JP2015223918A - Pneumatic tire provided with electronic component and method for manufacturing same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a pneumatic tire which has an excellent bondability between an electronic component and a tire rubber member, and a method for manufacturing the pneumatic tire.SOLUTION: A pneumatic tire to which an electronic component is bonded by an adhesive, in which the adhesive comprises a mixture of a polythiol compound (A), an isocyanate group-containing compound (B) and a radical generating agent (C), a ratio of the total mole number of an isocyanate group contained in a mixed isocyanate group-containing compound (B) to the total mole number of a thiol group contained in a mixed polythiol compound (A) (namely, isocyanate group/thiol group) is equal to or more than 0.2 and equal to or less than 0.78.

Description

  The present invention relates to a pneumatic tire in which electronic components are arranged and a method for manufacturing the same.

For example, there is a passive radio frequency identification transponder (hereinafter also referred to as “transponder”) as a non-contact type information recording / reproducing apparatus capable of writing or reading information using radio waves. The tire is managed by attaching a transponder to the tire and writing or reading information about the tire on the transponder.
The specifications for tires for vehicles such as automobiles are in production management, distribution management, maintenance management during tire use, and production management and maintenance management of retread tires that have been refurbished after the end of the primary life. It is necessary to grasp the unique information of each tire such as manufacturing history and usage history.
As a method of adding the unique information to the tire, conventionally, a method of sticking a barcode type sticker on the surface or the inner surface of the tire, a method of imprinting a recognition code on the surface of the tire, and the like have been proposed.
However, in the method of pasting a barcode or the like on the tire surface described above, there is a risk of peeling off due to an external stimulus or the like, and there is a risk that it may become unreadable due to dirt or scratches. As a result, wear and scratches may occur, making it unreadable.
Therefore, in place of these methods, a method for attaching a device capable of data communication without contact has been proposed in the following patent document.

Patent Document 1 discloses a radio frequency identifier (RFID) tag as a transponder, and discloses that a tire is managed by attaching a barcode label incorporating the RFID tag with an adhesive.
Furthermore, Patent Document 2 discloses a tire in which an electronic member or an electronic tag is embedded in a tire sidewall.

JP 2005-216077 A JP 2012-240680 A

On the other hand, in the case of the above-described method of attaching a device capable of data communication without contact, since it can be attached to the inside of the tire, there is no fear of dropping off or wearing out. The incorporated pneumatic tire also has room for improvement in the bondability between the electronic component and the tire member.
In other words, the tire rubber member is greatly deformed during use, but the electronic component embedded in the rubber member is composed of a resin or metal that hardly deforms, so that the interface between the rubber member and the electronic component is distorted. Cheap.
For this reason, if the electronic component is simply physically embedded in the tire, the interface between the electronic component and the rubber member may be worn away, or the end of the non-bonded portion may crack and the tire or the electronic component may break down. There is a risk. In particular, in the case of a pneumatic tire used at a high internal pressure, the non-adhered portion also has a high internal pressure, which may cause swelling and promote the progress of cracks.
However, in general, the compatibility between the base resin and metal member constituting the electronic component, or the resin cover or metal cover packed with the electronic component and the rubber material for the tire is poor. It may be difficult to keep the rubber member for tires adhered well for a long time.

  This invention makes it a subject to provide the manufacturing method of the pneumatic tire which was excellent in bondability, and the pneumatic tire by using the adhesive of a specific structure for the electronic component and the rubber member for tires.

  The present inventor uses an adhesive containing a component that causes a reaction in which a carbon atom constituting a carbon-carbon double bond forms a carbon-sulfur bond with a sulfur atom, thereby firmly bonding an electronic component and a rubber member. Thus, the inventors have found that the problems of the present invention can be solved, and have completed the present invention.

That is, the present invention relates to the following [1] to [8].
[1] A pneumatic tire in which electronic components are joined by an adhesive, wherein the adhesive is blended with a polythiol compound (A), an isocyanate group-containing compound (B), and a radical generator (C), The ratio (isocyanate group / thiol group) of the total number of isocyanate groups contained in the blended isocyanate group-containing compound (B) to the total number of moles of thiol groups contained in the blended polythiol compound (A) is 0.00. A pneumatic tire that is 2 or more and 0.78 or less.
[2] The pneumatic tire according to [1], wherein the radical generator (C) is a thermal radical generator made of a peroxide.
[3] Ratio of the total number of moles of the radical generator (C) to be blended to the total number of moles of thiol groups contained in the polythiol compound (A) in which the adhesive is blended (radical generator (C) / The pneumatic tire according to claim 1 or 2, wherein the thiol group is 0.025 or more.
[4] The pneumatic tire according to any one of [1] to [3], wherein the electronic component is a passive radio frequency identification transponder covered with metal or resin.
[5] The pneumatic tire according to [4], wherein the passive radio frequency identification transponder is an RFID tag.
[6] A step of applying an adhesive to the entire electronic component, a step of semi-curing the adhesive applied to the electronic component to form a coating layer that can adhere to the electronic component, and an unvulcanized rubber Vulcanizing after contacting a member or a semi-vulcanized rubber member and an electronic component on which a coating layer is formed, and the adhesive comprises a polythiol compound (A), an isocyanate group-containing compound Isocyanate contained in the isocyanate group-containing compound (B) to be blended with respect to the total number of moles of thiol groups contained in the blended polythiol compound (A), comprising (B) and the radical generator (C). The manufacturing method of a pneumatic tire whose ratio (isocyanate group / thiol group) of the total number of groups of groups is 0.2 or more and 0.78 or less.
[7] A step of bonding the vulcanized rubber member and the electronic component through an adhesive, and a step of curing the adhesive with heating or light, wherein the adhesive is a polythiol compound (A ), An isocyanate group-containing compound (B), and a radical generator (C), and an isocyanate group-containing compound to be blended with respect to the total number of moles of thiol groups contained in the blended polythiol compound (A) ( The manufacturing method of a pneumatic tire whose ratio (isocyanate group / thiol group) of the total number of moles of isocyanate groups contained in B) is 0.2 or more and 0.78 or less.
[8] The method for manufacturing a pneumatic tire according to [7], wherein the curing step further includes pressurization.

  According to the present invention, there is provided a pneumatic tire in which an electronic component and a rubber member are firmly bonded by using an adhesive having a specific structure between the electronic component and the rubber member, and a method for manufacturing the pneumatic tire. Can be provided.

