JP2001097002A - Tire consisting of thermo-reversible crosslinked polymer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a tire which can easily change only a worn or broken portion thereof when a part of the tire is worn or broken. SOLUTION: At least a part of the tire consists of a thermo-reversible crosslinked polymer composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a tire using a thermoreversible crosslinked polymer composition.

[0002]

2. Description of the Related Art At present, tires with worn treads are often incinerated and are rarely reused. As a means of reuse, there is a retread (correction of a tread), and a part of a tire for a passenger car is re-engraved with a tread groove and reused, but it is costly and inferior in quality. In addition, tires for trucks and buses are scraped off worn treads, replenished with raw rubber, vulcanized, re-formed to form treads, and reused. It is desired to simplify the process. Also, in addition to tread wear, a part of the tire may wear or break,
Even in such a case, it is not possible to replace only that part, and at present it is necessary to replace the entire tire. Therefore, there is a strong demand for a tire that can be easily replaced only when a part thereof is worn or damaged.
Furthermore, it is very preferable from the viewpoint of recycling a large amount of used tires if each constituent member of the tire can be disassembled and reused for each member.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a tire in which, when a part is worn or damaged, only the part can be easily replaced. Another object of the present invention is to provide a tire that can be easily disassembled for each constituent member during or after use.

[0004]

That is, the present invention provides a tire at least partially composed of a thermoreversible crosslinked polymer composition.

[0005] In one preferred embodiment, at least a part of the tire component that is in contact with another member is made of a thermoreversible crosslinked polymer composition.

It is a preferred embodiment that an adhesive layer made of a thermoreversible crosslinked polymer composition is provided on at least a part between the tire constituent member and another adjacent member.

[0007] In one preferred embodiment, the tire constituent member is a tread member.

In a preferred embodiment, the tire component is a belt member.

In a preferred embodiment, the tire component is a side member.

[0010] In one preferred embodiment, the tire constituent member is a bead filler member.

In a preferred embodiment, the tire component is an inner liner member.

In a preferred embodiment, at least a part of the member covering the at least one reinforcing cord comprises a thermoreversible crosslinked polymer composition.

In one preferred embodiment, at least a part of the part in contact with the part composed of the thermoreversible crosslinked polymer composition is composed of a pre-vulcanized rubber composition.

In the thermoreversible crosslinked polymer composition, the thermoreversible crosslinked polymer contained in at least one of the thermoreversible crosslinked polymer compositions comprises a group consisting of a hydroxyl group, a primary amino group and a secondary amino group. A preferred embodiment is a modified rubber having a reactive site capable of forming a hydrogen bond by at least one selected from the group consisting of at least one selected from the group consisting of a tertiary amino group and a carbonyl group.

[0015] Among the thermoreversible crosslinked polymer compositions, the thermoreversible crosslinked polymer contained in the thermoreversible crosslinked polymer composition used in at least one place has the following formula (1):
It is a preferred embodiment to have at least one group of (5).

[0016]

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In the thermoreversible crosslinked polymer composition, the thermoreversible crosslinked polymer contained in at least one of the thermoreversible crosslinked polymer compositions is preferably a modified rubber having an organic salt structure in a side chain. It is an aspect.

[0018] Among the thermoreversible crosslinked polymer compositions, the thermoreversible crosslinked polymer contained in the thermoreversible crosslinked polymer composition used in at least one place is a crosslink formed by a Diels-Alder reaction from a conjugated diene structure and a dienophile structure. One preferred embodiment is a modified rubber having a structure.

In the thermoreversible crosslinked polymer composition, the thermoreversible crosslinked polymer contained in at least one of the thermoreversible crosslinked polymer compositions is modified by utilizing a reaction between an acid anhydride group and a hydroxyl group for a crosslink reaction. One preferred embodiment is rubber.

The thermoreversible crosslinked polymer composition used in at least one of the thermoreversible crosslinked polymer compositions contains a thermoreversible crosslinked polymer, which is a modified rubber utilizing a reaction between a carboxyl group and a vinyl ether group for a crosslink reaction. Is a preferred embodiment.

In the thermoreversible crosslinked polymer composition, the thermoreversible crosslinked polymer contained in the thermoreversible crosslinked polymer composition used in at least one place is used for the crosslink reaction between the alkyl halide group and the tertiary amino group. In one preferred embodiment, the modified rubber used in the above is used.

In the thermoreversible crosslinked polymer composition, the thermoreversible crosslinked polymer contained in at least one of the thermoreversible crosslinked polymer compositions is modified by utilizing a reaction between an isocyanate group and a phenolic hydroxyl group for a crosslink reaction. One preferred embodiment is rubber.

In the thermoreversible crosslinked polymer composition, the thermoreversible crosslinked polymer contained in at least one of the thermoreversible crosslinked polymer compositions is modified by utilizing a reaction between an azlactone group and a phenolic hydroxyl group in a crosslink reaction. One preferred embodiment is rubber.

Among the thermoreversible crosslinked polymer compositions, the thermoreversible crosslinked polymer contained in the thermoreversible crosslinked polymer composition used in at least one place is a modified rubber utilizing a dimerization reaction of a nitroso group for a crosslink reaction. Is a preferred embodiment.

[0025]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail with reference to the drawings. The tire of the present invention is at least partially composed of a thermoreversible crosslinked polymer composition. The thermoreversible crosslinked polymer composition used in the present invention will be described in detail later.A composition containing a thermoreversible crosslinked polymer capable of reversibly forming and collapsing a crosslinked structure by a change in temperature, which can be repeated many times. It is.

The tire of the present invention is not particularly limited as long as it is at least partially composed of a thermoreversible crosslinked polymer composition. Hereinafter, the present invention will be described with reference to specific examples, but the present invention is not limited thereto. As a preferred embodiment of the tire of the present invention, a tire having a tread groove bottom made of a thermoreversible crosslinked polymer composition, and a tire having a coating layer made of a thermoreversible crosslinked polymer composition on at least a part of the side wall member surface No. FIG. 1A is a schematic diagram illustrating an example of a tread groove portion of a tire whose tread groove bottom is made of a thermoreversible crosslinked polymer composition, and FIG. 1B is an enlarged view thereof. The bottom of the tread groove is made of the thermoreversible crosslinked polymer composition 21, and the other parts of the tire are not particularly limited, and can be a normal rubber composition. When the tread groove becomes shallow due to wear of the tire surface due to use, the thermoreversible crosslinked polymer composition can be dissolved and removed by heating to increase the depth of the groove. In this case, the tread can be formed with higher accuracy than the conventional additional engraving, and the productivity is good.

The depth of the tread groove bottom is not particularly limited.
The tread groove bottom formed of a rubber composition other than the thermoreversible crosslinked polymer composition is made deeper than before, and filled with the thermoreversible crosslinked polymer composition to obtain a conventional depth, for example, 6.0 to 12 0.0 mm. on the other hand,
When a tire requiring strength such as a studless tire is used, a tread is designed in the same manner as before using a rubber composition other than the thermoreversible crosslinked polymer composition, and the groove bottom is formed with the thermoreversible crosslinked polymer composition. By filling, the depth of the tread groove bottom can be made shallow, for example, 5.0 to 8.0 mm. The thickness of the thermoreversible crosslinked polymer composition 21 used at the bottom of the tread groove is not particularly limited.
It can be 0 to 5.0 mm. The rubber thickness under the groove is
There is no particular limitation, and for example, it can be 1.5 to 5.0 mm. The method for providing the thermoreversible crosslinked polymer composition at the bottom of the tread groove is not particularly limited. For example, a thermoreversible crosslinked polymer composition that has been melted by heating may be extruded, and the thermoreversible crosslinked polymer composition may be pasted. May be combined.

FIG. 1C is a schematic diagram showing an example of a tire having a coating layer made of a thermoreversible crosslinked polymer composition on at least a part of the side wall member surface. The side wall 1 has a coating layer 22 made of a thermoreversible crosslinked polymer composition on the surface. Since the sidewall is on the tire surface, the surface may be damaged by the use of the tire,
The characters that display the brand are blurred. In such a case, by heating, the damaged portion of the coating layer 22 or the like is melted and partially repaired, or after removing the entire coating layer 22, a new coating layer is attached and the sidewall is reformed. Or you can.

The thickness of the coating layer 22 is not particularly limited, but may be, for example, 0.5 to 2.0 mm.
The method for providing the coating layer 22 is not particularly limited.
After molding the thermoreversible crosslinked polymer composition, it can be provided by bonding to the surface side of the sidewall 1.

Further, as a preferred embodiment of the tire of the present invention, (1) a tire structure in which at least one tire constituent member has at least a part of a portion in contact with another member made of a thermoreversible crosslinked polymer composition Examples of the tire include a tire that is a member and (2) a tire in which at least one tire constituent member has an adhesive layer made of a thermoreversible crosslinked polymer composition in at least a part between another adjacent member. The tire of (1) is an embodiment in which the tire component itself is composed of a thermoreversible crosslinked polymer composition,
The tire (2) is an embodiment in which a thermoreversible crosslinked polymer composition is used as an adhesive between tire constituent members.
In the tire of (1), at least one of the tire constituent members may have a portion in contact with another member made of a thermoreversible crosslinked polymer composition, and the entire portion in contact with the other member may have heat. It may be composed of a reversible crosslinked polymer composition, or the entire member may be composed of a thermoreversible crosslinked polymer composition. In the tire of (2), at least one tire constituent member may have an adhesive layer made of a thermoreversible crosslinked polymer composition at a part between another adjacent member and another adjacent member. A member having an adhesive layer made of a thermoreversible crosslinked polymer composition may be provided between all the members to be formed. The tire of the present invention may be a tire corresponding to both (1) and (2).

A common effect of the tires (1) and (2) is that, when heated, the thermoreversible crosslinked polymer composition dissolves, so that at least one tire constituent member is easily separated from other members. In addition, it is easy to disassemble, separate and collect, and reuse each component. The effect unique to the tire (1) is that the shape of each component is smoothed. The method for forming the tire component with the thermoreversible crosslinked polymer composition is not particularly limited, and examples include a method of injection molding. The unique effect of the tire (2) is that if a step of providing a layer of a thermoreversible crosslinked polymer composition is added, the tire can be manufactured using the conventional tire manufacturing process as it is. In the tire (2), the layer of the thermoreversible crosslinked polymer composition has a thickness of 0.1%.
This is because the thermoreversible crosslinked polymer composition does not melt and flow out even in the conventional vulcanization step because it can be thinned to about several mm. The method of providing the layer of the thermoreversible crosslinked polymer composition is not particularly limited, and includes a method of injection molding, a method of forming into a film, bonding and re-molding by heat melting, and a method of forming a molten thermoreversible crosslinked polymer. Examples include a method of applying the composition.

As one preferred embodiment of the present invention, the following:
Tires. A tire in which the tread member is a tread member in which at least a part of a portion in contact with another member is made of a thermoreversible crosslinked polymer composition, and the tread member has at least a portion between other adjacent members. FIG. 2 is a schematic diagram illustrating an example of the tire of the present invention. FIG.
The tread 2 shown in (a) includes a cap tread 3 and an under tread 4, and the under tread 4
An adhesive layer 23 made of a thermoreversible crosslinked polymer composition is provided between the side wall 1, the belt 5, and the carcass 6. When the tread member is worn due to use or the like, the adhesive layer 23 is melted by heating, the tread 2 is peeled off, and a new tread portion is re-bonded, so that other members of the tire can be reused as they are. it can. If a part of the adhesive layer 23 adheres to the tread 2 and is removed when the tread 2 is peeled off, it is possible to supplement the loss at the time of reattaching.

The tread 2 shown in FIG. 2B comprises a cap tread 3 and an undertread 4, and the undertread 4 comprises a thermoreversible crosslinked polymer composition.
By dissolving the undertread 4 by heating,
The same effect as the tread 2 shown in FIG. 2A can be obtained.

The thermoreversible crosslinked polymer composition used in the embodiment has a flow initiation temperature of preferably 100 ° C. or higher, more preferably 150 ° C. or higher. When the content is within the above range, the heat reversible crosslinked polymer composition does not soften due to the heat generated by the tire during running, so that the tire has excellent durability. Further, the thermoreversible crosslinked polymer composition used in the embodiment preferably has a flow start temperature of 190 ° C. or lower. Since the tread is most worn out of the tire members, if only the tread is replaced, the other members can often be reused as they are. Therefore, it is easier to replace only the tread when the flow start temperature is lower than the other members.

The thickness of the adhesive layer 23 is not particularly limited, but can be 0.1 to 4.0 mm. This is because the above range is sufficient for the adhesion between the tread member and the belt member. Preferably, it is 0.5 to 2.0 mm. The method for providing the adhesive layer 23 is not particularly limited. For example, the adhesive layer 23 can be provided by bonding the thermoreversible crosslinked polymer composition to the belt side of the undertread 4.

In the above example, the tread 2 is composed of the cap tread 3 and the undertread 4, but the tread may not be divided into the cap tread and the undertread, but may be composed of one member.

A tire in which the belt member is a belt member in which at least a part of a portion in contact with another member is made of a thermoreversible crosslinked polymer composition, and at least a belt member is provided between the tire and another adjacent member. Tires Having Partially Adhesive Layers Made of Thermoreversible Cross-Linked Polymer Composition FIGS. 3 (a), (b) and (c) are schematic diagrams showing an example of the tire. The belt 5 shown in FIG.
And an adhesive layer 24 made of a thermoreversible crosslinked polymer composition between the lower layer (1B) and the carcass 6 and between the upper layer (2B) and the undertread 4. The portion containing the metal cord of the belt 5 is taken out by melting the adhesive layer 24 by heating, and the metal cord can be reused, or another member of the tire can be reused as it is.

The belt 5 shown in FIG. 3B has two layers, and has an adhesive layer 25 made of a thermoreversible crosslinked polymer composition between 1B and the carcass 6. Adhesion layer 25 by heating
, It is possible to disassemble and correct the tread member and the belt member collectively.

The belt 5 shown in FIG. 3C is composed of two layers, between 2B and the undertread 4, and between 2B and 1B.
Adhesive layer 26 comprising a thermoreversible crosslinked polymer composition between
Having. By dissolving the adhesive layer 26 by heating, it is possible to repair / repair only 2B. Thus, if only the susceptible 2B is replaced, other parts can be reused as they are.

