limited, but is excellent in adhesion between the vulcanized tire and the rubber-based pressure-sensitive adhesive layer, and the vulcanized primer layer and the above-mentioned From the viewpoint that the adhesive strength of the rubber-based pressure-sensitive adhesive layer is also excellent, for example, 0.1 to 100 parts by weight is preferable, and more preferably 0.5 to 100 parts by weight of the above-mentioned pressure-sensitive adhesive (particularly, rubber-based pressure-sensitive adhesive). -100 parts by weight, more preferably 1.5-100 parts by weight.

  Although content of the said tackifying resin in the said rubber-based adhesive composition is not specifically limited, From viewpoints, such as temporary attachment to a green tire, it is 1-50 weight with respect to 100 weight part of said adhesives, for example. Part is preferred, more preferably 1 to 40 parts by weight.

  The rubber-based pressure-sensitive adhesive composition is, for example, 20 to 50 parts by weight (preferably 30 to 40 parts by weight) of the tackifier resin with respect to 100 parts by weight of a pressure-sensitive adhesive (particularly a rubber-based pressure-sensitive adhesive), and the vulcanization. It is preferable to contain 0.1 to 100 parts by weight (preferably 0.5 to 10 parts by weight) of an accelerator.

  The content of the anti-aging agent in the rubber-based pressure-sensitive adhesive composition is not particularly limited, but from the viewpoint of improving the storage stability, for example, with respect to 100 parts by weight of the pressure-sensitive adhesive (particularly the rubber-based pressure-sensitive adhesive), 0.5-80 weight part is preferable, More preferably, it is 0.5-50 weight part.

  Although the thickness of the said rubber-type adhesive layer is not specifically limited, For example, 10-50 micrometers is preferable, More preferably, it is 15-40 micrometers. If the thickness is less than 10 μm, the temporary attachment force to the raw tire may be poor, and if it exceeds 50 μm, the amount of paste may increase during processing.

  If the pressure-sensitive adhesive sheet of the present invention is within a range that does not impair the effects of the present invention, other layers (for example, a layer having a network structure such as a cloth or a resin applied in a mesh form, an extremely thin resin layer, etc.) May be provided.

  Although the thickness of the adhesive sheet of this invention is not specifically limited, For example, 25 micrometers or more (for example, 25-400 micrometers) are preferable, More preferably, it is 25-350 micrometers, More preferably, it is 25-300 micrometers.

  When the printed layer has a barcode shape (a space and a bar having different widths are appropriately arranged), the PCS value of the pressure-sensitive adhesive sheet of the present invention is not particularly limited, but is, for example, 60% or more. Is more preferable, and 70% or more is more preferable.

The PCS value is an index of barcode contrast, and is a value derived from the space reflectance of the barcode and the reflectance of the bar. The PCS value is a value obtained by subtracting the reflectance of the bar from the reflectance of the space and dividing it by the reflectance of the space. That is, the PCS value is a value calculated from the following equation.
PCS = {(space reflectance) − (bar reflectance)} / (space reflectance)
For example, a barcode composed of a white space and a black bar can be calculated from {(white space reflectance) − (black bar reflectance)} / (white space reflectance). Note that the closer the PCS value is to 1, the greater the separation between the reflectance of the space and the reflectance of the bar, so that the barcode has a higher contrast (easier to read).
The reflectance refers to the reflectance when, for example, red light having a wavelength of 660 nm is irradiated from a direction with an incident angle of 90 °. The reflectance can be measured using, for example, a bar code verifier (trade name “AUTOSCAN”, manufactured by RJS).

(Separator)
The rubber-based pressure-sensitive adhesive layer surface of the pressure-sensitive adhesive sheet of the present invention may be protected by a separator (release liner) until use. The separator is used as a protective material for the rubber-based pressure-sensitive adhesive layer, and is peeled off when the pressure-sensitive adhesive sheet of the present invention is attached to an adherend. Note that the separator is not necessarily provided.