It is a perspective view which shows an example of the structure of a RFID tag. It is a perspective view which shows an example of the structure of the RFID tag coat | covered with the adhesive agent of the specific structure used by this invention. It is a partial schematic sectional drawing along the tire width direction which shows an example of the pneumatic tire with which the RFID tag was embed | buried. It is a partial schematic sectional drawing along the tire width direction which shows the other example of the pneumatic tire with which the RFID tag was embed | buried. It is a partial schematic sectional drawing along the tire width direction which shows an example of the pneumatic tire by which the RFID tag was arrange | positioned on the back surface of the tread part. It is a flowchart which shows an example of the manufacturing method of the pneumatic tire of this invention. It is a flowchart which shows the other example of the manufacturing method of the pneumatic tire of this invention.

[Pneumatic tire and manufacturing method thereof]
The pneumatic tire of this invention is a pneumatic tire which joined the electronic component with the adhesive which has the specific structure mentioned later, as shown to FIGS.
Moreover, the manufacturing method of the pneumatic tire of the 1st form of this invention is a process (S100) of apply | coating an adhesive agent to the whole electronic component, and the adhesive agent apply | coated to the said electronic component, as shown in FIG. Forming a coating layer that can be semi-cured to adhere to the electronic component (S102), and contacting the unvulcanized rubber member or the semi-vulcanized rubber member and the electronic component on which the coating layer is formed Then, a vulcanizing step (S104), and a manufacturing method using an adhesive having a specific configuration described later as an adhesive.
Furthermore, in the method for manufacturing a pneumatic tire according to the second aspect of the present invention, as shown in FIG. 7, the step of bonding the vulcanized rubber member and the electronic component via an adhesive (S200), and heating Or the process of hardening the said adhesive agent with light (S202), It is a manufacturing method using the adhesive agent which has a specific structure mentioned later as an adhesive agent.

Here, the semi-vulcanized state means a state in which the degree of vulcanization is higher than that in the unvulcanized state, but does not reach the degree of vulcanization required for the final product. This means that the required degree of vulcanization has been reached.
In addition, “semi-cured” in an adhesive is a state in which the surface of the adhesive is gently rubbed with a fingertip and the surface is not scratched, but can be easily melted and bonded by heating and pressing. means.
In the present specification, the term “to” is a term indicating a lower limit value or more and an upper limit value or less.

In addition, the electronic component used in the present invention can store data relating to the identification of a pneumatic tire, so that it is possible to improve efficiency during maintenance and other service operations of the tire in manufacturing and logistics transportation. ing. Examples of the electronic component include a passive radio frequency identification transponder (hereinafter also referred to as “transponder”), and an RFID (radio frequency identifier) tag is used as the transponder.
FIG. 1 shows an example of the structure of an RFID tag.
As shown in FIG. 1, an RFID tag 10 used in the present invention includes antennas 20 and 22, an IC chip 12 having a communication function operated by dielectric electromotive force generated by weak radio waves received by the antenna, and an IC chip. And a conductive substrate 18 for electrically securing the IC chip and the antennas 20 and 22. Further, the RFID tag 10 may be packaged with metal or resin.
Examples of the exterior layer of the electronic component include a metal layer and a resin layer. The adhesive having a specific structure in the present invention can strongly bond these metal layers and resin layers, and the resin layer has a strength surface when used in a pneumatic tire, From the viewpoint of reactivity with the isocyanate group-containing compound in the adhesive, an epoxy resin is preferred.

The pneumatic tire manufacturing method according to the first aspect of the present invention is a method of embedding the RFID tag 10 inside the pneumatic tire. First, as shown in FIG. An adhesive having a specific configuration to be described later is applied (S100), and the adhesive applied to the RFID tag 10 which is the electronic component is semi-cured and adhered to the electronic component or the electronic component covered with metal or resin. A possible covering layer is formed (S102).
As shown in FIG. 2, a specific adhesive, which will be described later, is applied to the entire RFID tag 10 and left as it is for a predetermined time or irradiated with light as necessary, whereby the semi-cured coating layer 21 is applied to the RFID tag 10. The coated RFID tag 25 formed with the coating layer 21 that can be bonded is manufactured.
This coated RFID tag 25 is an example of an electronic component comprising a transbonder or an RFID tag in which the coated RFID tag 25 is entirely coated with an adhesive having a specific configuration, and a semi-cured adhesive coating layer is formed. is there.

When left for a predetermined time after application of the adhesive, the standing time is a time required for the adhesive to be semi-cured and not flow out, and is preferably 0 to 30 minutes, more preferably 1 to 15 minutes. .
Further, from the viewpoint of improving the adhesiveness between the cover layer 21 made of an adhesive and the RFID tag 10 described later, the coated RFID tag 25 on which the coat layer 21 that can be bonded may be pressed. The pressurization is preferably 0 to 5 MPa, and more preferably 0 to 2.5 MPa. Moreover, from the same viewpoint, the pressurization time is preferably 5 to 120 minutes, more preferably 10 to 60 minutes, and further preferably 15 to 45 minutes.
The thickness of the coating layer 21 is preferably 1 μm or more and 1 mm or less, and more preferably 30 μm or more and 300 μm or less, from the viewpoint of the balance between the distortion caused by the RFID tag 10 and the adhesive force in the pneumatic tire.

Next, the unvulcanized rubber member or the semi-vulcanized rubber member and the coated RFID tag 25 on which the coat layer 21 that can be bonded are brought into contact with each other, and then vulcanized (S104).
Thereby, the coating layer 21 which consists of an adhesive agent containing the component which raise | generates the reaction which the carbon atom which comprises a carbon-carbon double bond mentioned later forms a carbon atom and a carbon-sulfur bond, and a metal and a resin member are mentioned later. The RFID tag 10 formed of the combination is chemically bonded and the tire rubber material and the coating layer 21 are also chemically bonded, so that the RFID tag 10 as an electronic component is firmly bonded to the tire. In addition, there is an advantage that the RFID tag 10 which is an electronic component is protected from heat during vulcanization by the coating layer 21 made of an adhesive.

In FIG. 2, the RFID tag 10 that is not covered with metal or resin is described as an example. However, the RFID tag 10 may be covered with metal or resin.
As described above, since the compatibility of the resin cover or metal cover packed with electronic parts and the rubber material for tire is poor, the resin cover or metal cover and tire rubber that are packaged on the RFID tag 10 as in the present invention are used. Between the materials, a coating layer 21 made of an adhesive containing a component that causes a reaction in which a carbon atom constituting a carbon-carbon double bond forms a sulfur atom and a carbon-sulfur bond, which will be described later, is interposed. Thereafter, the resin cover or the metal cover and the coating layer 21 are chemically bonded by vulcanization, and the rubber material for the tire and the coating layer 21 are also chemically bonded. Therefore, the RFID tag 10 which is an electronic component is used. Is firmly bonded to the tire. In addition, there is an advantage that the RFID tag 10 which is an electronic component is protected from heat during vulcanization by the coating layer 21 made of an adhesive.