The thermoreversible crosslinked polymer composition used in the embodiment preferably has a flow initiation temperature of 100 ° C. or higher, more preferably 150 ° C. or higher. When the content is within the above range, the heat reversible crosslinked polymer composition does not soften due to the heat generated by the tire during running, so that the tire has excellent durability. Further, the thermoreversible crosslinked polymer composition used in the embodiment preferably has a flow start temperature of 190 ° C. or lower. This is because disassembly becomes easy.

The thickness of the adhesive layers 24, 25 and 26 is not particularly limited, but may be 0.1 to 2.0 mm. This is because the above range is sufficient for bonding the belt member to the tread member and the like, and the weight is sufficient.
Preferably, it is 0.5 to 1.0 mm. Adhesive layers 24, 2
The method for providing 5 and 26 is not particularly limited. For example, the method can be provided by winding the thermoreversible crosslinked polymer composition around the surface of the belt 5 or bonding the composition to the carcass side.

FIGS. 3 (a), (b) and (c) show the case where the belt 5 is composed of two layers 1B and 2B. It may consist of. Alternatively, the structure having the belt reinforcing ply, and further, the belt reinforcing ply may be handled in the same manner as the belt.

A tire in which the sidewall member is a sidewall member at least a part of which is in contact with another member is made of a thermoreversible crosslinked polymer composition, and a tire in which the sidewall member is in contact with another adjacent member. Tires having an adhesive layer made of a thermoreversible crosslinked polymer composition in at least a part between them. FIGS. 4A and 4B are schematic diagrams showing an example of the tire. The side wall 1 shown in FIG. 4A has an adhesive layer 27 made of a thermoreversible crosslinked polymer composition between the side wall 1 and the carcass 6 and between the side wall 6 ′ of the carcass 6. The adhesive layer 27 is melted by heating, and the side wall 1 is melted.
By peeling off and reattaching a new sidewall portion, other members of the tire can be reused as they are.

In the side wall 1 shown in FIG. 4B, a portion 1 'in contact with the undertread 4 and the carcass 6 is made of a thermoreversible crosslinked polymer composition. When the portion 1 ′ made of the thermoreversible crosslinked polymer composition is melted by heating, a peeling portion is formed at the end of the tread member. By peeling off the portion, the disassembling operation of the entire tread member can be performed efficiently. .

The thermoreversible crosslinked polymer composition used in the embodiment has a flow initiation temperature of preferably 80 ° C. or higher, more preferably 130 ° C. or higher. When the content is within the above range, the heat reversible crosslinked polymer composition does not soften due to the heat generated by the tire during running, so that the tire has excellent durability. Further, the thermoreversible crosslinked polymer composition used in the embodiment preferably has a flow start temperature of 190 ° C. or lower. This is because disassembly becomes easy.

The thickness of the adhesive layer 27 is not particularly limited, but can be 0.1 to 2.0 mm. This is because the above range is sufficient for the adhesion to the belt member and the like, and the lightness is sufficient. Preferably, it is 0.5 to 1.0 mm.
The method for providing the adhesive layer 27 is not particularly limited.
The thermoreversible crosslinked polymer composition can be provided by adhering it to the carcass side of the sidewall 1.

The tire in which the bead filler member is a bead filler member at least a part of which is in contact with another member is made of a thermoreversible crosslinked polymer composition, and the bead filler member is different from another adjacent member. Tires having an adhesive layer made of a thermoreversible crosslinked polymer composition in at least a part between them. FIGS. 5A, 5B and 5C are schematic views showing an example of the tire of FIG. The bead filler 7 shown in FIG. 5A has an adhesive layer 28 made of a thermoreversible crosslinked polymer composition between the sidewall 1, the carcass 6, and the bead core 8. Heating dissolves the adhesive layer 28 and makes it easy to separate it from the bead filler portion, so that the components can be separated and collected.

The bead filler 7 shown in FIG. 5B is entirely composed of a thermoreversible crosslinked polymer composition. In this case, in addition to the above effects, there is an advantage that the shape of the bead filler becomes smooth and the durability is improved.

The bead filler 7 and the bead core 8 shown in FIG. 5C are entirely made of a thermoreversible crosslinked polymer composition, and they are in contact with the sidewall 1 and the carcass 6. In this case, in addition to the above effects, the entire bead filler 7 and the bead core 8 are melted by heating, so that there is an advantage that the winding portion of the carcass 6 can be easily disassembled.

The thermoreversible crosslinked polymer composition used in the embodiment preferably has a flow start temperature of 80 ° C. or higher, more preferably 130 ° C. or higher. When the content is within the above range, the heat reversible crosslinked polymer composition does not soften due to the heat generated by the tire during running, so that the tire has excellent durability. Further, the thermoreversible crosslinked polymer composition used in the embodiment preferably has a flow start temperature of 190 ° C. or lower. This is because disassembly becomes easy.

The thickness of the adhesive layer 28 is not particularly limited, but can be 0.1 to 2.0 mm. This is because the above range is sufficient for the adhesion to the belt member and the like, and the lightness is sufficient. Preferably, it is 0.5 to 1.0 mm.
The method for providing the adhesive layer 28 is not particularly limited.
It can be provided by bonding the thermoreversible crosslinked polymer composition to the surface of the bead filler 7.

The tire in which the inner liner member is an inner liner member at least a part of which is in contact with another member is made of a thermoreversible crosslinked polymer composition, and the inner liner member is in contact with another adjacent member. Tire having an adhesive layer made of a thermoreversible crosslinked polymer composition in at least a part between them. FIGS. 6A and 6B are schematic diagrams showing an example of the tire of FIG. The inner liner 9 shown in FIG.
An adhesive layer 29 made of a thermoreversible crosslinked polymer composition is provided between the carcass 6 and the carcass 6. The adhesive layer 29 is melted by heating, and the inner liner portion can be easily peeled off, so that the components can be separated and collected.

The inner liner 9 shown in FIG.
The whole consists of a thermoreversible crosslinked polymer composition. In this case, in addition to the above effects, it is possible to repair the puncture hole generated in the inner liner by heating and melting the puncture hole,
In addition, since it becomes possible to heat and adhere a patch piece having a composition capable of adhering to the thermoreversible crosslinked polymer composition of the inner liner, it can be easily and completely repaired.

The thermoreversible crosslinked polymer composition used in the embodiment preferably has a flow start temperature of 80 ° C. or higher, more preferably 130 ° C. or higher. When the content is within the above range, the heat reversible crosslinked polymer composition does not soften due to the heat generated by the tire during running, so that the tire has excellent durability. Further, the thermoreversible crosslinked polymer composition used in the embodiment preferably has a flow start temperature of 190 ° C. or lower. This is because disassembly becomes easy.

The thickness of the adhesive layer 29 is not particularly limited, but can be 0.1 to 2.0 mm. This is because the above range is sufficient for the adhesion to the belt member and the like, and the lightness is sufficient. Preferably, it is 0.5 to 1.0 mm.
The method for providing the adhesive layer 29 is not particularly limited.
The thermoreversible crosslinked polymer composition can be provided by attaching the thermoreversible crosslinked polymer composition to the carcass side surface of the inner liner 9.

The tire in which the other member is a member in which at least a part of the portion in contact with the other member is made of the thermoreversible crosslinked polymer composition, and the other member is a member between the tire and another adjacent member. FIG. 7 is a schematic diagram illustrating an example of a tire having at least a part of an adhesive layer made of a thermoreversible crosslinked polymer composition. The belt edge cushion 10 shown in FIG. 7 is entirely made of a thermoreversible crosslinked polymer composition, and is in contact with the sidewall 1, the undertread 4, the belt 5, and the carcass 6. By heating, the tread 2 can be easily separated from the belt edge cushion portion, and the components can be separated and collected. In FIG. 7, the belt edge cushion is taken as an example, but in the embodiment, all members other than the members mentioned in the above are applicable.

FIG. 8 is a schematic diagram showing an example of a tire having the above combination. FIG.
The undertread 4 has an adhesive layer 30 made of a thermoreversible crosslinked polymer composition between the side wall 1 and the belt 5, and the side wall 1 and the belt 5
Is a tire having an adhesive layer 31 made of a thermoreversible crosslinked polymer composition between the carcass 6 and the winding portion 6 ′ of the carcass 6. Here, the thermoreversible crosslinked polymer composition used for the adhesive layer 30 has a lower flow start temperature than the thermoreversible crosslinked polymer composition used for the adhesive layer 31. When replacing only the tread portion, by heating to a temperature higher than the flow start temperature of the thermoreversible crosslinked polymer composition of the adhesive layer 30 and lower than the flow start temperature of the thermoreversible crosslinked polymer composition of the adhesive layer 31. Then, only the adhesive layer 30 is dissolved, and the tread portion is disassembled and corrected. When disassembling and correcting not only the tread portion but also the side wall portion and the belt portion, the adhesive layers 30 and 31 are heated to a temperature higher than the flow start temperature of the thermoreversible crosslinked polymer composition of the adhesive layer 31 so that the adhesive layers 30 and 31 are heated. Melt and disassemble, glue new tread, sidewall and belt and correct. Therefore, it is usually necessary to replace only the treads that are easy to wear, and if the sidewalls and belts are damaged while continuing to use after several tread replacements, repair the sidewalls and belts as well. Can be. Also, after the life of the casing body, the adhesive layers 30 and 31 are simultaneously melted and disassembled into parts, collected, and collected.
Can be reused.

The thermoreversible crosslinked polymer composition used for the adhesive layers 30 and 31 has a flow starting temperature of 100
The temperature is preferably from 170 to 170 ° C, more preferably from 150 to 160 ° C, and more preferably from 170 to 190 ° C, respectively, and the difference between the flow start temperatures is preferably 10 ° C or more. When the content is in the above range, the durability of the tire is excellent, the dissolution of only the adhesive layer 30 is easy, and the dismantling workability is also improved.

In the embodiment, the combination of the above-mentioned is not particularly limited, and may be any combination according to the possibility of reuse and the manner of repair / correction. Further, the thermoreversible crosslinked polymer compositions used at a plurality of locations may be the same or different. In particular, as in the example shown in FIG.
By combining the thermoreversible crosslinked polymer compositions having different flow initiation temperatures, the member can be selectively peeled off and disassembled, which is a preferable embodiment.

In the present invention, a tire can be obtained by appropriately combining all of the above-described embodiments. For example,
The tread groove bottom is made of a thermoreversible crosslinked polymer composition, and has a coating layer made of a thermoreversible crosslinked polymer composition on at least a part of the side wall member surface, and the undertread is between the sidewall and the belt. A tire having an adhesive layer made of a thermoreversible crosslinked polymer composition between the tire and the carcass can be obtained.

Further, as a preferred embodiment of the present invention, there is provided a tire in which at least a part of a member covering at least one reinforcing cord is made of a thermoreversible crosslinked polymer composition. FIG. 9A is a schematic diagram of an example of a tire in which each of a belt member covering a belt cord and a carcass member covering a carcass cord is made of a thermoreversible crosslinked polymer composition, and FIG. It is an enlarged view of one aspect of a member, and (c) is an enlarged view of another aspect of the belt member. The belt member 5 shown in FIG. 9B includes a belt cord 51 and a thermoreversible crosslinked polymer composition coating layer 52. Since the coating layer 52 is melted by heating, the collection, reuse and recycling of the belt cord 51 are possible.

The belt member 5 shown in FIG. 9C includes a belt cord 51, a rubber composition coating layer 53, and a thermoreversible crosslinked polymer composition coating layer 52. Belt code 51
Are coated one by one with a rubber composition coating layer 53, and the rubber composition coating layer 53 is a thermoreversible crosslinked polymer composition coating layer 52.
Coated. The coating layer 52 is melted by heating, and the belt cord 51 and the rubber composition coating layer 53 can be collected and reused. In addition, when a metal cord is used for the belt cord 51, a conventional metal-rubber bonding technique is used. It has the advantage that it can be used.

The thermoreversible crosslinked polymer composition used for the coating layer 52 preferably has a flow start temperature of 100 ° C. or higher, more preferably 150 ° C. or higher. When the content is within the above range, the heat reversible crosslinked polymer composition does not soften due to the heat generated by the tire during running, so that the tire has excellent durability. The thermoreversible crosslinked polymer composition used for the coating layer 52 preferably has a flow start temperature of 190 ° C. or lower. This is because disassembly becomes easy.
The rubber composition used for the coating layer 53 is not particularly limited, and a rubber composition generally used for a tire can be used. However, at the temperature at which the thermoreversible crosslinked polymer composition of the coating layer 52 starts flowing, the rubber composition deteriorates. Those that do not are preferred.

[0064] The member for covering the reinforcing cord in which the thermoreversible crosslinked polymer composition can be used is not particularly limited. A thermoreversible crosslinked polymer composition can be used for all members covering a reinforcing cord such as a belt cord, a belt cover cord, and a carcass cord, and the same or different types of thermoreversible crosslinked polymer compositions are used for a plurality of members. You can also.

The material of the reinforcing cord is not particularly limited, and for example, a metal cord or an organic fiber cord can be used. Examples of the metal cord include a steel cord. When using an organic fiber cord, at least one selected from the group consisting of polyester fiber, aromatic polyamide fiber, polyarylate fiber, polyparaphenylene benzobisoxazole fiber, polyvinyl alcohol fiber, rayon fiber, and nylon fiber is twisted. It is preferable to use a twist cord. As the polyester fiber, for example, polyethylene terephthalate fiber or polyethylene 2,6-naphthalate fiber is preferable, or extra high modulus polyester (EHM) having an ultra-high modulus of elasticity.
Polyester) is preferred.

Further, as a preferred embodiment of the present invention, there is provided a tire in which at least a part of a part which is in contact with a part made of a thermoreversible crosslinked polymer composition is made of a rubber composition which has been vulcanized in advance. In this case, all of the portion that comes into contact with the portion made of the thermoreversible crosslinked polymer composition may be made of a rubber composition that has been vulcanized in advance. FIG. 10 (a)
The undertread 4 has an adhesive layer 32 made of a thermoreversible crosslinked polymer composition between the sidewall 1, the belt 5, and the carcass 6, and the tread 2 and all other components are It is a tire comprising a vulcanized rubber composition. This tire can be obtained by laminating a thermoreversible crosslinked polymer composition to a vulcanized tread member in advance, laminating it to a separately vulcanized casing part, and then heating and integrating. As described later, the thermoreversible crosslinked polymer composition is strongly adhered to the pre-vulcanized rubber composition by heating, so that the pre-vulcanized rubber composition can be used as a tire component. is there.