  As the separator, a conventional release paper or the like can be used, and is not particularly limited. For example, a substrate having a release agent layer, a low adhesive substrate made of a fluorine-based polymer, or a low adhesive substrate made of a nonpolar polymer. Etc. Examples of the substrate having the release agent layer include a plastic film or paper surface-treated with a release agent such as a silicone release agent, a long-chain alkyl release agent, a fluorine release agent, and a molybdenum sulfide release agent. Can be mentioned. Examples of the fluorine polymer include polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, chlorofluoroethylene-vinylidene fluoride copolymer, and the like. Is mentioned. Moreover, as said nonpolar polymer, polyolefin resin (for example, polyethylene, a polypropylene, etc.) etc. are mentioned, for example. The separator can be formed by a known or common method. Further, the thickness of the separator is not particularly limited.

  The pressure-sensitive adhesive sheet of the present invention has a peel strength of 5.5 N / 10 mm or more (for example, 5.5 to 80 N / 10 mm) in the following peel test, preferably 10 N / 10 mm or more, more preferably 20 N / 10 mm or more, particularly preferably. Is 30 N / 10 mm or more. When the peeling force is 5.5 N / 10 mm or more, the adhesion between the tire after the vulcanization step and the pressure-sensitive adhesive sheet is excellent, and the pressure-sensitive adhesive sheet is difficult to peel between the respective layers after the vulcanization step. In particular, when the above range is 30 N / 10 mm or more, the adhesion between the tire after the vulcanization process and the pressure-sensitive adhesive sheet is further improved, and the pressure-sensitive adhesive sheet becomes more difficult to peel between the respective layers after the vulcanization process.

(Peel test)
The rubber-based pressure-sensitive adhesive layer surface of the pressure-sensitive adhesive sheet (width 10 mm, length 150 mm) of the present invention, and raw rubber of a tire (butadiene rubber (trade name “BR01”, manufactured by JSR Corporation): natural rubber (polyisoprene natural product): Fine sulfur (manufactured by Hosoi Chemical Co., Ltd.): rubber compounding oil (trade name “Diana Process Oil (PW380)”, manufactured by Idemitsu Kosan Co., Ltd.) = 30: 70: 3: 9), temperature 23 ° C., 2 kg roller After pasting under one reciprocating condition, and allowed to stand at a temperature of 23 ° C. for 1 hour, heat treatment (vulcanization treatment, vulcanization step) is performed at a temperature of 170 ° C. for 10 minutes.
Thereafter, the pressure-sensitive adhesive sheet was allowed to stand at a temperature of 23 ° C. for 1 hour, and then was used at a tensile speed of 300 mm / min and a temperature of 170 ° C. using a tensile tester (equipment trade name “Tensile Tester” manufactured by Shimadzu Corporation). The peel strength of the pressure-sensitive adhesive sheet to the rubber of the tire after heat treatment is measured.
In the peel test, the pressure-sensitive adhesive sheet is peeled off from the rubber of the tire. For example, the pressure-sensitive adhesive sheet is peeled between the layers of the pressure-sensitive adhesive sheet (for example, the rubber-based pressure-sensitive adhesive layer is peeled off between the plastic film and the primer layer). (Aspect as it is stuck to rubber of tire) (Aspect 1), Aspect in which the pressure-sensitive adhesive sheet peels off at the interface between the rubber-based pressure-sensitive adhesive layer and the rubber of the tire (Aspect 2), Part of the surface of the tire rubber is peeled off An embodiment (Aspect 3) is described in which the rubber-based pressure-sensitive adhesive layer is peeled off in a state where the rubber of the tire is adhered to the whole or the entire surface.