3 and 4 are partial schematic cross-sectional views along the tire width direction showing an example of a pneumatic tire in which the RFID tag 10 is embedded.
Here, the pneumatic tire is provided with a bead 30 and a pair of stiffeners 32 on the outer side in the radial direction of each bead 30, and the stiffener 32 is a rubber filling located in a region within the tire above the bead 30. Is configured. In addition, one or more tire plies 34, 44, an inner liner 36, and sidewalls 38 are further added in tire manufacture. The plies 34, 44 comprise a plurality of rubber-coated interwoven weave layers extending from bead to bead and folded around bead 30 to secure bead 30 into the assembly or carcass ( Not shown).
The ply turn 48 from the ply 44 is wound under the bead 30 as shown. Each stiffener 32 is located above each bead 30 and radially outward from each bead 30. A chafer part 54 is made of reinforcing material around the bead 30 and is located axially outward to engage the rim flange area and thereby prevent the rim part from scuffing the tire. The chafer part 54 extends to the chafer end 56.

  In the production process of the raw tire, it is preferable to incorporate a coated RFID tag 25 in which a coating layer 21 that can be adhered to the RFID tag 10 is formed as shown in FIG. 2, and as shown in FIG. (Shown in FIG. 2) may be located on the sidewall above the ply turn between the stiffener 32, chafer 54, ply 44 and sidewall 38, and contact the ply 44 and sidewall 38. It may be located as follows. Further, the antennas 20 and 22 (shown in FIG. 1) of the RFID tag 10 in the coated RFID tag 25 on which the adhesive coat layer 21 is formed so as to extend perpendicular to the ply 44 extending in the circumferential direction of the tire. Has been placed.

  As another position inside the raw tire, as shown in FIG. 4, the coated RFID tag 25 in which the coating layer 21 that can be adhered to the RFID tag 10 is formed, between the stiffener 32 and the ply 34, The stiffener 32 and the ply 34 may be disposed in contact with each other. Note that the direction of the antenna is the same as described above, and thus description thereof is omitted here.

The method for manufacturing a pneumatic tire according to the second aspect of the present invention is a method of attaching the RFID tag 10 to the inner surface of the pneumatic tire, and as shown in FIG. Are bonded through an adhesive having a specific configuration described later (S200), and the adhesive is cured by heating or light (S202).
When joining the vulcanized rubber member and the electronic component, an adhesive having a specific structure to be described later is applied to at least one of the back surface of the RFID tag 10 and the surface of the vulcanized rubber member to which the RFID tag 10 is joined. You may apply | coat and may affix the sheet | seat which consists of the adhesive agent mentioned later.
Further, as an example of joining the RFID tag 10 to a vulcanized pneumatic tire, for example, as shown in FIG. 5, the RFID tag 10 is attached to the back surface of the tread 62 of the vulcanized pneumatic tire via an adhesive. The tag 10 may be joined.

In addition, when heating to cure the adhesive, it is preferable that the radical generator in the adhesive described later includes a thermal radical generator, and a temperature at which radicals are efficiently generated is appropriately selected, and more preferably thermal radical generation is performed. Heat the agent at 1 minute half-life temperature around ± 30 ° C.
When curing the adhesive by light irradiation, it is preferable to use an ultraviolet lamp as a light source from the viewpoint of improving the adhesive force and reducing the cost, including a photo radical generator as a radical generator in the adhesive described later. . From the same viewpoint, the light irradiation time is preferably several seconds to several tens of seconds.
Furthermore, when pressurizing at the time of joining, from a viewpoint of improving adhesive force, pressurization is preferably 0.1 to 5.0 MPa, more preferably 0.4 to 4.0 MPa, and still more preferably 0.00. 5 to 3.0 MPa.

<Rubber materials for tires>
The rubber material before being bonded to the adhesive in the present invention may be vulcanized rubber, unvulcanized rubber, or semi-vulcanized rubber.
The rubber constituting the rubber material preferably has a carbon-carbon double bond. That is, it is speculated that the carbon atom of the carbon-carbon double bond of the rubber material in contact with the adhesive described later forms a carbon-sulfur bond with the sulfur atom of the thiol group of the polythiol compound (A) in the adhesive described later. Because.
Even if the rubber constituting the rubber material does not have a carbon-carbon double bond, the polythiol compound (A) in the adhesive extracts hydrogen from the carbon-carbon bond main chain present in the rubber. It is inferred that the sulfur atom of the thiol group of the polythiol compound (A) and the carbon atom of the carbon-carbon bond are chemically bonded by the reaction.
However, from the viewpoint of improving the adhesive strength, the rubber constituting the rubber material preferably has a carbon-carbon double bond.

  The rubber material is not particularly limited. For example, natural rubber; polyisoprene synthetic rubber (IR), polybutadiene rubber (BR), styrene-butadiene copolymer rubber (SBR), acrylonitrile butadiene rubber (NBR), chloroprene rubber (CR ), Conjugated diene synthetic rubbers such as butyl rubber (IIR); ethylene-propylene copolymer rubber (EPM), ethylene-propylene-diene copolymer rubber (EPDM), polysiloxane rubber, etc. Then, natural rubber and conjugated diene synthetic rubber are preferable. Moreover, you may use a rubber component in combination of 2 or more types.

<Adhesive>
The adhesive according to the present invention includes the following composition. These adhesives may contain components other than the above composition as long as the object of the present invention is not impaired. However, the content of the composition in the adhesive or coating agent is preferably 90% by mass or more, more preferably 95% by mass or more, and further preferably 99% by mass or more, from the viewpoint of satisfactorily expressing the effects of the present invention. More preferably, it is 100 mass%.

〔Composition〕
The composition according to the present invention comprises a polythiol compound (A), an isocyanate group-containing compound (B), and a radical generator (C). The total of thiol groups contained in the blended polythiol compound (A). It is a composition whose ratio (isocyanate group / thiol group) of the total number of moles of isocyanate groups contained in the blended isocyanate group-containing compound (B) with respect to the number of moles is 0.2 or more and 0.78 or less.