Conventionally, when manufacturing a tire, a tire constituent member such as a carcass member made of an unvulcanized rubber composition is pasted on a forming drum, and the tire is inflated from the inside in the radial direction of the tire to near the product size. A green tire is formed by bonding a belt member and a tread member made of an unvulcanized rubber composition, and the green tire is inserted into a mold and vulcanized, and at the same time, a tread pattern is formed on the tread member. That is, the rubber compositions of all tire components are used in an unvulcanized state. Also in the present invention, the portion that contacts the portion made of the thermoreversible crosslinked polymer composition,
When all are made of an unvulcanized rubber composition, it can be manufactured by the above-mentioned conventional method. On the other hand, in the present embodiment, it is possible to use a rubber composition which has been vulcanized in advance in at least a part of the part which comes into contact with the part comprising the thermoreversible crosslinked polymer composition.

Therefore, the tire of this embodiment has the following advantages. First, since the vulcanized rubber composition does not lose its shape, the place where the vulcanized rubber composition and the thermoreversible crosslinked polymer composition are bonded is not limited to a molding drum, and for example, The bonding can be performed on a rigid support base made of metal or the like. Thereby, the degree of freedom of the bonding operation is increased, and the operation is facilitated. Secondly, if vulcanization of all tire components is performed at one time, the vulcanization conditions desired for each component cannot be achieved, but in this embodiment, the components vulcanized in advance under optimal conditions Can be used. Third, productivity can be improved because the integral vulcanization step can be omitted. Fourth, if each component is stored after vulcanization, it can be commonly used for various types of tires. Fifth, as in the other aspects of the present invention, it can be easily peeled off by heating and recycled.

FIG. 10B shows that the undertread 4 is
It has an adhesive layer 32 made of a thermoreversible crosslinked polymer composition between the side wall 1, the belt 5, and the carcass 6, and the tread 2 is made of an unvulcanized rubber composition. Are all tires made of a pre-vulcanized rubber composition. In this tire, the thermoreversible crosslinked polymer composition is bonded to an unvulcanized tread member, and further bonded to a separately vulcanized casing portion, and then the whole is integrated with vulcanization of the tread member. Can be obtained by

Therefore, the tire of this embodiment has the following advantages. First, since vulcanization only needs to be performed on the tread member, vulcanization using a vulcanizing mold for a tread portion is sufficient. Therefore, vulcanization can be performed at lower cost than a conventional tire using a mold for vulcanizing the entire tire. Second, since the thickness of the rubber to be vulcanized is small, the vulcanization time can be shortened, and the vulcanization productivity is improved. Third, as in the other embodiments of the present invention, it can be easily peeled off by heating and recycled.

Next, the thermoreversible crosslinked polymer composition used for the tire of the present invention will be described in detail. The thermoreversible crosslinked polymer composition used in the present invention contains a thermoreversible crosslinked polymer. The thermoreversible crosslinked polymer refers to a polymer which is crosslinked at normal temperature, but is decrosslinked by heating and has fluidity, and this conversion can be performed reversibly many times. The thermoreversible crosslinked polymer composition used in the present invention includes, for example, a modified rubber (1) having a reactive site capable of forming a hydrogen bond, particularly a group consisting of a hydroxyl group, a primary amino group and a secondary amino group. Modified rubber (1) having a reactive site capable of forming a hydrogen bond by at least one selected from the group consisting of at least one selected from the group consisting of a tertiary amino group and a carbonyl group; (2) a modified rubber having an organic salt structure In particular, a modified rubber having an organic salt structure in a side chain (2); a modified rubber having a crosslinked structure formed by a Diels-Alder reaction from a conjugated diene structure and a dienophile structure (3), particularly a conjugated diene having a furan skeleton Rubber (3) having a crosslinked structure formed by Diels-Alder reaction from the structure and dienophile structure; acid anhydride group and hydroxyl group Modified rubber (4) utilizing the reaction for crosslinking reaction; Modified rubber (5) utilizing the reaction between carboxyl group and vinyl ether group for crosslinking reaction; Reaction between alkyl halide group and tertiary amino group for crosslinking reaction Modified rubber (6) utilized; Modified rubber (7) utilizing the reaction between isocyanate groups and phenolic hydroxyl groups for crosslinking reaction; Modified rubber (8) utilizing the reaction between azlactone groups and phenolic hydroxyl groups for crosslinking reaction; It contains at least one modified rubber (9) utilizing a dimerization reaction of a nitroso group for a crosslinking reaction. Hereinafter, the composition containing the modified rubbers (1) to (9) will be described.

First, the thermoreversible crosslinked polymer composition containing the modified rubber (1) will be described. Hydrogen bonds are formed from a donor and an acceptor. Therefore, the modified rubber (1) takes one of the following modes. Rubber with both donor and acceptor. Rubber having one of a donor and an acceptor. In this case, it is necessary that the thermoreversible crosslinked polymer composition contains the compound having the other.

The rubber may have both a donor and an acceptor in one side chain, or may have only a donor and an acceptor in one side chain. Among them, the rubber preferably has both a donor and an acceptor in one side chain.

In the rubber of the present invention, the reaction site of the rubber may be a donor or an acceptor.
When the rubber has a donor, the compound contained in the thermoreversible crosslinked polymer composition has an acceptor, and when the rubber has an acceptor, the compound contained in the thermoreversible crosslinked polymer composition has a donor.

The term “donor” as used herein means a hydrogen that forms a hydrogen bond and a negative atom or a substituent containing a negative atom that serves as a proton donor (proton donor) that forms a partially ionic covalent bond. Say. Examples of the negative atom include an oxygen atom and a nitrogen atom. Substituents containing these negative atoms, that is, donors include, for example, -O
H, -NH-. Specifically, preferred examples include an alcoholic hydroxyl group, a phenolic hydroxyl group, a hydroxyl group in a carboxyl group of a carboxylic acid (including a fatty acid) and an amino group (including an amide group).

The term “acceptor” means that a hydrogen bond forms a hydrogen bond.
And proton acceptors (proton acceptors)
Means a negative atom or a substituent containing a negative atom. A
Negative atoms in the acceptor include, for example, a nitrogen atom,
An oxygen atom and a sulfur atom are mentioned. These negative atoms
Including substituents, that is, as the acceptor, for example,-
-NR including CO-, -N =¹R^Two(Where R¹and
R^TwoIs a hydrogen atom or an alkyl having 1 to 20 carbon atoms, respectively.
Represents a kill group. R¹And R^TwoAre the same, but different
It may be. ), -COOH, -COOR^Three(formula
Medium, R^ThreeIs an alkyl group having 1 to 20 carbon atoms or aryl
Represents a hydroxyl group. ), -C≡N, -NCO, -SCN, = N
OH, -NHCONH_Two, -CONH-, = SO, -C
SSH, -SCNH_Two, -COSH, -CSOH, -O
P (= O) (OR^Four)_Two(Where R^FourIs a hydrogen atom,
Represents an enyl group or an alkyl group having 1 to 20 carbon atoms. 2
Two R ^FourMay be the same or different
No. ) And heterocyclic amine-containing groups.

The combination of the donor and the acceptor is not particularly limited, but the donor is at least one selected from the group consisting of a hydroxyl group, a primary amino group and a secondary amino group, and the acceptor is a tertiary amino group. It is preferably at least one selected from the group consisting of a group and a carbonyl group. Here, “hydroxyl group” includes a hydroxyl group in a carboxylic acid, and “primary amino group and secondary amino group” include an amide group. When a combination of these donors and acceptors is used, it has excellent heat resistance, low cold flow property, and a large decrease in viscosity at the time of hydrogen bond collapse at a high temperature as compared with the time of hydrogen bond formation, making the tire of the present invention easier to recycle. Becomes

In particular, the donor is preferably an amino group of the heterocyclic amine-containing group, and the acceptor is preferably a carbonyl group of the carbonyl group-containing group. The amino group contained in the heterocyclic amine-containing group is preferable because the modified rubber (1) has excellent heat flow resistance because it easily forms a hydrogen bond as compared with an amino group having no ring structure. is there. Here, (i) the carbonyl group-containing group is
Examples include a carbonyl group, a carboxyl group, an amide group, an ester group, and an imide group. Examples of the compound into which such a group can be introduced include, without particular limitation, carboxylic acids and derivatives thereof. Examples of the carboxylic acid compound include an organic acid having a saturated or unsaturated hydrocarbon group, and the hydrocarbon group may be any of aliphatic, alicyclic, and aromatic carboxylic acids. Further, as the carboxylic acid derivative, for example, carboxylic anhydride, ester, ketone, amino acid, amide,
Examples include imides and thiocarboxylic acids (mercapto group-containing carboxylic acids).

(I) Specific examples of the compound capable of introducing a carbonyl group-containing group include malonic acid, maleic acid, succinic acid, glutaric acid, phthalic acid, isophthalic acid, terephthalic acid, p-phenylenediacetic acid, carboxylic acids such as p-hydroxybenzoic acid, p-aminobenzoic acid, and mercaptoacetic acid; and carboxylic acids having a substituent; such as succinic anhydride, maleic anhydride, glutaric anhydride, phthalic anhydride, propionic anhydride, and benzoic anhydride; Acid anhydrides; aliphatic esters such as maleic acid esters, malonic acid esters, succinic acid esters, glutaric acid esters, and ethyl acetate;
Aromatic esters such as phthalic acid ester, isophthalic acid ester, terephthalic acid ester, ethyl-m-aminobenzoate, methyl-p-hydroxybenzoate; ketones such as quinone, anthraquinone, naphthoquinone; glycine, tricine, bicine, alanine, valine, Leucine, serine, threonine, lysine, aspartic acid, glutamic acid, cysteine, methionine, proline, N-
Amino acids such as (p-aminobenzoyl) -β-alanine; maleamide, maleamic acid (malemonoamide), succinic monoamide, 5-hydroxyvaleramide, N-acetylethanolamine, N, N′-hexamethylenebisacetamide And amides such as malonamide, cycloserine, 4-acetamidophenol and p-acetamidobenzoic acid; and imides such as maleimide and succinimide.

(Ii) The heterocyclic amine-containing group is introduced from a nitrogen-containing heterocyclic ring or a compound containing the heterocyclic ring. The nitrogen-containing heterocyclic ring may be any structure that contains or generates a hydrogen-bonding amino group in the heterocyclic ring. Examples of such a nitrogen-containing heterocycle include pyrrole, histidine, imidazole, triazolidine, triazole, triazine, pyridine, pyrimidine, pyrazine, indole, quinoline, purine, phenazine, pteridine, and melamine. The nitrogen-containing heterocyclic ring may include another hetero atom in the ring.

The compound containing a nitrogen-containing heterocyclic ring may have any of the above-described heterocyclic skeletons, and is not particularly limited. For example, a compound capable of chemically (covalently) bonding to a main chain carbon of a polymer. May be provided. Examples of such a group include an amino group, a hydroxyl group, a methylene group, an ethylene group, and a carboxylic acid. Specific examples of such a compound containing a nitrogen-containing heterocyclic ring include dipyridyl, ethylenedipyridyl, trimethylenedipyridyl, dipyridylamine, 1,2-dimethylimidazole, 2-benzimidazoleurea, pyrrole-2-carboxylic acid, -Methyl-pyrazole, pyridine, 4-methylpyridine, 4
(Or2) -hydroxymethylpyridine, 2 (or4)
-(Β-hydroxyethyl) -pyridine, 2 (or4)
-(2-aminoethyl) -pyridine, 2 (or4) -aminopyridine, 2,6-diaminopyridine, 2-amino-6-hydroxypyridine, 6-azathymine, acetoguanamine, benzoguanamine, citrazinic acid, 1,2,2
4-triazole, 3-amino-1,2,4-triazole, 3-aminomethyl-1,2,4-triazole,
3-methylamino-1,2,4-triazole, 3-methylol-1,2,4-triazole, 3-hydroxy-1,2,4-triazole, 2-hydroxytriazine, 2-aminotriazine, 2-hydroxy -5-methyltriazine, 2-amino-5-methyltriazine, 2
-Hydroxypyrimidine, 2-aminopyrimidine, 2-
Examples include aminopyrazine, 2-hydroxypyrazine, 6-aminopurine, and 6-hydroxypurine.

The modified rubber (1) contains the above-mentioned donor and / or
Alternatively, a rubber modified or synthesized to have a substituent serving as an acceptor can be used. The rubber to be modified is not particularly limited, and a general rubber can be used. Such rubbers include ordinary rubbers (including liquid rubbers), thermoplastic elastomers, and thermosetting elastomers. Specifically, examples of the normal rubber include, for example, isoprene rubber (IR), butadiene rubber, 1,2-polybutadiene rubber, styrene-butadiene rubber (SBR), chloroprene rubber, nitrile rubber, butyl rubber, ethylene-propylene rubber, Chlorosulfonated polyethylene, acrylic rubber, epichlorohydrin rubber, polysulfide rubber, silicone rubber, fluoro rubber,
Urethane rubber. Examples of the thermoplastic elastomer include, for example, polystyrene (eg, styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SBS)
IS), hydrogenated styrene-butylene-styrene block copolymer (SEBS)), polyolefin-based,
Examples thereof include polyurethane-based, polyester-based, polyamide-based, and polyvinyl chloride-based thermoplastic elastomers. Examples of the thermosetting elastomer include urethane-based and silicone-based thermosetting elastomers.

The modified rubber (1) comprises a rubber having (i) a carbonyl group-containing group and (ii) a heterocyclic amine-containing group in a side chain and in one molecule as described above. Is preferred. The groups (i) and (ii) are pendant to the side chain of the rubber as the main chain, and form a chemically stable bond as described above. In this case, (i) and (ii) may be bonded to the rubber main chain as mutually independent side chains, or (i) and (ii) may be bonded to the main chain through different groups. ) May form one side chain.

As an example of the modified rubber (1) in which (i) and (ii) are independently bonded to the rubber main chain, (i) a carboxyl group and (ii) 1,2,4 −
The structure of the modified rubber (α) bonded with triazole is schematically shown below.