In the peel test, the pressure-sensitive adhesive sheet of the present invention is preferably peeled off from the tire without delamination. That is, in the pressure-sensitive adhesive sheet of the present invention, in the above peel test, the aspect in which the pressure-sensitive adhesive sheet peels from the rubber of the tire is preferably the above aspect 2 or the above aspect 3, and more preferably the above aspect 3.
By the vulcanization treatment, the rubber pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet and the tire are firmly bonded. That is, after the vulcanization treatment, the adhesive force may be weaker between the layers in the pressure-sensitive adhesive sheet than in the interface between the pressure-sensitive adhesive sheet and the tire. The pressure-sensitive adhesive sheet of the present invention is excellent in adhesiveness between each layer in the pressure-sensitive adhesive sheet (for example, a layer between a plastic film and a primer layer, a layer between a primer layer and a rubber-based pressure-sensitive adhesive layer). The sheet is difficult to delaminate.

  Although the use of the adhesive sheet of this invention is not specifically limited, For example, it is preferable that it is an adhesive sheet for tires, More preferably, it is an adhesive sheet affixed on the tire for motor vehicles, and the tire for aircrafts. The pressure-sensitive adhesive sheet of the present invention may be affixed to a raw tire before vulcanization or may be affixed to a tire after vulcanization.

  The example of the preferable specific aspect of the adhesive sheet of this invention is shown below.

  FIG. 1 is a schematic view (cross-sectional view) showing an example of the pressure-sensitive adhesive sheet of the present invention. The pressure-sensitive adhesive sheet shown in FIG. 1 has a printing layer 1, a plastic film 2, a primer layer 3, and a rubber-based pressure-sensitive adhesive layer 4. A printing layer 1 is provided on one surface side of the plastic film 2. A rubber-based pressure-sensitive adhesive layer 4 is provided on the surface of the plastic film 2 opposite to the side on which the printing layer 1 is provided (the other surface) via a primer layer 3.

[Method for producing adhesive sheet]
Although it does not specifically limit as a manufacturing method of the adhesive sheet of this invention, For example, the process (primer layer formation process) of providing a primer layer on one surface of the said plastic film, and the said rubber-type adhesive layer on the said primer layer It is preferable to include at least a step of providing (rubber-based pressure-sensitive adhesive layer forming step) and a step of providing a printing layer on the plastic film (printing step). Especially, it is preferable that the rubber-type adhesive layer formation process is provided after the primer layer formation process from a viewpoint of the adhesiveness between each layer of a plastic film, a primer layer, and a rubber-type adhesive layer. The printing process may be performed at any time, for example, before the primer layer forming process, between the primer layer forming process and the rubber adhesive layer forming process, or after the rubber adhesive layer forming process.

(Primer layer formation process)
The method for forming the primer layer in the primer layer forming step is not particularly limited. For example, the primer agent is applied to the surface of the plastic film by a known application method or impregnation method using a kiss coater or a doctor blade, and then dried. And the like.

  The plastic film is preferably surface-treated on the surface to which the primer agent is applied. Examples of the surface treatment include those described above. When surface treatment is performed on the plastic film, a primer agent may be applied immediately after the surface treatment (for example, continuously with the surface treatment) or after standing for a while after the surface treatment (for example, 1 hour to 1). A primer agent may be applied after standing for about a week).

  Even if a plastic film is placed on the dried primer layer, the adhesion between the plastic film and the primer layer may be insufficient. From the viewpoint of adhesion between the plastic film and the primer layer, it is particularly preferable to form a primer layer by applying a primer agent on the plastic film.

(Rubber adhesive layer forming process)
The method for forming the rubber-based pressure-sensitive adhesive layer is not particularly limited. For example, a rubber-based pressure-sensitive adhesive in which the pressure-sensitive adhesive, the vulcanization accelerator, the tackifier resin, the cross-linking agent, the anti-aging agent, and the like are uniformly mixed. The agent composition is diluted with an organic solvent (for example, toluene, etc.) as necessary, and coated on the primer layer by the phanten method, comma roll method, doctor blade method, calendar roll method, gravure roll coater method, etc. And a method of drying. In addition, you may transfer and form the rubber-type adhesive layer formed on the separator on the said primer layer.