According to the composition of the present invention, not only unvulcanized rubber but also vulcanized rubber can be strongly bonded. The reason is estimated as follows.
It is considered that the composition is strongly cured by causing a urethanization reaction between a part of the polythiol compound (A) and the isocyanate group-containing compound (B). Further, it is considered that another part of the polythiol compound (A) reacts with the radical generator (C) to generate a thiyl radical, and this thiyl radical reacts with a carbon-carbon double bond present in the rubber. Such a thiol-ene reaction is considered to cause the composition to be strongly bonded to the rubber by chemically bonding the composition to the rubber. In particular, since carbon-carbon double bonds exist not only in unvulcanized rubber but also in vulcanized rubber, it is considered that according to the composition of the present invention, rubber, particularly vulcanized rubber, can be strongly bonded. .
Further, it is considered that the sulfur atom of the thiol group of the polythiol compound (A) and the carbon atom of the carbon-carbon bond are chemically bonded by a hydrogen abstraction reaction from the carbon-carbon bond main chain existing in the rubber. Therefore, it is not always necessary to have a carbon-carbon double bond in the rubber.
In the present specification, the polythiol compound (A), the isocyanate group-containing compound (B), the radical generator (C), the urethanization catalyst (D) and the surface conditioner (E) are respectively added to the component (A), It may be called a component (B), a component (C), a component (D), and a component (E).

<Polythiol compound (A)>
In the present invention, the polythiol compound (A) refers to a compound having two or more thiol groups in one molecule.
Although there is no restriction | limiting in particular in a polythiol compound (A), From a viewpoint of improving adhesiveness, what has 2-6 thiol groups in 1 molecule is preferable.
In addition, the polythiol compound (A) includes primary, secondary and tertiary compounds, but the primary is more preferable from the viewpoint of improving adhesiveness.
From the viewpoint of improving adhesiveness, the molecular weight of the polythiol compound (A) is preferably 3000 or less, more preferably 2000 or less, still more preferably 1000 or less, still more preferably 900 or less, more More preferably, it is 800 or less. In addition, when a polythiol compound (A) is a polymer, molecular weight means the number average molecular weight of styrene conversion.

Examples of the polythiol compound (A) include aliphatic polythiols that may contain heteroatoms and aromatic polythiols that may contain heteroatoms. From the viewpoint of improving adhesiveness, polythiol compounds (A) may contain heteroatoms. Good aliphatic polythiols are preferred.
Here, the aliphatic polythiol which may contain a hetero atom refers to an aliphatic compound which may contain a hetero atom having two or more thiol groups in one molecule. Moreover, the aromatic polythiol which may contain the hetero atom means the aromatic compound which may contain the hetero atom which has two or more thiol groups in 1 molecule.
The heteroatom is preferably at least one selected from oxygen, nitrogen, sulfur, phosphorus, halogen atoms, and silicon, more preferably oxygen, nitrogen, sulfur, phosphorus, and halogen atoms, from the viewpoint of improving adhesive strength. It is at least one selected, and more preferably at least one selected from oxygen, nitrogen and sulfur.

Examples of the aliphatic polythiol that may contain a hetero atom include, for example, a polythiol other than a thiol group, such as an alkanedithiol having 2 to 20 carbon atoms, and a halogen atom of a halohydrin adduct of alcohol. Thioglycolic acid ester obtained by esterification of polythiol substituted with thiol group, polythiol composed of hydrogen sulfide reaction product of polyepoxide compound, polyhydric alcohol having 2-6 hydroxyl groups in the molecule and thioglycolic acid Contains a mercapto fatty acid esterified product obtained by esterification of a polyhydric alcohol having 2 to 6 hydroxyl groups in the molecule and a mercapto fatty acid, a thiol isocyanurate compound obtained by reacting an isocyanurate compound and a thiol, and a polysulfide group Thiol Silicones modified with thiol groups, silsesquioxane or the like which is modified with a thiol group.
The polyhydric alcohols having 2 to 6 hydroxyl groups in the molecule include alkanediol having 2 to 20 carbon atoms, poly (oxyalkylene) glycol, glycerol, diglycerol, trimethylolpropane, ditrimethylolpropane, Examples include pentaerythritol and dipentaerythritol.

  Among these, from the viewpoint of improving adhesiveness, polythiols other than thiol groups are aliphatic hydrocarbons, polythiols obtained by substituting halogen atoms of alcohol halohydrin adducts with thiol groups, hydrogen sulfides of polyepoxide compounds A polythiol, a thioglycolic acid ester, a mercapto fatty acid ester, and a thiol isocyanurate compound are more preferable, a mercapto fatty acid ester and a thiol isocyanurate compound are more preferable, and a mercapto fatty acid ester is more preferable. From the same viewpoint, a thiol containing no polysulfide group or siloxane bond is more preferable.

(Polythiol whose part other than thiol group is aliphatic hydrocarbon)
Examples of the polythiol in which the portion other than the thiol group is an aliphatic hydrocarbon include alkanedithiol having 2 to 20 carbon atoms.
Examples of the alkanedithiol having 2 to 20 carbon atoms include 1,2-ethanedithiol, 1,1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol, 1,4 -Butanedithiol, 2,3-butanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, 1,8-octanedithiol, 1,10-decanedithiol, 1,1-cyclohexanedithiol, 1,2- And cyclohexanedithiol.

(Thioglycolic acid ester)
Examples of the thioglycolic acid ester include 1,4-butanediol bisthioglycolate, 1,6-hexanediol bisthioglycolate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthioglycolate, and the like.

(Mercapto fatty acid esterified product)
As the mercapto fatty acid ester product, a mercapto fatty acid ester product having a primary thiol group is preferable from the viewpoint of improving adhesiveness, and a β-mercaptopropionic acid ester product of a polyhydric alcohol having 2 to 6 hydroxyl groups in the molecule. Is more preferable. The mercapto fatty acid esterified product having a primary thiol group preferably has 4 to 6 thiol groups in one molecule from the viewpoint of improving adhesiveness, and preferably 4 or 6. Preferably, it is four.

  The β-mercaptopropionate esterified product having a primary thiol group is preferably tetraethylene glycol bis (3-mercaptopropionate) (EGMP-4), trimethylolpropane tris (3-mercaptopropionate). (TMMP), pentaerythritol tetrakis (3-mercaptopropionate) (PEMP), and dipentaerythritol hexakis (3-mercaptopropionate) (DPMP). Among these, PEMP and DPMP are preferable, and PEMP is more preferable.

  Examples of the β-mercaptopropionic acid esterified product having a secondary thiol group include esterified products of polyhydric alcohols having 2 to 6 hydroxyl groups in the molecule and β-mercaptobutanoic acid. 1,4-bis (3-mercaptobutyryloxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate) and the like.