[0085]

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Further, as an example of the modified rubber (1) in which (i) and (ii) form one side chain by bonding to the main chain via different groups, the rubber main chain is A modified isoprene rubber, wherein (i) the carbonyl group-containing group is a group derived from maleic anhydride, and (ii) the heterocyclic amine-containing group is a group derived from 3-amino-1,2,4-triazole. The structure of the rubber (β) is schematically shown below. This modified rubber (β) is 3-amino-1,2,4-
By the reaction of triazole with maleic anhydride, maleic anhydride has an amide bond group formed by ring opening and a carboxyl group in one side chain in a branched manner.

[0087]

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In the present invention, among the above,
(I) As the carbonyl group-containing group, a group derived from a cyclic acid anhydride such as succinic anhydride, maleic anhydride, glutaric anhydride, and phthalic anhydride is preferable, and a group derived from maleic anhydride is more preferable.

As the (ii) heterocyclic amine-containing group, a heterocyclic ring having one or more nitrogen atoms in the skeleton is preferable.
A heterocyclic ring having two or more nitrogens is more preferable, and a group derived from a triazole ring is particularly preferable. Specifically, 3
-Amino-1,2,4-triazole, 3-hydroxy-1,2,4-triazole, 3-aminomethyl-1,
2,4-triazole, 3-methylamino-1,2,4
Groups derived from -triazole, 3-methylol-1,2,4-triazole and the like are preferably exemplified.

Further, as shown above as a modified rubber (β), a structure in which (i) a heterocyclic amine-containing group is bonded to a main chain via a (i) carbonyl group-containing group to form one side chain. Are preferred. In a structure in which (i) a carbonyl group-containing group and (ii) a heterocyclic amine-containing group form one side chain, the heterocyclic amine-containing group (ii) and the carbonyl group of the above (i) form an amide (1) , (4), ester (2),
It is preferable that at least one kind of bond of (5) and imide (3) is formed, or that at least one kind of bond and a carboxyl group are formed. In particular, the side chain formed by the bond between the cyclic acid anhydride and (ii) the heterocyclic amine-containing group includes bonds (1), (2), (4),
(5) Both have a carboxyl group. Specific examples of the side chain having such a bond (1), (2), (4), (5) or (3) are shown below.

[0091]

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The heterocyclic amine represented by R above is not particularly limited.

[0093]

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[0094]

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[0095]

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[0096]

(I) the carbonyl group-containing group is a group derived from a cyclic acid anhydride, and / or (ii)
When the heterocyclic amine-containing group is a group derived from a triazole compound, those in which these groups are independently bonded to the main chain are also preferable.

When the modified rubber (1) is the above rubber, the thermoreversible crosslinked polymer composition containing the modified rubber (1) may contain a donor or a compound other than the modified rubber (1). All compounds having two or more substituents serving as acceptors can be used. Among them, a compound having two or more donors or two or more acceptors, or a compound having two or more pairs of a donor and an acceptor is particularly preferable as the crosslinking agent. Specifically, dipyridyl,
Heterocyclic compounds having only two or more nitrogen atoms as isomers such as ethylenedipyridyl, trimethylenedipyridyl, phenazine, purine, pteridine, dipyridylamine, and melamine; quinone, anthraquinone, naphthoquinone,
Compounds having two or more carbonyl groups such as piperazine; compounds having two or more nitrogen atoms and carbonyl groups as ring components such as cyanuric acid; nylon 6, nylon-66, nylon-610, nylon-6
A compound having -CO- contained in an amide group such as 12;
Isonicotinic acid, pyrazine dicarboxylic acid, picolinic acid,
3-carbamoyl-pyrazine carboxylic acid, pyrazine monocarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid,
Compounds having a nitrogen atom and a carboxyl group as ring components such as quinaldic acid; other urea; aliphatic diols such as ethylene glycol, 1,4-butanediol, pinacol; malonic acid, succinic acid, glutaric acid, etc. Aliphatic dicarboxylic acids; amino acids such as glycine, tricine, bicine, alanine, valine, leucine, serine, threonine, lysine, aspartic acid, glutamic acid, cysteine, methionine, and proline; 5-hydroxyvaleramide, N-acetylethanolamine, N Aliphatic amides such as N, N'-hexamethylenebisacetamide, malonamide and cycloserine; phenols such as hydroquinone, biphenol and 4,4'-isopropylidenediphenol; aromatic alcohols such as 1,4-benzenedimethanol; , 4'- Chi range aniline, aromatic amines such as phenylenediamine; p-phenylenediamine acetate, p
Aromatic carboxylic acids such as -hydroxybenzoic acid and p-aminobenzoic acid; aromatic amino acids such as N- (p-aminobenzoyl) -β-alanine; ethyl-m-aminobenzoate, methyl-p-hydroxybenzoate and the like Aromatic esters; aromatic amides such as 4-acetamidophenol and p-acetamidobenzoic acid; imidazole;
-Imidazoles such as dimethylimidazole and 2-benzimidazoleurea; pyrrole-2-carboxylic acid, N
-Methylpyrrole-2-carboxylic acid, pyrazole, 3-
5-membered heterocyclic compounds such as methylpyrazole, histidine and 1,2,4-triazole; 1,2-bis- (4
-Pyridyl) -ethane, 2 (or4)-(β-hydroxyethyl) -pyridine, 2 (or4)-(2-aminoethyl) -pyridine, 2 (or4) -aminopyridine,
Examples thereof include 6-membered heterocyclic compounds such as 2,6-diaminopyridine, 2-amino-6-hydroxypyridine, and 6-azathymine. Among these, dipyridyl and melamine have an aromatic tertiary amino group in the molecule, nylon-6 has a carbonyl group in the molecule, and cyanuric acid has a structure having a carbonyl group in the pyridyl group. Have
The formation of hydrogen bonds with the above rubber is preferable because heat resistance becomes excellent.

Specific examples of the combination of the above-mentioned modified rubber and compound include low-modified carboxyl liquid isoprene rubber, highly modified carboxyl liquid isoprene rubber, carboxyl-terminated BR, carboxyl-terminated NBR, carboxyl-modified polybutane, and carboxyl-modified highly reactive polybutene. Combinations of each with each of dipyridyl, melamine, cyanuric acid, and nylon-6 may be mentioned.

A cross-linking system by hydrogen bonding of the modified rubber (1) will be exemplified. As a specific example when the modified rubber (1) is a rubber having both a donor and an acceptor, a heterocyclic amine containing a heterocyclic amine of the formula (1) in which R is 1,2,4-triazole is contained in an isoprene rubber main chain. Examples include those in which a group is introduced, and the crosslinked state is represented by the following formula (4).

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A specific example of the case where the modified rubber (1) is a rubber having one of a donor and an acceptor is one in which a carboxyl group as a donor is introduced into the isoprene rubber main chain. Specific examples of the compound having an acceptor contained in the thermoreversible crosslinked polymer composition include bipyridyl, melamine, cyanuric acid, and nylon. The crosslinked state is represented by the following formula (5) (two-point hydrogen bond), It is represented by the following formula (6) (6-point hydrogen bond), the following formula (7) (6-point hydrogen bond), and the following formula (8) (polymer-type hydrogen bond).

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When the modified rubber (1) is the above rubber, the content of the compound in the thermoreversible crosslinked polymer composition is based on 1 equivalent of a reactive site capable of forming a hydrogen bond in the rubber. Is preferably 0.1 to 5 equivalents, more preferably 0.5 to 1.5 equivalents. If it exceeds 5 equivalents, the number of substituents not involved in hydrogen bonding increases, and the viscosity becomes too large, which is not preferable.
If the amount is less than 0.1 equivalent, the effect of hydrogen bond formation is not sufficient, which is not preferable.

The density of crosslinks due to hydrogen bonding in the thermoreversible crosslinked polymer composition containing the modified rubber (1) differs depending on the purpose of use, application, molecular weight of the main chain, etc., and cannot be determined unconditionally. It is desirable that the crosslink density exhibit excellent rubber elasticity and excellent mechanical strength. Specifically, when a conjugated diene rubber such as isoprene or butadiene is used as a main chain and (i) and (ii) are present in a side chain,
The unit having side chain groups (i) and (ii) may be contained in an amount of about 0.1 to 30 mol%, preferably about 1 to 10 mol% of (1) based on the diene unit of each rubber. desirable. (I) and (ii)
(I) / (ii) The molar ratio may be about 0.5-2.

The thermoreversible crosslinked polymer composition containing the modified rubber (1) impairs the object of the present invention in addition to the modified rubber (1) and the above-mentioned compound when the modified rubber (1) is the above rubber. The polymer may contain unmodified polymer and various additives (for example, various stabilizers, flame retardants, antistatic agents, coloring agents, and fillers) within a range not to be described.
The content of the modified rubber (1) in the thermoreversible crosslinked polymer composition containing the modified rubber (1) is 30% of the total polymer amount.
To 100% by weight, more preferably 60 to 1% by weight.
The content is more preferably 00% by weight, particularly preferably 90 to 100% by weight.

The thermoreversible crosslinked polymer composition containing the modified rubber (1) forms a hydrogen bond at room temperature, and the hydrogen bond breaks down when heated. The formation and collapse of hydrogen bonds is reversible and can be repeated any number of times by applying temperature changes.

Next, the thermoreversible crosslinked polymer composition containing the modified rubber (2) will be described. Modified rubber (2)
Is a modified rubber having an organic salt structure, preferably a modified rubber having an organic salt structure in a side chain. In the present invention, the organic salt structure is a structure having an ion-binding portion (moiety) in which a functional group-modified product of a rubber constituting a modified rubber and a functional group of a compound are bonded via an ionic bond. In which no metal ions are present. Ionic bonds refer to bonds formed by electrostatic attraction between cations and anions. Therefore, the organic salt structure is formed by cations and anions other than metal ions.

Cations forming the organic salt structure include:
Although not particularly limited as long as it is other than a metal ion, an onium ion is preferable. An onium ion is generated by coordination of a proton or a cation-type reagent to an atom having an unshared electron pair, for example, ammonium ([R ₄ N] ⁺ (wherein R represents a hydrogen or an alkyl group; A plurality of Rs may be the same or different.
same as below. )), Phosphonium ([R ₄ P] ⁺ ), arsonium ([R ₄ As] ⁺ ), stibonium ([R ₄ S
b] ⁺ ), oxonium ([R ₃ O] ⁺ ), sulfonium ([R ₃ S] ⁺ ), selenonium ([R ₃ S
e] ⁺ ), stanonium ([R ₃ Sn] ⁺ ) and iodonium ([R ₂ I] ⁺ ).

The anions forming the organic salt structure include:
Although not particularly limited, examples include a halide ion, a carboxylate anion, an alcoholate anion, a phenolate anion, a thiocarboxylate anion, and a sulfonate anion.

In the present invention, the organic salt structure is not particularly limited, and can be appropriately selected from the above-mentioned cations and anions in combination. As described above, the structure in which the cation is the above-mentioned onium ion, And an onium salt structure, and an organic salt structure comprising a combination of an ammonium cation and a carboxylate anion is particularly preferable.

The modified rubber (2) comprises a raw rubber having a reactive site capable of forming an ionic bond and a compound having a reactive site capable of forming an ionic bond with the reactive site of the raw rubber via an ionic bond. Combine. That is, the modified rubber (2) comprises a raw material rubber having a reactive site capable of generating one of a cation and an anion, and a compound having a reactive site capable of generating the other. The reactive site capable of generating a cation is not particularly limited, and examples thereof include a site containing an atom having an unshared electron pair such as an amino group and an imino group. The reaction site that can generate an anion is not particularly limited. Examples thereof include halides (fluoride, chloride, bromide, iodide, and astatinide), carboxyl groups, hydroxyl groups, phenoxy groups, thiocarboxyl groups, sulfonyl groups, and substituted products thereof.

The raw material rubber having a reaction site capable of forming an ionic bond used in the present invention is modified or synthesized so as to have a reaction site capable of generating a cation or a reaction site capable of generating an anion. Rubber can be used. As the rubber to be modified, the same rubber as described above as the rubber to be modified used as a raw material of the modified rubber (1) can be used.

Raw rubber modified to have a reaction site capable of generating an anion includes low carboxyl-modified liquid isoprene rubber, high carboxyl-modified liquid isoprene rubber, carboxyl-terminated butadiene rubber, carboxyl-terminated nitrile rubber, carboxyl-modified polybutene, and carboxyl-modified polybutene. Modified high-reactivity polybutene, ethylene-acrylic acid copolymer and the like can be mentioned. Among them, highly modified carboxyl liquid isoprene rubber is preferred.

As the compound having a reactive site capable of forming an ionic bond, the above-described compound having a reactive site capable of generating a cation or a reactive site capable of generating an anion can be used.

In the present invention, the organic salt structure is preferably an organic salt structure having a hydrocarbon group. That is, the compound having a reactive site capable of forming an ionic bond preferably has a hydrocarbon group at the reactive site capable of generating a cation or an anion. Here, the hydrocarbon group generally refers to a group consisting only of carbon and hydrogen, but in the present invention, those containing an oxygen atom in the form of ether, carbonyl, ester and the like are also included. Among the hydrocarbon groups, an alkyl group, particularly a linear alkyl group, is preferable, and an alkyl group having 6 or more carbon atoms is more preferable. This is because, at room temperature, the alkyl chains are liable to form a pseudo-crosslinked structure due to ionic bonding with the raw rubber, and the rubber chains are easily formed. As the compound having a reactive site capable of generating a cation, a primary amine is preferable, and a methylamine having a linear alkyl group, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, Nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, cetylamine, stearylamine and the like can be suitably used.

Preferred specific examples of the combination of the raw material rubber and the compound include a carboxyl-modified isoprene rubber and dodecylamine. The modified rubber (2) obtained from these is represented by the following formula (9).

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The ratio of the raw rubber to the compound in the modified rubber (2) is such that the reaction site capable of forming an ionic bond in the compound is 0.1 equivalent to 1 equivalent of the reactive site capable of forming an ionic bond in the raw rubber. To 5 equivalents, preferably 0.5 to 5 equivalents.
More preferably, it is set to 1.5 equivalents. If it exceeds 5 equivalents, or if it is less than 0.1 equivalent, the number of reaction sites not involved in ionic bonding increases, and the crosslinking efficiency deteriorates.