(Printing process)
The means for forming the printing layer on the plastic film in the printing step is not particularly limited, and various printing means such as a thermal transfer method (thermal transfer), an inkjet method, and a gravure printing method can be employed. . Among these, the thermal transfer method and digital printing are preferable from the viewpoint that variable information can be printed. That is, the printing layer is preferably a printing layer formed by thermal transfer of the ink (a printing layer formed by a thermal transfer method). An ink layer is formed from the ink, and the ink layer is thermally transferred. More preferably, the printed layer is formed.

  Examples of a method for forming a print layer by thermally transferring an ink layer include a method using an ink sheet in which an ink layer is provided on a support substrate. Specifically, there is a method (thermal transfer method) in which the ink layer of the ink sheet is superposed so that the surface of the substrate is in contact, and the ink sheet is heated to transfer (thermal transfer) the ink layer to form a print layer (thermal transfer method). Can be mentioned.

  Although it does not specifically limit as said support substrate in the said ink sheet, For example, the cloth which consists of synthetic films, such as plastic films, such as polyester, a polyimide, a fluororesin, polyamide, polyester, etc. are mentioned. The support substrate may be coated with wax or the like from the viewpoint of improving the adhesion of the ink layer. As an ink layer provided on the support substrate, for example, a layer formed from the ink is preferable. The print layer and the ink layer are layers having the same composition except when the composition changes during thermal transfer.

  The method for forming the ink sheet is not particularly limited. For example, i) the resin, the colorant and the like are heated and mixed with a kneader of a roll mill, ii) the resin, the colorant, and as necessary. Examples include a method of preparing an ink having fluidity such as a paste by adding a solvent and mixing with a kneader such as a roll mill or pot mill, and applying or impregnating the ink to a support substrate to provide an ink layer. It is done.

  As an apparatus used when the ink layer of the ink sheet is thermally transferred to form a printing layer, for example, a printing apparatus adopting a commercially available thermal transfer system (for example, Dura Printer series, manufactured by Nitto Denko Corporation) should be used. Can do.

[tire]
The tire of the present invention is a tire having the pressure-sensitive adhesive sheet of the present invention. In the present specification, a tire before vulcanization is referred to as a “raw tire”, and a vulcanized tire is referred to as a “tire”.

  Although the tire of this invention is not specifically limited, From a viewpoint that it is excellent in log | history management, it is preferable that it is a tire by which the adhesive sheet of this invention was stuck to the beat part (part covered with the wheel), for example. In addition, the adhesive sheet of this invention should just be affixed so that at least one part of the said printing layer may enter into a bead part, for example, a part of said printing layer may protrude from the bead part.

  Although the manufacturing method of the tire of this invention is not specifically limited, For example, it is preferable to include at least the process of sticking the adhesive sheet of this invention to a green tire (especially bead part of a green tire), and a vulcanization process.

  Although it does not specifically limit as said raw tire, For example, it is preferable that it is a tire containing a vulcanizing agent. Examples of the vulcanizing agent include the aforementioned sulfur compounds. If the content of the vulcanizing agent in the green tire is small, delamination between the primer layer and the plastic film may easily occur. From the viewpoint of adhesion between the vulcanized tire and the pressure-sensitive adhesive sheet of the present invention, and delamination between the primer layer and the plastic film is less likely to occur, the vulcanizing agent content is based on the total weight of the tire (100 parts by weight) The amount is preferably 0.5 to 100 parts by weight.

  Although it does not specifically limit as conditions which affix the adhesive sheet of this invention on a green tire, For example, the conditions of a sticking temperature-10-60 degreeC (preferably 20-50 degreeC) are mentioned.

  The said vulcanization | cure process may be provided continuously after the process of sticking the adhesive sheet of this invention to a green tire, and you may leave an interval for 1 hour or more.