(Thiol isocyanurate compound)
As a thiol isocyanurate compound obtained by reacting an isocyanurate compound with a thiol, a thiol isocyanurate compound having a primary thiol group is preferable from the viewpoint of improving adhesive strength. Moreover, as a thiol isocyanurate compound which has a primary thiol group, it is preferable that the number of thiol groups in 1 molecule is 2-4, and it is more preferable that it is three from a viewpoint of an adhesive improvement. .
As the thiol isocyanurate compound having a primary thiol group, tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate (TEMPIC) is preferable.

(Silicone modified with thiol group)
Examples of silicones modified with a thiol group include trade names KF-2001, KF-2004, X-22-167B (Shin-Etsu Chemical), SMS042, SMS022 (Gelest), PS849, PS850 (UCT). .

(Aromatic polythiol)
Aromatic polythiols include 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis (mercaptomethyl) benzene, 1,3-bis (mercaptomethyl) Benzene, 1,4-bis (mercaptomethyl) benzene, 1,2-bis (mercaptoethyl) benzene, 1,3-bis (mercaptoethyl) benzene, 1,4-bis (mercaptoethyl) benzene, 1,2, 3-trimercaptobenzene, 1,2,4-trimercaptobenzene, 1,3,5-trimercaptobenzene, 1,2,3-tris (mercaptomethyl) benzene, 1,2,4-tris (mercaptomethyl) Benzene, 1,3,5-tris (mercaptomethyl) benzene, 1,2,3-tris (mercaptoethyl) benze 1,2,4-tris (mercaptoethyl) benzene, 1,3,5-tris (mercaptoethyl) benzene, 2,5-toluenedithiol, 3,4-toluenedithiol, 1,3-di (p-methoxy) Phenyl) propane-2,2-dithiol, 1,3-diphenylpropane-2,2-dithiol, phenylmethane-1,1-dithiol, 2,4-di (p-mercaptophenyl) pentane and the like.

<Isocyanate group-containing compound (B)>
Examples of the isocyanate group-containing compound (B) include aromatic, aliphatic and alicyclic diisocyanates, and modified products thereof.

  Examples of aromatic, aliphatic and alicyclic diisocyanates include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), xylylene diisocyanate (XDI), naphthylene diisocyanate (NDI), phenylene diisocyanate (PPDI), m. -Tetramethylxylylene diisocyanate (TMXDI), methylcyclohexane diisocyanate (hydrogenated TDI), dicyclohexylmethane diisocyanate (hydrogenated MDI), cyclohexane diisocyanate (hydrogenated PPDI), bis (isocyanatomethyl) cyclohexane (Hydrogenated XDI), norbornene diisocyanate (NBDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), butanediiso Aneto, hexamethylene diisocyanate 2,2,4-trimethyl hexamethylene diisocyanate to 2,4,4-trimethyl like.

  When the blended polythiol compound (A) is a mercapto fatty acid ester and a thiol isocyanurate compound, the blended isocyanate group-containing compound (B) is hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), tri One or more of diisocyanate (TDI), xylylene diisocyanate (XDI), and diphenylmethane diisocyanate (MDI) are preferred. Among these, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), xylylene diisocyanate (XDI), bis (isocyanatomethyl) cyclohexane (hydrogenated XDI) and tolylene diisocyanate (TDI). 1 type or 2 types or more are more preferable.

  In addition, as modified products of aromatic, aliphatic and alicyclic diisocyanates, TMP (trimethylolpropane) adduct modified products obtained by reaction of trimethylolpropane and isocyanate, isocyanurate obtained by trimerization of isocyanate Type modified products, burette modified products obtained by reaction of urea and isocyanate, allophanate modified products obtained by reaction of urethane and isocyanate, prepolymers obtained by reaction with polyol, etc. Can be used.

In addition, as a TMP adduct type modified body, an isocyanurate type modified body, a burette type modified body, and an allophanate type modified body, the following modified body is preferable from a viewpoint of an adhesive improvement.
That is, as the TMP adduct type modified product, a TMP adduct type modified product obtained by the reaction of TMP and TDI, a TMP adduct type modified product obtained by the reaction of TMP and XDI, and a reaction of TMP and hydrogenated XDI are obtained. TMP adduct-type modified product, TMP adduct-type modified product obtained by reaction of TMP and IPDI, TMP adduct-type modified product obtained by reaction of TMP and HDI, and TMP adduct type obtained by reaction of TMP and MDI Modified products are preferred.
Further, the isocyanurate-type modified product is an isocyanurate-type modified product obtained by trimming HDI, an isocyanurate-type modified product obtained by trimming IPDI, an isocyanurate-type modified product obtained by trimming TDI, and An isocyanurate type modified product obtained by trimerization of hydrogenated XDI is preferred.
Moreover, as a burette type modified body, the burette type modified body obtained by reaction of urea and HDI is preferable.
Moreover, as an allophanate type modified body, the allophanate type modified body obtained by reaction of urethane and IPDI is preferable.

The polythiol compound (A) used in combination with at least one of the above-mentioned TMP adduct type modified product, isocyanurate type modified product, burette type modified product and allophanate modified product is preferably β having a primary thiol group -One or two mercaptopropionic acid ester compounds and a thiol isocyanurate compound having a primary thiol group.
Here, as the β-mercaptopropionate esterified product having a primary thiol group, preferably pentaerythritol tetrakis (3-mercaptopropionate) (PEMP) and dipentaerythritol hexakis (3-mercaptopropionate) DPMP At least one of the following. The thiol isocyanurate compound having a primary thiol group is preferably a thiol isocyanurate compound having a primary thiol group having 3 thiol groups in one molecule, and more preferably tris- [ (3-mercaptopropionyloxy) -ethyl] -isocyanurate (TEMPIC).

<Radical generator (C)>
As the radical generator (C), at least one of a thermal radical generator and a photo radical generator can be used. Among these, from the viewpoint of improving the adhesive force and from the viewpoint of being able to adhere rubber that is not transparent (not transmitting light), a thermal radical generator is preferable, a thermal radical generator composed of peroxide is more preferable, and organic A thermal radical generator made of peroxide is more preferred.
A radical generator (C) can also be used individually by 1 type or in combination of 2 or more types.