The crosslinking density of the pseudo-crosslinked structure in the thermoreversible crosslinked polymer composition containing the modified rubber (2) varies depending on the purpose of use, application, molecular weight of the main chain and the like, and cannot be determined unconditionally. It is desirable that the crosslink density exhibit excellent rubber elasticity and excellent mechanical strength. Specifically, when using a modified rubber (2) obtained from a carboxyl-modified liquid isoprene rubber and stearylamine,
The onium salt structure of stearylamine is preferably contained in an amount of 0.1 to 30 mol%, more preferably 1 to 10 mol%, based on the diene unit of the isoprene rubber.

The thermoreversible crosslinked polymer composition containing the modified rubber (2) can be used in addition to the modified rubber (2) as long as the object of the present invention is not impaired. , Various stabilizers, flame retardants, antistatic agents, coloring agents, fillers). The content of the modified rubber (2) in the thermoreversible crosslinked polymer composition containing the modified rubber (2) is 60 to 100 of the total polymer amount.
%, More preferably 90 to 100% by weight.

The thermoreversible crosslinked polymer composition containing the modified rubber (2) has an organic salt structure, that is, the raw material rubber and the compound are bonded through an ionic bond, and at room temperature, the molecular A pseudo-crosslinked structure is formed, and the pseudo-crosslinked structure is collapsed by heating. The formation and collapse of the quasi-crosslinked structure is reversible, and can be repeated any number of times by applying a temperature change.

Further, the thermoreversible crosslinked polymer composition containing the modified rubber (3) will be described. Modified rubber (3)
Is a rubber having a crosslinked structure formed by a Diels-Alder reaction from a conjugated diene structure and a dienophile structure. The modified rubber (3) is composed of a raw material rubber having one of a conjugated diene structure and a dienophile structure, and
One or more compounds are crosslinked by a Diels-Alder reaction. That is, as an example of the modified rubber (3), a rubber (C) obtained by crosslinking a rubber (A) having a conjugated diene structure in a side chain with a compound (B) having two or more dienophile structures, and A rubber (C ′) obtained by crosslinking a rubber (A ′) having a dienophile structure in a side chain with a compound (B ′) having two or more conjugated diene structures.

The raw rubber used for the modified rubber (3) is
Rubber (A) having a conjugated diene structure in the side chain or rubber (A ') having a dienophile structure in the side chain. That is,
The rubber (A) has a conjugated diene in the side chain of the rubber, and the rubber (A ′) has a dienophile structure in the side chain of the rubber.

The conjugated diene is not particularly limited, and a chain conjugated diene and a cyclic conjugated diene can be used.
Cyclic conjugated dienes are preferred because of their excellent stability to heat and the like. The conjugated dienes used in the present invention are listed in Table 1.

[0126]

[Table 1]

(In Table 1, R ^{5 to} R ¹⁰ represent H, CH ₃ ,
_{C 2 H 5, C 3 H} 7, C 6 H 5, F, Cl, represents a group selected from the group consisting of Br and I, or different from each other were respectively the same. Among them, those having a hetero atom, particularly those having a furan skeleton can be suitably used.

Dienophiles are unsaturated compounds which additionally react with dienes in a Diels-Alder reaction to give cyclic compounds. The dienophile used in the present invention is not particularly limited. The dienophiles used in the present invention are listed in Table 2.

[0129]

[Table 2]

The rubber to which the conjugated diene or dienophile is bonded is not particularly limited, and any of those having or without an olefin structure in the main chain can be used. Rubber having an olefin structure in the main chain is, for example, natural rubber, butadiene rubber, isoprene rubber, chloroprene rubber, styrene-butadiene rubber, ethylene-propylene-diene rubber, acrylonitrile-butadiene rubber, nitrile rubber, butyl rubber, liquid polyisoprene, liquid Examples include polybutadiene, liquid styrene-butadiene rubber, and liquid polychloroprene. Rubbers having no olefin structure in the main chain include, for example, 1,2-polybutadiene rubber, ethylene-propylene rubber, chlorosulfonated polyethylene, acrylic rubber, epichlorohydrin rubber, polysulfide rubber, silicone rubber, fluorine rubber, urethane rubber , Liquid 1,2-polybutadiene, liquid silicone rubber, and liquid fluorine rubber can be used. Among them, those having an olefin structure in the main chain are preferable.

As the dienophile of the compound (B), the dienophile used for the compound (A ') can be used. The conjugated diene of the compound (B') is
The conjugated diene used for the compound (A) described above can be used.

Since the compound (B) used in the present invention has two or more dienophile structures, it is not particularly limited as long as it is a compound to which two or more of the dienophiles listed in Table 2 are bonded. Instead, it may be a polymer.
The compound (B) has two or more dienophile structures,
They may be the same or different. Specific examples include bisdienofils such as bismaleimide and tridienofils such as trimaleimide. As the bismaleimide, those represented by the following formula (10) can be suitably used. Among them, 4,4'-bismaleimidediphenylmethane is particularly preferably used.

[0133]

Embedded image

(Wherein R ^{5 to} R ⁸ are H, CH ₃ , C _{2
H 5, C 3 H 7,} F, Cl, represents a group selected from the group consisting of Br and I, or different from each other were respectively the same. X represents a group selected from the group listed in Table 3, and in Table 3, p and q represent an integer of 1 or more. )

[0135]

[Table 3]

[0136]

[Table 4]

[0137]

[Table 5]

[0138]

[Table 6]

The compound (B ') used in the present invention is represented by 2
Since it has two or more conjugated diene structures, it is not particularly limited as long as it is a compound to which two or more of the conjugated dienes listed in Table 1 are bonded. 2 of compound (B ′)
The one or more conjugated diene structures may be the same or different.

The ratio of (A) to the compound (B) in the rubber (C) or the ratio of (A ′) to the compound (B ′) in (C ′) is determined by the conjugated diene that (A) has in the side chain. The dienophile structure of the compound (B) or the conjugated diene structure of the compound (B ′) is 0.01 to 1.5 relative to 1 equivalent of the structure or 1 equivalent of the dienophile structure of the side chain of (A ′).
The equivalent is preferably used, and more preferably 0.1 to 1.0 equivalent.

The crosslink density of the crosslinked structure formed by the Diels-Alder reaction in the thermoreversible crosslinked polymer composition containing the modified rubber (3) varies depending on the purpose of use, application, molecular weight of the main chain and the like. I can't say,
At the time of crosslinking, it is desirable to have a crosslinking density that shows sufficient rubber elasticity and excellent mechanical strength. Specifically, when a modified rubber (3) obtained from a butadiene rubber having a furan skeleton in a side chain and 4,4'-bismaleimidediphenylmethane is used, 0.1 to 30 to the diene unit of the butadiene rubber is used. Mol%, preferably 1 to 10 mol%, preferably contains a unit having a furan skeleton introduced therein,
4,4′-Bismaleimidodiphenylmethane is 0.1 to
It is necessary to contain 5 equivalents, and 0.5 to 1.0 equivalent is more preferable.

The thermoreversible crosslinked polymer composition containing the modified rubber (3) can be used in addition to the modified rubber (3) as long as the object of the present invention is not impaired. , Various stabilizers, flame retardants, antistatic agents, coloring agents, fillers). The content of the modified rubber (3) in the thermoreversible crosslinked polymer composition containing the modified rubber (3) is 30 to 100 of the total polymer amount.
%, More preferably 60 to 100% by weight, particularly preferably 90 to 100% by weight.

The thermoreversible crosslinked polymer composition containing the modified rubber (3) can contain the rubber (C) and the compound (D) having a conjugated diene structure. A compound (D ′) having a dienophile structure may be contained.

Compound (D) having a conjugated diene structure is
There is no particular limitation, and a chain conjugated diene and a cyclic conjugated diene can be used. As the compound (D), the conjugated dienes listed in Table 1 are suitably used (in Table 1, R ⁵
To R ¹⁰ are H, CH ₃ , C ₂ H ₅ , C ₃ H ₇ , C
₆ H _5, F, Cl, represents a group selected from the group consisting of Br and I, or different from each other were respectively the same. ). These may be the same as or different from the diene bonded to the side chain of the rubber (A) constituting the rubber (C). Among them, furan, thiophene, cyclohexadiene and the like are preferably used. The contents of the rubber (C) and the compound (D) are not particularly limited. As the compound (D ') having a dienophile structure, dienophiles listed in Table 2 are preferably used. These may be the same as or different from the dienophile bonded to the side chain of the rubber (A ') constituting the rubber (C').

The crosslinking reaction that occurs when kneading under heating to produce the rubber (C) is represented by the following formula (11). (A) + (B) → (C) (11) The Diels-Alder reaction exemplified in the above formula (11) is a reversible reaction, and the crosslinked rubber (C) is reversed (retro) by heating. A Diels-Alder reaction is caused to dissociate (decrosslink) the rubber (A) and the compound (B) (formula (12)). (A) + (B) ← (C) (12)

When the rubber composition containing the rubber (C) and the compound (D) having a conjugated diene structure is kneaded under heating, a decrosslinking reaction occurs, and the compound (B)
To give a composition containing the reactant (E) of the compound (D) with the rubber (A) (formula (13)). (C) + (D) → (E) + (A) (13) Conversely, when the composition containing the reactant (E) and the rubber (A) is kneaded under heating, a crosslinking reaction occurs and the rubber ( C)
And a rubber composition containing the compound (D) having a conjugated diene structure (Formula (14)). (C) + (D) ← (E) + (A) (14) The reactions of the above formulas (13) and (14) can be carried out in the presence of a solvent such as toluene, if necessary.

Specific examples of the above formulas (11) and (12) and the above formulas (13) and (14) are represented by the following formula (15).

[0148]

Embedded image (Where X is the following formula

Embedded image Is a group represented by )

The reactions represented by the above formulas (11) to (15) use rubber (C) as a rubber having a crosslinked structure formed by a Diels-Alder reaction from a conjugated diene structure and a dienophile structure. But rubber (C
A similar reaction occurs for ′).

The reaction of the above formulas (13) and (14) has a higher reaction rate than the reaction of the above formulas (11) and (12).
The formation and collapse of the cross-linked structure can be caused quickly by using. The same applies to the rubber (C ′).

The thermoreversible crosslinked polymer composition containing the modified rubber (3) can form and collapse a crosslinked structure by heating. The formation and collapse of the crosslinked structure formed by the Diels-Alder reaction is reversible, and can be repeated any number of times by applying a temperature change.

The thermoreversible crosslinked polymer composition containing the modified rubber (3) contains a compound having a conjugated diene structure or a compound having a dienophile structure, so that the rate of crosslinking and decrosslinking due to a temperature change can be increased. Therefore, workability and the like in each application can be improved.

Next, the thermoreversible crosslinked polymer composition containing the modified rubbers (4) to (9) will be described. at first,
The modified rubbers (4) to (9) will be described. The modified rubbers (4) to (9) are modified rubbers utilizing a specific thermoreversible reaction for a crosslinking reaction. Here, the specific thermoreversible reaction is
The modified rubber (4) is an ester forming reaction between an acid anhydride group and a hydroxyl group, and the modified rubber (5) is a hemiacetal ester forming reaction between a carboxyl group and a vinyl ether group. Is an ionene forming reaction between a halogenated alkyl group and a tertiary amine, a modified rubber (7) is a urethane forming reaction between a phenolic hydroxyl group and an isocyanate group, and a modified rubber (8) is This is a reaction between an azlactone group and a phenolic hydroxyl group. In the modified rubber (9), a nitroso dimer formation reaction is caused by two nitroso groups. Each of these reactions is a binding reaction between one reaction site and another reaction site, and is common in that a bond is dissociated by heating, and a bond is formed again by cooling. Hereinafter, the modified rubbers (4) to (9) will be described by generalizing these thermoreversible reactions to a thermoreversible reaction between the reaction site A and the reaction site B.

The modified rubbers (4) to (9) utilize the reaction between the reaction sites A and B for the crosslinking reaction, and are crosslinked at room temperature. Dissociates and then forms crosslinks again when cooled. The modified rubbers (4) to (9) take one of the following modes. A rubber having both or one of the reaction sites A and B, wherein the reaction sites A and B react with each other to form a bond between molecules and form a crosslinked rubber at room temperature (modified rubber ( In (9), since the reaction sites A and B are the same, a rubber having a nitroso group, in which the nitroso groups react with each other and bond between the molecules, and are crosslinked at room temperature) . A rubber having a rubber molecule having one of the reaction sites A and B and a compound having the other, wherein the reaction sites A and B react with each other and are bonded between the rubber molecule and the compound. In the case of a rubber crosslinked at normal temperature (modified rubber (9), since reaction sites A and B are the same, a rubber having a rubber molecule having a nitroso group and a compound having a nitroso group, , A rubber in which a nitroso group reacts with each other to bond between a rubber molecule and a compound and a crosslink is formed at room temperature).

Since the modified rubbers (4) to (9) have a cross-linked structure at room temperature, each of the modified rubbers exists in a state in which the rubber molecules are bonded to each other. And the compound are present in a bonded state, but at a certain temperature or higher, the crosslinked structure is dissociated.In the embodiment, each rubber molecule exists in a separated state, and in the embodiment, the rubber molecule and the compound are separated. It exists in a state where it has been done.

In the embodiment of the present invention, the rubber may have both the reaction sites A and B in one molecule, and the rubber having only the reaction site A in one molecule and the rubber having only the reaction site B in one molecule May be mixed. Among them, it is preferable to have both the reaction sites A and B in one rubber molecule. Further, a rubber having both reactive sites A and B in one molecule of rubber and at least one of a rubber having only reactive site A in one molecule and a rubber having only reactive site B in one molecule are mixed. Is also good.

In the embodiment, the reaction site of the rubber molecule may be the reaction site A or the reaction site B. When the rubber molecule has a reaction site A, the compound has a reaction site B, and when the rubber molecule has a reaction site B, the compound has a reaction site A.