  Although the vulcanization temperature in the said vulcanization | cure process is not specifically limited, For example, 100-200 degreeC is preferable, More preferably, it is 140-180 degreeC, More preferably, it is 140-170 degreeC. Although the vulcanization time in the said vulcanization | cure process is not specifically limited, For example, 5-200 minutes are preferable, More preferably, it is 10-90 minutes.

  The absorption and vulcanization of the vulcanizing agent in the vulcanization process are considered to occur also in the primer layer and the plastic film, and the adhesive force between the primer layer and the plastic film after the vulcanization process is further improved. It is done.

  Examples of the tire of the present invention include automobile tires and aircraft tires.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited at all by these.

Example 1
On one surface of a polyethylene terephthalate film (trade name “U292W”, manufactured by Teijin DuPont Films Ltd., melting point 260 ° C., thickness 125 μm), an ink (trade name “Durainque DLH” manufactured by Nitto Denko Corporation) is used. The barcode was printed by a thermal transfer method to form a printed layer having a thickness of about 5 μm.
Thereafter, a corona treatment (treatment speed 50 m / min, corona output 2.7 kW) was performed on the surface (the other surface) opposite to the surface on which the printed layer of the polyethylene terephthalate film was formed. Next, on the other surface of the polyethylene terephthalate film (corona-treated surface), a primer agent (resorcin, formalin, latex mixed solution (RFL solution) (chlorphenol-based primer (Valkabond E, manufactured by ICI) 100) Parts (parts by weight, the same shall apply hereinafter), 4.1 parts of resorcinol (resorcinol, manufactured by Sumitomo Chemical Co., Ltd.), 3.6 parts of formaldehyde (formaldehyde solution, manufactured by Kisuda Chemical Co., Ltd.), vinylpyridine latex (solid content: 41% by weight) 47.4 parts (2518FS, manufactured by Nippon Zeon Co., Ltd.), SBR latex (solid content: 40% by weight) 11.7 parts (LX110, manufactured by Nippon Zeon Co., Ltd.), and 6.4 parts of a 5% by weight caustic soda solution were mixed with soft water 26. .8 parts mixed uniformly))) and dried at 150 ° C. for 2 minutes , To form a primer layer having a thickness of 10 [mu] m.
Thereafter, on the primer layer, a rubber-based pressure-sensitive adhesive composition (a rubber-based pressure-sensitive adhesive composition in which a blend polymer of natural rubber and synthetic rubber and a crosslinking agent is blended) (a graft rubber-based pressure-sensitive adhesive composition is 85 parts of graft rubber) (Polyisoprene natural product / MMA (Mitsubishi Gas Chemical Co., Ltd.) = 80 parts: 20 parts), Natural rubber 15 parts (Polyisoprene, natural products), Petroleum resin 35 parts (YS Resin PX1150, Yasuhara Chemical Co., Ltd.) , 4 parts of thiuram vulcanization accelerator (Noxeller TRA (manufactured by Ouchi Shinsei Chemical Co., Ltd.) / Noxeller PZ (manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.) = 50 parts: 50 parts), and phenolic antioxidant 3 Part (IRGANOX1010, manufactured by Ciba Japan Co., Ltd.) was dissolved in 200 parts of toluene and dried at 140 ° C. for 2 minutes. Thereby to form a rubber adhesive layer having a thickness of 25 [mu] m, to obtain an adhesive sheet.

(Example 2)
A pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1 except that the conditions for the corona treatment were a treatment speed of 100 m / min and a corona output of 1.5 kw.

(Example 3)
Instead of polyethylene terephthalate film (trade name “U292W”, manufactured by Teijin DuPont Films, Ltd., melting point 260 ° C., thickness 125 μm), polyethylene naphthalate film (trade name “Q51”, manufactured by Teijin DuPont Films, Inc., melting point 270 ° C. The pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1 except that the thickness was 125 μm.