  Examples of the thermal radical generator composed of an organic peroxide include t-butyl-2-ethylperoxyhexanoate, dilauroyl peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexa. Noate, 1,1-di (t-hexylperoxy) cyclohexanone, di-t-butyl peroxide, t-butylcumyl peroxide, 1,1-di (t-hexylperoxy) -3,3,5 -Trimethylcyclohexane, t-amylperoxy-2-ethylhexanoate, di (2-t-butylperoxyisopropyl) benzene, di (t-butyl) peroxide, benzoyl peroxide 1,1'-di (2 -T-butylperoxyisopropyl) benzene, benzoyl peroxide, 1,1'-di (t-butylperoxy) cyclohexane Sun, di (3,5,5-trimethyl hexanoyl) peroxide, t- butyl peroxyneodecanoate, t-hexyl peroxyneodecanoate, dicumyl peroxide and the like. Among these, preferably t-butyl-2-ethylperoxyhexanoate, dilauroyl peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 1,1-di It is at least one of (t-hexylperoxy) cyclohexanone, di-t-butyl peroxide, and t-butylcumyl peroxide. The thermal radical generator composed of an organic peroxide can be used alone or in combination of two or more.

  Redox generation consisting of a combination of oxidizing agent and reducing agent such as a combination of hydrogen peroxide and iron (II) salt, a combination of persulfate and sodium bisulfite, etc. Agents. The thermal radical generator composed of an inorganic oxide can be used alone or in combination of two or more.

As the photoradical generator, known ones can be widely used and are not particularly limited.
For example, an intramolecular cleavage type photo radical generator may be mentioned, and benzoin alkyl ether photo radical generators such as benzoin ethyl ether, benzoin isobutyl ether and benzoin isopropyl ether; 2,2-diethoxyacetophenone, 4′-phenoxy-2 Acetophenone photoradical generators such as 2-dichloroacetophenone, 2-hydroxy-2-methylpropiophenone, 4′-isopropyl-2-hydroxy-2-methylpropiophenone, 4′-dodecyl-2-hydroxy- Propiophenone photoradical generators such as 2-methylpropiophenone; anthraquinone photoradical generators such as benzyldimethyl ketal, 1-hydroxycyclohexyl phenyl ketone and 2-ethylanthraquinone, 2-chloroanthraquinone; Sill phosphine oxide-based photo-radical generating agent, and the like.

Other hydrogen abstraction type photo radical generators include benzophenone / amine photo radical generator, Michler ketone / benzophenone photo radical generator, thioxanthone / amine photo radical generator, and the like. In order to avoid migration of the unreacted photoradical generator, a non-extractable photoradical generator can be used. For example, there are those obtained by polymerizing an acetophenone radical generator and those obtained by adding a double bond of an acrylic group to benzophenone.
These photo radical generators can be used alone or in combination of two or more.

<Optional component>
The composition according to the present invention may further contain an optional component. Optional components include urethanization catalysts, surface conditioners, solvents, binders, fillers, pigment dispersants, conductivity imparting agents, UV absorbers, antioxidants, anti-drying agents, penetrants, pH adjusters, metal sequestering agents. , Fungicides, fungicides, surfactants, plasticizers, waxes, leveling agents and the like.

(Urethane catalyst (D))
Any urethanization catalyst can be used as the urethanization catalyst (D). Examples of the catalyst for urethanization reaction include dibutyltin dilaurate, dibutyltin diacetate, dibutyltin thiocarboxylate, dibutyltin dimaleate, dioctyltin thiocarboxylate, tin octenoate, monobutyltin oxide and the like; stannous chloride, etc. Inorganic lead compounds; organic lead compounds such as lead octenoate; bis (2-dimethylaminoethyl) ether, N, N, N ′, N′-tetramethylhexamethylenediamine, triethylenediamine (TEDA), benzyldimethylamine, Amines such as 2,2′-dimorpholinoethyl ether and N-methylmorpholine; organic sulfonic acids such as p-toluenesulfonic acid, methanesulfonic acid and fluorosulfuric acid; inorganic acids such as sulfuric acid, phosphoric acid and perchloric acid Sodium alcoholate, lithium hydroxide Beam, aluminum alcoholate, bases such as sodium hydroxide; tetrabutyl titanate, tetraethyl titanate, titanium compounds such as tetraisopropyl titanate; bismuth compounds; quaternary ammonium salts, and the like. Among these, the above amines are preferable, and triethylenediamine (TEDA) is more preferable. These catalysts may be used alone or in combination of two or more.
It is preferable that 0.0001-0.1 mass% of urethanization catalysts (D) are contained in a composition.

(Surface conditioner (E))
Any surface conditioning agent can be used as the surface conditioning agent (E). Examples of the surface conditioner include acrylic, vinyl, silicone, and fluorine. Among these, a silicone type is preferable from the viewpoint of compatibility and surface tension reducing ability.
It is preferable that 0.001-10 mass% of surface conditioning agents (E) are contained in a composition.

(solvent)
The solvent is not particularly limited as long as it does not react with other compounding components, and examples thereof include aromatic solvents and aliphatic solvents.
Specific examples of the aromatic solvent include toluene, xylene and the like. Hexane etc. are mentioned as an aliphatic solvent.

<Amount of each component>
The ratio of the total number of moles of isocyanate groups contained in the blended isocyanate group-containing compound (B) to the total number of moles of thiol groups contained in the blended polythiol compound (A) (isocyanate group / thiol group) is 0. .2 or more and 0.78 or less. When the ratio (isocyanate group / thiol group) is less than 0.2, the composition is not sufficiently hardened and the adhesive strength is reduced. Further, when the ratio (isocyanate group / thiol group) is larger than 0.78, the thiol-ene reaction is sufficiently performed between the thiol group and the carbon-carbon double bond of the rubber member because there are few thiol groups. Otherwise, the composition cannot be firmly bonded to the rubber member, and the adhesive strength is reduced. Therefore, the ratio (isocyanate group / thiol group) is preferably 0.30 or more, preferably 0.70 or less, and preferably 0.40 to 0.70.
Here, the total number of moles of thiol groups contained in the blended polythiol compound (A) is obtained by multiplying the number of moles of the blended polythiol compound (A) by the number of thiol groups possessed by one molecule of the polythiol compound (A). Can be calculated.
Moreover, the total mole number of the isocyanate group contained in the isocyanate group containing compound (B) mix | blended can be measured by JISK1603-1 B method.
Furthermore, the ratio of the number of moles (isocyanate group / thiol group) is the polythiol compound blended with the total number of moles of isocyanate groups contained in the blended isocyanate group-containing compound (B) obtained as described above. It can be determined by dividing by the total number of moles of thiol groups contained in (A).