In the modified rubber (4), the reaction sites A and B are an acid anhydride group and a hydroxyl group. The acid anhydride group refers to an acid anhydride group of an aliphatic or aromatic carboxylic acid, and any of a cyclic acid anhydride group and an acyclic anhydride group can be used. Is preferably used. Examples of the cyclic acid anhydride group include a maleic anhydride group, a phthalic anhydride group, a succinic anhydride group, and a glutaric anhydride group.Examples of the non-cyclic acid anhydride group include an acetic anhydride group and a propionic anhydride group. And a benzoic anhydride group. Among them,
Succinic anhydride groups to which maleic anhydride has been added are preferred.
In the modified rubber (5), the reaction sites A and B are a carboxyl group and a vinyl ether group. In the modified rubber (6), the reaction sites A and B are a halogenated alkyl group and a tertiary amino group. Examples of the halogenated alkyl group include alkyl bromide, alkyl chloride, phenyl bromide, phenyl chloride, benzyl bromide, and benzyl chloride. Among them, benzyl bromide is preferred. Examples of the tertiary amino group include a dimethylamino group, a diethylamino group, and a diphenylamino group. Among them, a dimethylamino group is preferable. The combination of the halogenated alkyl group and the tertiary amino group is not particularly limited, but a combination of benzyl bromide and a dimethylamino group is preferred. In the modified rubber (7),
Reaction sites A and B are phenolic hydroxyl groups and isocyanate groups. In the modified rubber (8), the reaction sites A and B are an azlactone group and a phenolic hydroxyl group. In the modified rubber (9), the reaction sites A and B are the same and are nitroso groups.

The modified rubber of the embodiment is obtained by modifying the rubber as a raw material in a state where the reaction sites A and B have already reacted, or in a state where the reaction sites A and B have already reacted. It may be obtained directly by direct polymerization, or may be obtained by modifying a rubber as a raw material to have both reaction sites A and B, or have both reaction sites A and B To the polymerized rubber,
In some cases, it can be obtained by adding actions such as heating and cooling. In the modified rubber according to the embodiment, the rubber which forms a crosslink with the compound is obtained by modifying a rubber as a raw material so as to have one of the reaction sites A and B, or
And B are obtained by polymerizing a rubber having one of them. It is also obtained by polymerization or modification in a state where the reaction sites A and B have reacted.

In these cases, the rubber to be modified may be the same as that described above as the rubber to be modified used in the raw material of the modified rubber (1).

The method for producing a rubber having both the reaction sites A and B according to the embodiment is not particularly limited.
And at the same time or separately in the state of reacting with the rubber. Hereinafter, a method for introducing the reaction site A into the rubber and a method for introducing the reaction site B into the rubber will be specifically described. The reaction site A of the embodiment
The method for producing the rubber having either one of B and B is not particularly limited, and the following method for introducing the reaction site A into the rubber and the method for introducing the reaction site B into the rubber, or the reaction site A and the B Manufactured using any of the methods of introducing into the rubber in a reacted state.

A method for introducing an acid anhydride group used in the modified rubber (4) into rubber and a method for introducing a hydroxyl group into rubber will be described. Methods for introducing an acid anhydride group into rubber include, for example, a method of copolymerizing an olefin-containing acid anhydride monomer such as maleic anhydride, and a method of reacting an acid anhydride skeleton-containing compound with a rubber to be modified, specifically, In
A method in which maleic anhydride is ene-reacted with a diene rubber is used. Methods for introducing hydroxyl groups into rubber include, for example,
After copolymerizing a monomer such as vinyl acetate, a method of performing hydrolysis or a method of reacting a hydroxyl group-containing compound with a rubber to be modified, specifically, reacting a diene rubber with a hydroxyl group-containing mercapto compound such as mercaptoethanol There is a method to make it. As a method of introducing the reaction sites A and B into the rubber in a state where the reaction sites A and B are reacted, for example, a method of introducing a compound having a half ester skeleton in which an acid anhydride skeleton and a hydroxyl group have reacted by a polymer reaction or a method of copolymerizing the compound. No.

A method for introducing a carboxyl group into the rubber and a method for introducing a vinyl ether group into the rubber used in the modified rubber (5) will be described. Methods for introducing a carboxyl group into a rubber include, for example, a method of copolymerizing a carboxyl group-containing monomer such as acrylic acid and methacrylic acid, and a method of reacting a carboxyl group-containing compound with a rubber to be modified, specifically, diene. A method of reacting a carboxylic acid-containing mercapto compound such as thioglycolic acid with a system rubber is exemplified. Methods for introducing vinyl ether groups into rubber include, for example, a method of copolymerizing a vinyl ether group-containing monomer such as divinyl ether, and a method of reacting a vinyl ether group-containing compound with a rubber to be modified, specifically, a diene rubber. A method of reacting a vinyl ether-containing mercapto compound such as mercaptoethyl vinyl ether is exemplified. Examples of a method of introducing the reaction site A and B into the rubber in a state where the reaction sites A and B are reacted include a method of introducing a compound having a hemiacetal ester skeleton in which a carboxyl group and a vinyl ether group have reacted by a polymer reaction or a method of copolymerizing the compound. No.

A method for introducing a halogenated alkyl group used in the modified rubber (6) into the rubber and a method for introducing a tertiary amino group into the rubber will be described. The method of introducing a halogenated alkyl group into the rubber includes, for example, a method of copolymerizing a halogenated alkyl group-containing monomer such as bromomethylstyrene and chloromethylstyrene, and a method of mercaptobromotoluene, mercaptochlorotoluene, and the like for a rubber to be modified. A method of reacting a halogenated alkyl group-containing compound is exemplified. Methods for introducing a tertiary amino group into a rubber include, for example, a method of copolymerizing a tertiary amino group-containing monomer such as dimethylaminostyrene and diethylaminostyrene, and a method of applying dimethylaminothiophenol and diethylaminothiophenol to a rubber to be modified. And the like. As a method for introducing the reaction sites A and B into the rubber in a reacted state, for example, a method of introducing a compound having an ionene skeleton in which an alkyl halide group and a tertiary amino group are reacted by a polymer reaction or copolymerization Method.

A method for introducing a phenolic hydroxyl group into the rubber used in the modified rubber (7) and a method for introducing an isocyanate group into the rubber will be described. Examples of a method of introducing a phenolic hydroxyl group into a rubber include a method of copolymerizing a phenolic hydroxyl group-containing monomer such as hydroxystyrene and a method of reacting a phenolic hydroxyl group-containing compound such as mercaptophenol with a rubber to be modified. . Examples of the method of introducing an isocyanate group into a rubber include a method of copolymerizing an isocyanate group-containing monomer such as isocyanate styrene and isocyanate acrylate, and a method of containing a protected isocyanate group such as phenol-capped isocyanate thiophenol in a rubber to be modified. After reacting the compound, the protecting group is removed. Examples of a method of introducing the compound having a urethane skeleton in which an isocyanate group and a phenolic hydroxyl group have been reacted or a method of copolymerizing a compound having a urethane skeleton in which the reaction sites A and B are reacted with each other include, for example, a method of introducing the compound into the rubber. Can be

A method for introducing an azlactone group used in the modified rubber (8) into rubber and a method for introducing a phenolic hydroxyl group into rubber will be described. The method of introducing an azlactone group into a rubber includes, for example, a method of copolymerizing an azlactone group-containing monomer such as azlactone styrene and azlactone acrylate, and a step of reacting an azlactone group-containing compound such as azlactone thiophenol with a rubber to be modified. Method. The method for introducing the phenolic hydroxyl group into the rubber includes the same method as the method used for the rubber according to the fourth aspect of the present invention. Examples of a method of introducing the reaction sites A and B into the rubber in a state where the reaction sites A and B are reacted include a method of introducing a compound having a skeleton in which an azlactone group and a phenolic hydroxyl group are reacted by a polymer reaction or a method of copolymerizing the compound. .

A method for introducing a nitroso group used in the modified rubber (9) into the rubber will be described. The method of introducing a nitroso group into a rubber is, for example, a method of copolymerizing a nitroso group-containing monomer such as nitrosostyrene or nitrosoacrylate, or a method of reacting a nitroso group-containing compound such as nitrosothiophenol or nitrosyl chloride with a rubber to be modified. Method. Examples of a method of introducing the compound into the rubber in a state where the nitroso group has been reacted include a method of introducing a compound having a skeleton in which the nitroso group is dimerized by a polymer reaction or a method of copolymerizing the compound.

The compound used in the embodiment preferably has two or more reaction sites A or B in the molecule. However, the compound having one reaction site A or B in the molecule is mixed. Is also good.

The compound used in the embodiment is a compound having an acid anhydride group or a compound having a hydroxyl group in the modified rubber (4). Examples of the compound having an acid anhydride group include a bisphthalic anhydride compound, a bissuccinic anhydride compound, a bisglutaric anhydride compound, and a bismaleic anhydride compound. Examples of the compound having a hydroxyl group include glycols such as ethylene glycol, diethylene glycol, and triethylene glycol;
1,4-butanediol, 1,6-hexanediol,
1,8-octanediol, 1,10-decanediol, trimethylolethane, trimethylolpropane,
Alcohol compounds such as pentaerythritol. Among them, 1,6-hexanediol, ethylene glycol and diethylene glycol are preferred.

In the modified rubber (5), the compound used in the embodiment is a compound having a carboxyl group or a compound having a vinyl ether group. As the compound having a carboxyl group, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, phthalic acid,
Maleic acid and fumaric acid; As the compound having a vinyl ether group, for example, ethylene glycol divinyl ether, butanediol divinyl ether,
2,2-bis [p- (2-vinyloxyethoxy) phenyl] propane. Among them, ethylene glycol divinyl ether and butanediol divinyl ether are preferred.

In the modified rubber (6), the compound used in the embodiment is a compound having a halogenated alkyl group or a compound having a tertiary amino group. Examples of the compound having a halogenated alkyl group include α,
α'-dibromoxylene, α, α'-dichloroxylene, bisbromomethylbiphenyl, bischloromethylbiphenyl, bisbromodiphenylmethane, bischlorodiphenylmethane, bisbromomethylbenzophenone, bischloromethylbenzophenone, bisbromodiphenylpropane, bischlorodiphenyl Propane. Examples of the compound having a tertiary amino group include tetramethylethylenediamine, tetramethylhexanediamine, and bisdimethylaminobenzene. Among them, tetramethylhexanediamine is preferred.

In the modified rubber (7), the compound used in the embodiment is a compound having a phenolic hydroxyl group or a compound having an isocyanate group. Examples of the compound having a phenolic hydroxyl group include dihydroxybenzene, dihydroxybiphenyl, resole type phenol resin, and novolak type phenol resin. Examples of the compound having an isocyanate group include aromatic compounds such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, and p-phenylene diisocyanate. Examples thereof include aliphatic diisocyanates such as diisocyanate and hexamethylene diisocyanate, alicyclic diisocyanates such as isophorone diisocyanate, and aryl aliphatic diisocyanates such as xylylene diisocyanate.

The compound used in the embodiment is a compound having an azlactone group or a compound having a phenolic hydroxyl group in the modified rubber (8). Examples of the compound having an azlactone group include bisazlactone butane, bisazlactonebenzene, and bisazlactonehexane. Examples of the compound having a phenolic hydroxyl group include the same compounds as those used in the above-described fourth embodiment of the present invention.

The compound used in the embodiment is a compound having a nitroso group in the modified rubber (9).
Examples of the compound having a nitroso group include dinitrosopropane, dinitrosohexane, dinitrosobenzene, and dinitrosotoluene.

The combination of the rubber having one of the reaction sites A and B and the compound having the other in the embodiment is not particularly limited, but in the modified rubber (4), the rubber is a maleic anhydride group-containing diene diene. System rubber,
Combinations wherein the compound is an aliphatic diol such as 1,6-hexanediol are preferred.

In the modified rubber (5), a combination in which the rubber is a carboxyl group-containing diene rubber and the compound is a divinyl ether of an alkyl diol such as butanediol divinyl ether is preferable.

In the modified rubber (6), a combination in which the rubber is an alkyl halide-containing diene rubber and the compound is an alkyldiamine such as tetramethylhexanediamine is preferable.

In the modified rubber (7), a combination in which the rubber is a phenolic hydroxyl group-containing diene rubber and the compound is an aromatic diisocyanate such as diphenylmethane diisocyanate is preferred.

In the modified rubber (8), the rubber is preferably a phenolic hydroxyl group-containing diene rubber, and the compound is preferably an alkyl bisazlactone such as bisazlactone butane.

In the modified rubber (9), it is preferred that the rubber is a nitroso group-containing diene rubber alone.

In the embodiment, the amount of the cross-linking site in the rubber, that is, the amount of the bonding portion formed by the reaction between the reaction sites A and B in the rubber molecule is 0.1 mol% or more with respect to the rubber monomer unit. It is preferred that Within the above range, the modified rubbers (4) to (9) have excellent strength and the like.

In the embodiment of the present invention, the amount of the cross-linking site in the rubber, that is, the amount of the bonding portion generated by the reaction between one of the reaction sites A and B in the rubber molecule and the other in the compound is determined by the following formula. 0.1 mol% based on the monomer unit of
It is preferable that this is the case. Within the above range, modified rubber (4)
To (9) are excellent.

In the embodiment, the ratio of the rubber having one of the reactive sites A and B to the compound having the other is such that the reactive site in the compound is 0.1 equivalent to 1 equivalent of the reactive site in the rubber molecule. ５5 equivalents, preferably 0.5〜
More preferably, it is 1.5 equivalents. Within the above range, the number of reaction sites involved in crosslinking increases, and the crosslinking efficiency increases.

The method for producing the modified rubbers (4) to (9) is not particularly limited. For example, a solution mixing method or a dry mixing method can be used. The solution mixing method is a method in which a cross-linking reaction is performed in a soluble solvent, and then the solvent is distilled off. The dry mixing method is a method of performing a mixing and crosslinking reaction using a kneader or the like without using a solvent. Modified rubber (4)-
For the production of (9), any of a solution mixing method and a dry mixing method can be used, and in all cases, the reaction temperature is 50 ° C. or higher.

In the modified rubbers (4) to (9), in the case where the modified rubber is of the form described above, one or more rubbers having both the reaction sites A and B are used for the production thereof. be able to. Further, in the modified rubbers (4) to (9), when the modified rubber is in the form of, the production of the rubber having one of the reaction sites A and B may be carried out.
Species or two or more can be used, and one or more compounds having the other can be used.

In the modified rubbers (4) to (9), the reaction sites A and B react with each other to bond between the rubber molecules or between the rubber molecules and the compound, and crosslinks are formed at room temperature. When the denatured rubbers (4) to (9) are heated to a certain temperature or higher, the bonds are dissociated and the crosslinks are broken.