Example 4
Instead of corona treatment (processing speed 50 m / min, corona output 2.7 kw), a coating agent (trade name “Byron 29SS”, manufactured by Toyobo Co., Ltd.) is applied and dried at 140 ° C. for 2 minutes to form a coating layer A pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1 except that a coating treatment was performed to apply and a primer agent was applied onto the coated surface.

(Example 5)
Polyisoprene natural product / MMA (Mitsubishi Gas Chemical Co., Ltd.) instead of using polyisoprene natural product / MMA (Mitsubishi Gas Chemical Co., Ltd.) = 80 parts: 20 parts as the graft rubber contained in the rubber-based pressure-sensitive adhesive composition Product) = 10 parts: An adhesive sheet was obtained in the same manner as in Example 1 except that 90 parts were used.

(Example 6)
In the rubber-based pressure-sensitive adhesive composition, a pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1 except that 100 parts of thiuram vulcanization accelerator was used instead of 4 parts. The thiuram vulcanization accelerator used was the same as in Example 1.

(Comparative Example 1)
Instead of polyethylene terephthalate film (trade name “U292W”, manufactured by Teijin DuPont Films, Ltd., melting point 260 ° C., thickness 125 μm), polyester film (trade name “F-2-706-PS-125”, Teijin DuPont Film Co., Ltd.) A pressure-sensitive adhesive sheet was prepared in the same manner as in Example 1 except that a company-made melting point of 260 ° C. and a thickness of 125 μm was used, and that no corona treatment (treatment speed 50 m / min, corona output 2.7 kw) was performed. Obtained.

[Evaluation]
(Wet tension)
The wetting tension of the plastic film surface subjected to corona treatment or coating treatment in the examples and the wetting tension of the plastic film surface in the comparative example were measured by a wetting tension test according to JIS K6768: 1999.

(Peeling force after vulcanization)
Sheet pieces (width 10 mm, length 150 mm, thickness 165 μm) were cut out from the pressure-sensitive adhesive sheets obtained in Examples and Comparative Examples. The rubber-based adhesive layer surface of the cut sheet piece and the raw rubber of the tire (butadiene rubber (trade name “BR01”, manufactured by JSR Corporation): natural rubber (polyisoprene natural product): fine sulfur (made by Hosoi Chemical Co., Ltd.) ): Rubber compounding oil (trade name “Diana Process Oil”, manufactured by Idemitsu Kosan Co., Ltd.) = 30: 70: 3: 9) After standing for 1 hour, heat treatment (vulcanization treatment) was performed at a temperature of 170 ° C. for 10 minutes.
Thereafter, the pressure-sensitive adhesive sheet was allowed to stand at a temperature of 23 ° C. for 1 hour, and then a tensile tester (apparatus product name “Tensile Tester”, manufactured by Shimadzu Corporation) was used at a tensile speed of 300 mm / min and a temperature of 23 ° C. The peel strength of the pressure-sensitive adhesive sheet with respect to the raw rubber of the tire after heat treatment was measured.

(State of pressure-sensitive adhesive sheet after vulcanization)
Ten sheet pieces (width 10 mm, length 150 mm, thickness 165 μm) were cut out from the pressure-sensitive adhesive sheets obtained in Examples and Comparative Examples. The rubber-based adhesive layer surface of the cut sheet piece and the raw rubber of the tire (butadiene rubber (trade name “BR01” manufactured by JSR Corporation): natural rubber (polyisoprene natural product): fine powder sulfur (manufactured by Hosoi Chemical Co., Ltd.) : Rubber compounded oil (trade name “Diana Process Oil (PW380)”, manufactured by Idemitsu Kosan Co., Ltd.) = 30: 70: 3: 9) was pasted under the conditions of a temperature of 23 ° C. and a reciprocation of 2 kg rollers, and a temperature of 23 After leaving still at 1 degreeC for 1 hour, it heat-processed at the temperature of 170 degreeC for 10 minutes (vulcanization process).
Thereafter, the pressure-sensitive adhesive sheet was allowed to stand at a temperature of 23 ° C. for 1 hour, and then the adhesion state between the layers of the pressure-sensitive adhesive sheet was visually confirmed.
The above evaluation was performed on 10 sheet pieces, and “excellent” (◎) when all sheet pieces did not peel between the layers (◎) and “good” when less than 3 sheet pieces were peeled between the layers (○ ) When the layers were separated by three or more sheet pieces, “bad” (×) and “state of pressure-sensitive adhesive sheet after vulcanization” were evaluated.