  The ratio of the total number of moles of the radical generator (C) to be blended to the total number of moles of thiol groups contained in the blended polythiol compound (A) (radical generator (C) / thiol group) is 0.025. The above is preferable. Thereby, adhesiveness improves. From this viewpoint, the ratio (radical generator (C) / thiol group) is preferably 0.03 or more, more preferably 0.035 or more, and further preferably 0.04 or more. In addition, from the viewpoint of improving adhesion and / or adhesion, the ratio (radical generator (C) / thiol group) is preferably 0.5 or less, more preferably 0.45 or less, and further Preferably it is 0.4 or less.

  When the compounded radical generator (C) contains a photo radical generator, the ratio of the total number of moles of the photo radical generator to the total number of moles of thiol groups contained in the polythiol compound (A) (light The radical generator / thiol group is preferably 0.0005 or more. Thereby, adhesiveness and / or adhesiveness improve. From this viewpoint, the ratio (photo radical generator / thiol group) is more preferably 0.001 or more, and further preferably 0.005 or more. Moreover, since an excessive photoradical generator causes high cost, it is preferably 0.2 or less, more preferably 0.1 or less, and further preferably 0.05 or less from the viewpoint of economy. It is.

  When the radical generator (C) contains a thermal radical generator, the ratio of the total number of moles of the thermal radical generator to the total number of moles of thiol groups contained in the polythiol compound (A) (radical generator) (C) / thiol group) is preferably 0.025 or more. Thereby, adhesiveness and / or adhesiveness improve. From this viewpoint, the ratio (thermal radical generator / thiol group) is preferably 0.03 or more, more preferably 0.035 or more, and further preferably 0.04 or more. Further, from the viewpoint of improving adhesiveness and / or adhesion, the ratio (thermal radical generator / thiol group) is preferably 0.5 or less, more preferably 0.45 or less, and still more preferably. 0.4 or less.

  When the radical generator (C) includes a photoradical generator and a thermal radical generator, the photoradical generator and the thermal radical generator with respect to the total number of moles of thiol groups contained in the polythiol compound (A). The ratio of the total number of moles {(photo radical generator and thermal radical generator) / thiol group} is preferably 0.025 or more. Thereby, adhesiveness and / or adhesiveness improve. From this viewpoint, the ratio {(photo radical generator and thermal radical generator) / thiol group} is preferably 0.03 or more, more preferably 0.035 or more, and further preferably 0.04 or more. It is. Further, from the viewpoint of improving adhesiveness and / or adhesion, the ratio {(photo radical generator and thermal radical generator) / thiol group} is preferably 0.5 or less, more preferably 0.45. Or less, more preferably 0.4 or less.

As an optional component, a compound containing a carbon-carbon double bond may be blended. However, when the compounding quantity of this compound containing a carbon-carbon double bond increases, a polythiol compound (A) will react with the compound containing this carbon-carbon double bond. Thereby, the thiol-ene reaction between the polythiol compound (A) and the carbon-carbon double bond in the rubber becomes difficult to occur, and the adhesive force of the composition to the rubber may be reduced. Alternatively, a reaction in which the sulfur atom of the thiol group of the polythiol compound (A) and the carbon atom of the carbon-carbon bond are chemically bonded hardly occurs due to the hydrogen abstraction reaction from the carbon-carbon bond main chain of the rubber. Therefore, the adhesive strength of the composition to rubber may be reduced. Therefore, the ratio of the total number of moles of carbon-carbon double bonds contained in the compound containing carbon-carbon double bonds to be blended to the total number of moles of thiol groups contained in the blended polythiol compound (A) (carbon -Carbon double bond / thiol group) is preferably less than 0.4, preferably less than 0.1, more preferably 0.08 or less, and 0.05 or less. More preferably, it is still more preferably 0.01 or less.
Here, the total number of moles of carbon-carbon double bonds contained in the compound containing a carbon-carbon double bond to be blended is the carbon-carbon of one molecule of the compound in the number of moles of the compound to be blended. It can be determined by multiplying the number of double bonds.
Further, the ratio of the number of moles (carbon-carbon double bond / thiol group) includes the total number of moles of carbon-carbon double bonds obtained as described above in the blended polythiol compound (A). It can be determined by dividing by the total number of moles of thiol groups.

As described above, the composition according to the present invention may contain an optional component in addition to the components (A) to (C) which are essential components. However, from the viewpoint of strongly bonding rubber, particularly vulcanized rubber, the total content of components (A) to (C) in the composition is preferably 80% by mass or more, more preferably 90% by mass or more. Preferably it is 95 mass% or more, More preferably, it is 98 mass% or more.
From the same viewpoint, the total content of the components (A) to (E) is preferably 90% by mass or more, more preferably 95% by mass or more, further preferably 99% by mass or more, and further preferably 100% by mass. .

<Adhesive sheet>
The sheet-like adhesive in the present invention is formed using the above-described composition.
This adhesive sheet can be suitably manufactured by applying the composition onto a release sheet such as release paper or release film and maintaining the sheet shape. By this holding, it is considered that at least a part of the thiol group and the isocyanate group in the composition undergo a thiolurethane reaction to form a sheet shape. In addition, an adhesive sheet can be suitably manufactured by leaving it at normal temperature after application | coating. Moreover, you may manufacture an adhesive sheet by heating so that the radical reaction by a radical generator may not start after application | coating.
The holding time can be adjusted by the amount of the urethanization catalyst. From the viewpoint of workability in forming a sheet and maintaining the shape to such an extent that the sheet shape can be maintained during the bonding operation, it is preferably 1 minute or longer, more preferably 3 minutes or longer. The holding temperature can usually be made into a sheet at room temperature, but it can also be heated to such an extent that the radical generator in the material is not cleaved. From the above viewpoint, it is preferably 0 to 60 ° C, more preferably 15 to 40 ° C.

The material of the release sheet is not particularly limited, but polyester resins such as polyethylene terephthalate, polycyclohexylene terephthalate and polyethylene naphthalate, polyamide resins such as nylon 46, modified nylon 6T, nylon MXD6 and polyphthalamide, polyphenylene sulfide In addition to ketone resins such as polythioether sulfone, sulfone resins such as polysulfone and polyether sulfone, polyether nitrile, polyarylate, polyetherimide, polyamideimide, polycarbonate, polymethyl methacrylate, triacetyl cellulose, polystyrene A transparent resin substrate mainly composed of an organic resin such as polyvinyl chloride can be suitably used.
Although the thickness of an adhesive sheet can be suitably selected according to the object to adhere | attach, the adhesive strength requested | required, etc., it is 20-1000 micrometers, for example, Preferably it is 30-300 micrometers, More preferably, it is 30-200 micrometers. It is.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples. In the following examples, “part” and “%” are based on mass unless otherwise specified.