In the modified rubber (4), an acid anhydride group and a hydroxyl group form an ester and are crosslinked. The collapse (decrosslinking) and regeneration (recrosslinking) of this crosslink are represented by the following formula (1)
6). The temperature at which de-crosslinking and re-crosslinking occur (flow initiation temperature) depends on the crosslinking density and the like.
It is about 00 to 200 ° C.

[0188]

Embedded image

In the modified rubber (5), the carboxyl group and the vinyl ether group form a hemiacetal ester and are crosslinked. Disintegration (decrosslinking) and regeneration (recrosslinking) of this crosslinking are exemplified by the following formula (17). The temperature at which decrosslinking and recrosslinking occur (flow initiation temperature) depends on the crosslinking density and the like, but is usually about 100 to 200 ° C.

[0190]

Embedded image

In the modified rubber (6), the alkyl halide group and the tertiary amine form ionene and are crosslinked. Disintegration (decrosslinking) and regeneration (recrosslinking) of this crosslinking are exemplified by the following formula (18). The temperature at which decrosslinking and recrosslinking occur (flow initiation temperature) depends on the crosslinking density and the like, but is usually about 100 to 200 ° C.

[0192]

Embedded image

In the modified rubber (7), the phenolic hydroxyl group and the isocyanate group form urethane and are crosslinked. The collapse (de-cross-linking) and regeneration (re-cross-linking) of this cross-link are exemplified by the following formula (19). The temperature at which decrosslinking and recrosslinking occur (flow initiation temperature) depends on the crosslinking density and the like, but is usually about 100 to 200 ° C.

[0194]

Embedded image

In the modified rubber (8), the azlactone group and the phenolic hydroxyl group form a bond and are crosslinked. Collapse (decrosslinking) and regeneration (recrosslinking) of this crosslink
Is exemplified by the following equation (20). The temperature at which decrosslinking and recrosslinking occur (flow initiation temperature) depends on the crosslinking density and the like, but is usually about 100 to 200 ° C.

[0196]

Embedded image

In the modified rubber (9), two nitroso groups are crosslinked by forming a nitroso dimer. The collapse (decrosslinking) and regeneration (recrosslinking) of this crosslink are exemplified by the following formula (21). The temperature at which decrosslinking and recrosslinking occurs (flow initiation temperature) depends on the crosslinking density and the like, but is usually
It is about 100 to 200 ° C.

[0198]

Embedded image

The modified rubbers (4) to (9) exhibit rubber elasticity due to the formation of cross-links at ordinary temperature, and when heated to a certain temperature (processing temperature, usually 50 ° C. or higher) or more, the cross-links break down, It shows fluidity, is excellent in heat aging resistance, can be continuously melt-molded stably for a long time, and rapidly forms a crosslinked structure in a cooling process after molding. When heated again above the processing temperature, the crosslinks are completely dissociated, and when cooled again, crosslinks are formed. The modified rubbers (4) to (9) can repeat the dissociation and formation of the crosslinked structure three or more times. Therefore, the modified rubbers (4) to (9) are excellent in rubber elasticity, and are easily heat molded and recycled.

Next, the thermoreversible crosslinked polymer composition containing the modified rubbers (4) to (9) will be described. The thermoreversible crosslinked polymer composition containing the modified rubbers (4) to (9) contains at least one of the modified rubbers (4) to (9) described above. The modified rubber contained may be one type,
Two or more types may be used. The thermoreversible crosslinked polymer composition containing the modified rubbers (4) to (9) can contain additives such as various stabilizers, flame retardants, antistatic agents, coloring agents, and fillers. These additives are modified rubbers (4) to
It can be added during the production of (9) or can be added after the production.

The thermoreversible crosslinked polymer composition containing the modified rubbers (4) to (9) further comprises a rubber other than the modified rubbers (4) to (9) as long as the object of the present invention is not impaired. One or more kinds can be contained. This makes it possible to adjust the strength characteristics and the like of the thermoreversible crosslinked polymer composition containing the modified rubbers (4) to (9), and to reduce raw material costs. Modified rubber (4)-
The rubber other than (9) may be unvulcanized rubber or vulcanized rubber. For example, a rubber which is a raw material of the above-described modified rubbers (4) to (9) may be mentioned. Above all, when the rubber other than the modified rubbers (4) to (9) is vulcanized, a thermoplastic elastomer is preferable. In particular, considering the rubber elasticity, workability, recyclability, etc. of the thermoreversible crosslinked polymer composition containing the modified rubbers (4) to (9), the elastomer and the thermoplastic resin are heated at a temperature higher than the softening point of the resin. Thermoplastic elastomer obtained by crosslinking performed while kneading, so-called dynamic crosslinking, in which a vulcanized rubber phase in which at least a part is a continuous phase and at least a part is a discontinuous phase in a resin phase is finely dispersed. Compositions are preferred.

The content of the modified rubbers (4) to (9) in the thermoreversible crosslinked polymer composition containing the modified rubbers (4) to (9) is preferably at least 10% by weight of the whole composition. More preferably, it is 50% by weight or more. Within the above range, the rubber elasticity, processability, and recyclability of the thermoreversible crosslinked polymer composition containing the modified rubbers (4) to (9) are sufficient.

[0203] In the tire of the present invention, all parts except the cord may be composed of one or more thermoreversible crosslinked polymer compositions.
The portion other than the portion composed of the thermoreversible crosslinked polymer composition is 1
It may consist of one or more rubber compositions. At least a part of the part other than the part composed of the thermoreversible crosslinked polymer composition is composed of a rubber composition containing rubber and a vulcanizing agent. As described later, the tire of the present invention is obtained by bonding the thermoreversible crosslinked polymer composition and the rubber composition by high-temperature pressing (hot pressing). However, at the time of hot pressing, the rubber composition has already been vulcanized. Or unvulcanized.

As the rubber used in the rubber composition, the same rubber as described above as the rubber subjected to the modification used as the raw material of the modified rubber (1) can be used.

As a vulcanizing agent, a general rubber vulcanizing agent can be used. For example, a sulfur-based vulcanizing agent, an organic peroxide-based vulcanizing agent, a phenolic resin-based vulcanizing agent, and other vulcanizing agents can be used. Among them, sulfur-based vulcanizing agents are preferred. Specifically, examples of the sulfur-based vulcanizing agent include powdered sulfur, precipitated sulfur, highly dispersible sulfur, surface-treated sulfur, insoluble sulfur, dimorpholine disulfide, alkylphenol disulfide, and the like. For example, rubber 100 parts by weight For 0.
About 5 to 4 parts by weight may be used. Examples of the organic peroxide-based vulcanizing agent include benzoyl peroxide, t-butyl hydroperoxide, 2,4-dichlorobenzoyl peroxide, and 2,5-dimethyl-2,5-di (t
-Butylperoxy) hexane, 2,5-dimethylhexane-2,5-di (peroxylbenzoate) and the like.
A part by weight may be used. Further, as a phenolic resin-based vulcanizing agent, brominated alkylphenol resin,
A mixed crosslinking system containing a halogen donor such as tin chloride and chloroprene and an alkylphenol resin, and the like,
For example, about 1 to 20 parts by weight may be used for 100 parts by weight of rubber. In addition, zinc white (about 5 parts by weight based on 100 parts by weight of rubber), magnesium oxide (about 4 parts by weight), litharge (about 10 to 20 parts by weight), p-quinonedioxime, p-dibenzoyl Quinone dioxime, tetrachloro-p-benzoquinone, poly-
p-Dinitrosobenzene (also about 2 to 10 parts by weight), methylene dianiline (also about 0.2 to 10 parts by weight) and the like.

The rubber composition contains, in addition to the rubber and the vulcanizing agent,
Other additives, for example, a vulcanization accelerator, a reinforcing agent, an antioxidant, a processing aid, various stabilizers, a flame retardant, an antistatic agent, a coloring agent, a filler, etc. within a range not to impair the object of the present invention. Can be contained.

The tire of the present invention is obtained by bonding the thermoreversible crosslinked polymer composition and the rubber composition by hot pressing. The conditions for hot pressing are not particularly limited. The temperature is preferably from 120 to 200 ° C., preferably from 150 to 200 ° C.
More preferably, it is 180 ° C. Pressure is 0.1MP
a to 5 MPa, preferably 0.1 MPa to 1 M
More preferably, it is Pa.

When a rubber composition that has already been vulcanized is used, when the thermoreversible crosslinked polymer composition and the rubber composition are bonded and hot pressed, the thermoreversible crosslinked polymer melts and anchors. As a result, the thermoreversible crosslinked polymer and the rubber are crosslinked by the migration of the vulcanizing agent remaining near the interface between the thermoreversible crosslinked polymer composition and the rubber composition. Thereby, the thermoreversible crosslinked polymer composition and the rubber composition,
Adheres very firmly. When an unvulcanized rubber composition is used, when the thermoreversible crosslinked polymer composition and the rubber composition are bonded and hot pressed, the rubber composition is cured by the vulcanizing agent contained in the rubber composition. The whole crosslinks,
Simultaneously, crosslinking occurs between the thermoreversible crosslinked polymer and the rubber due to migration of the vulcanizing agent near the interface between the thermoreversible crosslinked polymer composition and the rubber composition. Thereby, the thermoreversible crosslinked polymer composition and the rubber composition adhere very firmly.

The structure of the tire of the present invention is not particularly limited, and may be any structure including a portion composed of a thermoreversible crosslinked polymer composition. For example, a bias tire, a tubeless tire, a radial tire, and a belted bias tire can be used. Further, a pneumatic tire is preferable.

[0210] The tire of the present invention has a temperature lower than the temperature at which crosslinking of the thermoreversible crosslinked polymer collapses (for example, the temperature of the tire rises to about 100 to 130 ° C during running, but the crosslinking collapse temperature of the thermoreversible crosslinked polymer ( Lower than the flow start temperature), the thermoreversible crosslinked polymer composition exhibits excellent heat resistance, and the bond between the thermoreversible crosslinked polymer composition and the rubber composition is strong, and the adhesive portion Is comparable to the strength of rubber alone. On the other hand, at a temperature equal to or higher than the temperature at which the crosslink of the thermoreversible crosslinked polymer collapses, the crosslink of the thermoreversible crosslinked polymer collapses and the thermoreversible crosslinked polymer layer is softened, so that the thermoreversible crosslinked polymer composition can be easily converted from the rubber composition. Can be peeled. Therefore, the tire of the present invention exhibits the same strength characteristics and heat resistance as a tire made of a normal rubber alone, and when heated to a certain temperature, the thermoreversible crosslinked polymer composition and the rubber composition can be easily separated. As a result, it can be made a recyclable product.

[0211] In the tire of the present invention, the temperature at which the thermoreversible crosslinked polymer composition and the rubber composition are peeled off may be at least the temperature at which the crosslinking of the thermoreversible crosslinked polymer composition breaks down. Preferably, the temperature is lower than the temperature at which the heat treatment is performed. Even at a temperature equal to or higher than the temperature at which the rubber composition deteriorates, if the heat treatment time is short, the thermoreversible crosslinked polymer composition can be dissolved before the rubber composition substantially deteriorates. it can.

The application of the tire of the present invention is not particularly limited. For example, it can be used for passenger car tires, truck / bus tires, light truck / light truck tires, construction vehicle tires, agricultural machine tires, industrial vehicle tires, aircraft tires, motorcycle tires, snow tires. it can.

[0213]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. 1. Preparation of Thermo-Reversible Cross-Linked Polymer Composition The raw materials shown below were used in the weight ratios shown in Table 4, respectively, and the thermo-reversible cross-linked polymer composition of each Example shown in Table 4 and the rubber composition of each Comparative Example were used. I got something. In addition,
Thermoreversible crosslinked polymer composition A, B, C, E, F, J,
K, L, O and P contain the above-mentioned modified rubber (1), and thermoreversible crosslinked polymer compositions D, G and M contain the above-mentioned modified rubber (2), and a thermoreversible crosslinked polymer composition H and N contain the modified rubber (3) described above, the thermoreversible crosslinked polymer compositions Q and R contain the modified rubber (4) described above, and the thermoreversible crosslinked polymer composition S contains the modified rubber described above. The thermoreversible crosslinked polymer composition T containing the rubber (5) contains the modified rubber (6) described above, and the thermoreversible crosslinked polymer composition U contains the modified rubber (7) described above, and is thermoreversible. The crosslinked polymer composition V contains the modified rubber (8) described above, and the thermoreversible crosslinked polymer composition W contains the modified rubber (9) described above.

Rubber i) SBR (styrene-butadiene rubber): Nipol
1502, manufactured by Zeon Corporation, styrene content 23% ii) SBR / maleic anhydride adduct: SBR (Nipo
The method for producing a modified rubber in which maleic anhydride is added to 11502) in an amount of 3 mol% per butadiene unit is shown below. Styrene-butadiene rubber (N
ipol 1502) 300 g (butadiene unit 4.3 mol) was dissolved in xylene 2.54 l, and 105 g (1.1 mol) of maleic anhydride and 180 g (0.43 mol) of Irganox 1520 were added.
Stirred at 0 ° C. for 20 hours. The reaction solution was precipitated in acetonitrile and dried under reduced pressure to obtain a modified styrene-butadiene rubber into which maleic anhydride was introduced. SBR
The ratio of maleic anhydride to the monomer unit was 3.0 mol. iii) IR (isoprene rubber) / maleic anhydride adduct: maleic anhydride added to IR (Nipol IR-2200, manufactured by Zeon Corporation) at 3 m per butadiene unit
The method for producing modified rubber to which ol% is added is shown below. Isoprene rubber (Nipol
IR-2200) 260 g (3.8 isoprene units)
mol) was dissolved in 2.54 l of xylene, and 186 g (1.9 mol) of maleic anhydride and Irganox 15 were dissolved.
20 162 g (0.38 mol) were added, and the mixture was stirred at 140 ° C. for 20 hours. The reaction solution was precipitated in acetonitrile and dried under reduced pressure to obtain a modified isoprene rubber into which maleic anhydride was introduced. The ratio of maleic anhydride to the isoprene unit was 3.0 mol. iv) SEBS (hydrogenated product of styrene-butylene-styrene block copolymer) / maleic anhydride adduct: S
Maleic anhydride was added to EBS (Clayton G1652, manufactured by Shell, 29/71 wt% styrene / rubber ratio).
Modified thermoplastic elastomer which is considered to be added at 0.02 mol per 0 g

V) Alkyl halide-containing butyl rubber:
Exxpro89-1, Exxon Chemical Co., Ltd., bromine content 1.2 wt% vi) Modified rubber (ester-forming rubber) using a reaction between an acid anhydride group and a hydroxyl group for a crosslinking reaction: The production method is described below. Styrene-butadiene rubber (Nipol 150
2) Dissolve 300 g (4.3 mol of butadiene unit) in 2.54 L of xylene, and add 105 g of maleic anhydride.
(1.1 mol) and Irganox 1520 18
0 g (0.43 mol) was added, and the mixture was stirred and reacted at 140 ° C. for 20 hours. The reaction solution was precipitated in acetonitrile and dried under reduced pressure to obtain a styrene-butadiene rubber having a maleic anhydride group introduced therein (maleic anhydride group-containing SBR). The obtained maleic anhydride group-containing S
The ratio of the introduced maleic anhydride group in BR was 3.0 mol% based on the butadiene unit. The resulting maleic anhydride group-containing SBR (modification rate 3 mol
%) To 100 g, 4.3 g of 1,6-hexanediol was added, and the mixture was stirred and mixed at 120 ° C. and 60 rpm for 20 minutes by a kneader to utilize a reaction between an acid anhydride group and a hydroxyl group for a crosslinking reaction. Thus, a modified rubber (ester-formed rubber) was obtained.