  The evaluation results are shown in Table 1.

As is apparent from Table 1, when the wetting tension is 45 dyne / cm or more, the peeling force of the pressure-sensitive adhesive sheet to the raw rubber of the tire after vulcanization treatment is improved. In particular, when the wetting tension was 50 dyne / cm or more, the peeling force was rapidly improved.
Further, when the wetting tension was 45 dyne / cm or more, delamination of the pressure-sensitive adhesive sheet after vulcanization treatment was eliminated.

1 Print layer 2 Plastic film 3 Primer layer 4 Rubber adhesive layer

Claims (9)

A pressure-sensitive adhesive sheet having a rubber-based pressure-sensitive adhesive layer formed of a printing layer, a plastic film, a primer layer, and a rubber-based pressure-sensitive adhesive composition,
Having the printed layer on one surface side of the plastic film;
The rubber-based pressure-sensitive adhesive layer is provided on the other surface of the plastic film via the primer layer,
A pressure-sensitive adhesive sheet having a peel strength of 5.5 N / 10 mm or more in the following peel test.
(Peel test)
Rubber-based pressure-sensitive adhesive layer surface of pressure-sensitive adhesive sheet (width 10 mm, length 150 mm) and tire raw rubber (butadiene rubber (trade name “BR01”, manufactured by JSR Corporation): natural rubber (polyisoprene natural product): fine powder sulfur ( Hosoi Chemical Co., Ltd.): rubber compounding oil (trade name “Diana Process Oil (PW380)”, manufactured by Idemitsu Kosan Co., Ltd.) = 30: 70: 3: 9) Affixing is performed under conditions, and left to stand at a temperature of 23 ° C. for 1 hour, followed by heat treatment at a temperature of 170 ° C. for 10 minutes.
Then, after leaving the pressure-sensitive adhesive sheet to stand at a temperature of 23 ° C. for 1 hour, using a tensile tester (trade name “Tensile Tester”, manufactured by Shimadzu Corporation), a tensile speed of 300 mm / min and a temperature of 23 ° C. It peels in the direction of 180 degree | times and measures the peeling force of the adhesive sheet with respect to the raw rubber of the tire after heat processing.   The pressure-sensitive adhesive sheet according to claim 1, wherein the plastic film is a plastic film having a melting point of 170 ° C or higher, and the other surface of the plastic film is subjected to corona treatment.   The pressure-sensitive adhesive sheet according to claim 1 or 2, wherein a wetting tension of the plastic film measured by a wetting tension test according to JIS K6768: 1999 is 45 dyne / cm or more.   The pressure-sensitive adhesive sheet according to claim 1, wherein the rubber-based pressure-sensitive adhesive composition contains a vulcanization accelerator.   The pressure-sensitive adhesive sheet according to any one of claims 1 to 4, wherein the rubber-based pressure-sensitive adhesive composition contains a natural rubber pressure-sensitive adhesive.   The pressure-sensitive adhesive sheet according to claim 1, wherein the rubber-based pressure-sensitive adhesive composition contains a natural rubber-modified pressure-sensitive adhesive having a structural unit derived from methyl methacrylate.   The pressure-sensitive adhesive sheet according to claim 1, wherein the print layer is a barcode.   It is an adhesive sheet for tires, The adhesive sheet of any one of Claims 1-7.   A tire having the pressure-sensitive adhesive sheet according to claim 1.

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