<Method for producing adhesive>
Adhesives 1 to 3 were prepared by blending and mixing the components shown in Table 1 below.

* 1: PEMP: Pentaerythritol tetrakis (3-mercaptopropionate): manufactured by SC Organic Chemical Co., Ltd. * 2: DPMP: Dipentaerythritol hexakis (3-mercaptopropionate): manufactured by SC Organic Chemical Co., Ltd. * 3 : Product name “Desmodule N3200”: HDI burette modified isocyanate: manufactured by Sumitomo Bayer Urethane Co., Ltd. * 4: Product name “Desmodule Z4470BA”: IPDI isocyanurate modified isocyanate: manufactured by Sumika Bayer Urethane Co., Ltd. * 5: Product name “Perbutyl O”: t-butyl-2-ethylperoxyhexanoate: NOF Corporation

The total number of moles of thiol groups contained in the polythiol compound (A) was calculated by dividing the blending amount by the theoretical molecular weight and multiplying by the number of thiol groups possessed by one molecule of the polythiol compound (A).
Moreover, the total mole number of the isocyanate group contained in the isocyanate group containing compound (B) mix | blended was measured by JISK1603-1 B method.

-Creation of adhesive sheet-
The obtained adhesive 1 was applied on a PET release film and dried at 25 ° C. for 15 minutes to prepare an adhesive sheet. The adhesive sheet was adjusted to have a thickness (for example, 50 μm in Example 4) shown in the column “Adhesive coating layer or adhesive layer” in Table 2 by adjusting the amount of adhesive 1 applied.

<Production of test tire>
After the RFID tag is entirely covered with the adhesives 1 to 3 in Table 1, as shown in FIG. 3, the RFID tag is placed on a raw tire, and an 11R225 size heavy duty tire is molded and vulcanized by a normal method. Test tires were prepared.
Moreover, after making the adhesive 1 of Table 1 into an adhesive sheet, as shown in FIG. 5, it stuck on the back surface of the tread of 11R22.5 size heavy duty tire which was shape | molded and vulcanized by the normal method, and was a test tire. Was made.

  As shown in FIG. 3, the rubber material forming the sidewall or the tread back surface shown in FIG. 5 has the composition shown in Table 2.

* 10: Natural rubber STR-20
* 11: Show Black N330 (made by Showa Cabot Corporation)
* 12: Three types of zinc oxide (Shodo Chemical Industry Co., Ltd.)
* 13: Bead stearic acid YR (manufactured by NOF Corporation)
* 14: SANTOFLEX 6PPD (manufactured by Flexsys)
* 15: NOCRACK 224 (Ouchi Shinsei Chemical Co., Ltd.)
* 16 Extract 4 (made by Showa Shell Co., Ltd.)
* 17: Fine powder sulfur with Jinhua seal oil (manufactured by Tsurumi Chemical Co., Ltd.)
* 18: Noxeller NS-P (Ouchi Shinsei Chemical Co., Ltd.)

<Test method>
・ Communication distance:
The RFID scanner AWID MRR 1510 was slowly approached from a position sufficiently away from the fixed test tire, and the distance at which the scanner first read the RFID signal was recorded. Each tire was measured five times, and the average value was taken as the communication distance.

・ Durability test / presence or absence of destruction:
The test tire was filled with air to 850 kPa, an indoor drum test was performed with a load of 53.46 kN, a speed of 30 km / hour, and no steering angle, and the presence or absence of breakage due to running near the RFID tag was visually confirmed.
The evaluation results of the above test are shown in Table 3.

  From the comparison between Examples 1 to 4 and Comparative Example 1, the pneumatic tire joined with the RFID tag through the adhesive used in the present invention is similar to the case without the adhesive while maintaining the tire durability. It was found that an excellent communication distance can be secured.

  DESCRIPTION OF SYMBOLS 10 RFID tag, 12 IC chip, 14 18 Conductive pad support substrate, 20, 22 Antenna, 21 Adhesive coating layer, 25 Coated RFID tag formed with coating layer, 30 beads, 32 stiffener, 34, 44 Tire Ply, 36 inner liner, 38 sidewalls, 54 chafer parts, 56 chafer end, 62 tread.

Claims (8)

A pneumatic tire in which electronic components are joined by an adhesive,
The adhesive comprises a polythiol compound (A), an isocyanate group-containing compound (B), and a radical generator (C),
The ratio (isocyanate group / thiol group) of the total number of isocyanate groups contained in the blended isocyanate group-containing compound (B) to the total number of moles of thiol groups contained in the blended polythiol compound (A) is 0.00. A pneumatic tire that is 2 or more and 0.78 or less.   The pneumatic tire according to claim 1, wherein the radical generator (C) is a thermal radical generator made of a peroxide.   Ratio of the total number of moles of the radical generator (C) to be blended with respect to the total number of moles of thiol groups contained in the polythiol compound (A) in which the adhesive is blended (radical generator (C) / thiol group) The pneumatic tire according to claim 1 or 2, wherein is 0.025 or more.   The pneumatic tire according to any one of claims 1 to 3, wherein the electronic component is a passive radio frequency identification transponder covered with metal or resin.   The pneumatic tire according to claim 4, wherein the passive radio frequency identification transponder is an RFID tag. Applying an adhesive to the entire electronic component;
Semi-curing an adhesive applied to the electronic component to form a coating layer capable of adhering to the electronic component;
A step of vulcanizing after contacting an unvulcanized rubber member or a semi-vulcanized rubber member and an electronic component on which a coating layer is formed;
Have
The adhesive comprises a polythiol compound (A), an isocyanate group-containing compound (B), and a radical generator (C),
The ratio (isocyanate group / thiol group) of the total number of isocyanate groups contained in the blended isocyanate group-containing compound (B) to the total number of moles of thiol groups contained in the blended polythiol compound (A) is 0.00. The manufacturing method of the pneumatic tire which is 2 or more and 0.78 or less. A step of bonding the vulcanized rubber member and the electronic component via an adhesive;
Curing the adhesive with heat or light;
Have
The adhesive comprises a polythiol compound (A), an isocyanate group-containing compound (B), and a radical generator (C),
The ratio (isocyanate group / thiol group) of the total number of isocyanate groups contained in the blended isocyanate group-containing compound (B) to the total number of moles of thiol groups contained in the blended polythiol compound (A) is 0.00. The manufacturing method of the pneumatic tire which is 2 or more and 0.78 or less.   The method for manufacturing a pneumatic tire according to claim 7, wherein the curing step further includes pressurization.

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