Vii) Modified Rubber (Hemiacetal Ester-Forming Rubber) Utilizing a Reaction between Carboxyl Group and Vinyl Ether Group for Crosslinking Reaction: The production method is described below. 260 g (3.8 mol of isoprene unit) of isoprene rubber (Nipol IR-2200) was dissolved in 2.54 L of xylene, and 186 g (1.9 mol) of maleic anhydride and 162 g of Irganox 1520 (0.38 mol) were dissolved.
l) was added, and the mixture was stirred at 140 ° C. for 20 hours to react. The reaction solution was precipitated in acetonitrile and dried under reduced pressure to obtain a maleic anhydride group-introduced isoprene rubber (maleic anhydride group-containing IR). The ratio of the introduced maleic anhydride group in the obtained maleic anhydride group-containing IR was 3.0 mol per isoprene unit.
1%. The obtained maleic anhydride group-containing IR is reacted with methanol in a pyridine catalyst to introduce a carboxyl group into isoprene rubber (carboxyl group-containing IR).
I got 134.3 g of the obtained carboxyl group-containing IR
4.91 g (69.1 mmol) of 1,4-butanediol divinyl ether and 2.77 g (2% by weight of total) of Irganox 1520 were added to (69.1 mmol), and the mixture was kneaded at 180 ° C. and 60 rpm for 10 minutes. Under a condition, the mixture was stirred and mixed to obtain a modified rubber (hemiacetal ester-formed rubber) using a reaction between a carboxyl group and a vinyl ether group for a crosslinking reaction.

Viii) Modified rubber (ionene-forming rubber) utilizing a reaction between a halogenated alkyl group and a tertiary amino group for a crosslinking reaction: The production method is described below. 459 g of alkyl halide-containing butyl rubber (Exxpro89-1)
(68.94 mmol) was added with 5.94 g of tetramethylhexanediamine, and the mixture was heated at 120 ° C. and 60 ° C. with a kneader.
The mixture was stirred and stirred at 20 rpm for 20 minutes to obtain a modified rubber (ionene-forming rubber) using a reaction between an alkyl halide group and a tertiary amino group for a crosslinking reaction.

Ix) Modified rubber (urethane-forming rubber) using a reaction between an isocyanate group and a phenolic hydroxyl group for a crosslinking reaction: The production method is described below. Isoprene rubber (N
200 g of ipol IR-2200) was dissolved in 2 L of xylene, and 126 g of 4-mercaptophenol (1.0 m
ol), stirred at 140 ° C. for 20 hours, and reacted. The reaction solution was precipitated in methanol and dried under reduced pressure to obtain an isoprene rubber having a phenolic hydroxyl group introduced therein (phenolic hydroxyl group-containing IR). The ratio of the introduced phenolic hydroxyl group in the obtained phenolic hydroxyl group-containing IR was 3.
It was 0 mol%. 4. Diphenylmethane diisocyanate was added to 100 g of the obtained phenolic hydroxyl group-containing IR.
43 g was added and the mixture was kneaded at 120 ° C., 60 rpm,
The mixture was stirred under a condition of 20 minutes to obtain a modified rubber (urethane-forming rubber) using a reaction between an isocyanate group and a phenolic hydroxyl group for a crosslinking reaction.

X) Modified rubber (azlactone / phenol-added rubber) utilizing a reaction between an azlactone group and a phenolic hydroxyl group for a crosslinking reaction: The production method is described below. ix)
In the same manner as described above, a phenolic hydroxyl group-containing IR was obtained. The obtained phenolic hydroxyl group-containing IR1
Then, 6.08 g of bisazlactone butane was added to the mixture, and the mixture was stirred and mixed with a kneader at 120 ° C. and 60 rpm for 20 minutes to obtain a modified rubber (azlactone. (Phenol-added rubber).

Xi) Modified Rubber (Nitroso Dimer Forming Rubber) Using Nitroso Group Dimerization Reaction for Crosslinking Reaction: The production method is described below. Isoprene rubber (Nipol IR-
2200) 200 g of chloroform was dissolved in 2 L of chloroform, and 65.5 g (1.0 mmol) of nitrosyl chloride was added.
And stirred for 20 hours. The reaction solution was precipitated in methanol and dried under reduced pressure to obtain a modified rubber (nitroso dimer-formed rubber) utilizing a dimerization reaction of a nitroso group for a crosslinking reaction. The ratio of the introduced nitroso groups in the obtained nitroso dimer-forming rubber was 4.0 mol% with respect to the isoprene unit.

Ingredients Zinhua: Ginrei Zinhua R, manufactured by Toho Zinc Co., Ltd. Stearic acid: beaded stearic acid, manufactured by NOF Carbon Black: Show Black N339 HAF-
HS aroma oil: Desolex No. 3, anti-aging agent 1 (N- (1,3-dimethylbutyl) -N 'manufactured by Showa Shell Sekiyu KK)
-Phenyl-P-phenylenediamide): Santoflex 13, manufactured by Nippon Monsanto Antioxidant 2 (pentaerythrityl-tetrakis [3-
(3,5-Di-tert-butyl-4-hydroxyphenyl) propionate]): Irganox101
0, manufactured by Nippon Ciba Geigy Co., Ltd. Sulfur: oil treated sulfur, manufactured by Karuizawa Seirensho Co., Ltd. 6-hexanediol 1,8-hexanediol aminotriazole (3-amino-1,2,4-triazole) aminopyridine dodecylamine stearylamine methanol furfuryl alcohol DPBM (diphenylbismaleimide)

[0222] 2. Physical properties of thermoreversible crosslinked polymer composition and the like Physical properties of each thermoreversible crosslinked polymer composition and rubber composition obtained above were evaluated. (1) Tensile test Tensile strength (rupture strength), elongation (elongation at break) and 200% modulus were measured in accordance with the provisions of JIS K6251. (2) Flow start temperature Using a Koka type flow tester (Shimadzu CFT-500), heating was performed under a pressure of 10 Mpa to obtain a length of 1
The temperature at which outflow from a 0 mm, 1 mm diameter capillary was measured. (3) Recyclability In the case where the step of melting by a hot press at 190 ° C. and then cooling to room temperature was reversibly repeated, the number of times that the repetition was possible without deteriorating the appearance was observed. The recyclability was evaluated as good (◎) for 3 or more times, acceptable (○) for 1 or 2 times, and no (×) for 0 times.

Table 4 shows the physical properties of the thermoreversible crosslinked polymer compositions A to W and rubber compositions A to L. Among the thermoreversible crosslinked polymer compositions containing the modified rubber (1) described above,
Further, it can be seen that those containing a compound having a donor (B, E, and L) have characteristics that the flow start temperature is not so high and the recyclability is excellent. Among the thermoreversible crosslinked polymer compositions containing the above-mentioned modified rubber (1), those which do not further contain a compound having a donor (A, C, F, J, K, O and P) have a high flow starting temperature. It has a characteristic that it has excellent recyclability. It can be seen that the thermoreversible crosslinked polymer compositions (D, G, and M) containing the modified rubber (2) described above have characteristics that the flow start temperature is not so high and the recyclability is excellent. The thermoreversible crosslinked polymer composition (H and N) containing the above-mentioned modified rubber (3) forms a chemical bond, and thus has a feature that the flow start temperature is high, the heat resistance is excellent, and the recyclability is excellent. You can see that. Thermoreversible crosslinked polymer composition (Q and R) containing modified rubber (4) described above, thermoreversible crosslinked polymer composition (S) containing modified rubber (5), modified rubber (6)
, A thermoreversible crosslinked polymer composition (U) containing a modified rubber (7), a thermoreversible crosslinked polymer composition (V) containing a modified rubber (8), and modification Since the thermoreversible crosslinked polymer composition (W) containing the rubber (9) forms a chemical bond, it can be seen that the thermoreversible crosslinked polymer composition has characteristics of high flow start temperature, excellent heat resistance, and excellent recyclability.

[0224]

[Table 7]

[0225]

[Table 8]

[0226]

[Table 9]

[0227] 3. Manufacture of tire using thermoreversible crosslinked polymer composition Tires were manufactured using thermoreversible crosslinked polymer compositions A to D. (Example 1) In FIG. 1 (a) and its enlarged view (b), the thermoreversible crosslinked polymer composition 21 at the bottom of the tread groove was
A tire that was thermoreversible crosslinked polymer composition A was produced.
In this tire, the thermoreversible crosslinked polymer composition was dissolved and removed by heating to increase the depth of the groove. Treads can be formed with higher precision than conventional additional engraving,
Productivity was also good.

Example 2 In FIG. 1C, a tire having a coating layer 22 made of the thermoreversible crosslinked polymer composition A on the surface of the sidewall 1 was manufactured. In this tire, by heating, the damaged portion of the coating layer 22 or the like could be dissolved, or after removing the entire coating layer 22, a new sidewall could be attached and reformed. (Comparative Example 1) A tire similar to that of Example 2 was manufactured except that the coating layer 22 was not provided. This tire was not recyclable.

Example 3 In FIG. 2A, a tire was manufactured in which the adhesive layer 23 was composed of the thermoreversible crosslinked polymer composition A. In this tire, the adhesive layer 23 was melted by heating, the tread 2 was peeled off, and a new tread portion was reattached, so that other members of the tire could be reused as they were.

Example 4 In FIG. 2B, a tire was manufactured in which the undertread 4 was made of the thermoreversible crosslinked polymer composition A. This tire is heated to tread 2
By peeling off and reattaching a new tread portion, other members of the tire could be reused as they were.

Example 5 In FIG. 3A, a tire was manufactured in which the adhesive layer 24 was composed of the thermoreversible crosslinked polymer composition C. In this tire, the portion containing the metal cord of the belt 5 was taken out by melting the adhesive layer 24 by heating, and the metal cord could be reused, or another member of the tire could be reused as it was.

Example 6 In FIG. 3B, a tire was manufactured in which the adhesive layer 25 was composed of the thermoreversible crosslinked polymer composition C. This tire dissolves the adhesive layer 25 by heating, so that the tread member and the belt member are
Correction was possible.

Example 7 In FIG. 3C, a tire was manufactured in which the adhesive layer 26 was composed of the thermoreversible crosslinked polymer composition C. This tire was capable of repairing and correcting only 2B by melting the adhesive layer 26 by heating.

Example 8 In FIG. 4A, a tire was manufactured in which the adhesive layer 27 was made of the thermoreversible crosslinked polymer composition B. In this tire, the adhesive layer 27 was melted by heating, the side wall 1 was peeled off, and a new side wall portion was re-bonded, so that other members of the tire could be reused as they were.

(Example 9) In FIG. 4 (b), a tire was manufactured in which the portion 1 'of the sidewall 1 in contact with the undertread 4 and the carcass 6 was made of the thermoreversible crosslinked polymer composition C. In this tire, when the portion 1 ′ made of the thermoreversible crosslinked polymer composition C is melted by heating, a peeling portion is formed at the end of the tread member, so that the entire tread member can be dismantled efficiently by peeling off the portion. Could do well.

Example 10 In FIG. 5A, a tire was manufactured in which the adhesive layer 28 was made of the thermoreversible crosslinked polymer composition B. In this tire, the adhesive layer 28 was melted by heating, and it was easy to peel it off from the bead filler portion, and it was possible to separate and collect components.

Example 11 In FIG. 5B, a tire was manufactured in which the entire bead filler 7 was composed of the thermoreversible crosslinked polymer composition B. This tire has the same effect as that of the tenth embodiment, and also has the advantage that the shape of the bead filler becomes smooth and the durability is improved.

Example 12 In FIG. 5C, a tire was manufactured in which the entire bead filler 7 and bead core 8 were made of the thermoreversible crosslinked polymer composition B. In this tire, bead filler 7 and bead core 8 as a whole are melted by heating, in addition to the same effects as in Example 11, so that
There is an advantage that the winding portion (rim cushion) of the carcass 6 can be easily disassembled.

Example 13 In FIG. 6A, a tire was manufactured in which the adhesive layer 29 was made of the thermoreversible crosslinked polymer composition B. In this tire, the adhesive layer 29 was melted by heating, the inner liner portion could be easily peeled off, and the components could be separated and collected.

Example 14 In FIG. 6B, a tire was manufactured in which the entire inner liner 9 was made of the thermoreversible crosslinked polymer composition B. In addition to the same effects as in Example 13, this tire can be repaired by heating and melting a puncture hole formed in the inner liner, and can be bonded to the thermoreversible crosslinked polymer composition of the inner liner. Since it became possible to heat-bond a patch piece made of, it could be easily repaired.

Example 15 In FIG. 7, the entire belt edge cushion 10 was made of a thermoreversible crosslinked polymer composition C.
Was manufactured. By heating, the tire is moved from the belt edge cushion portion to the side wall 1.
Etc. could be easily peeled off, and parts could be separated and collected.

(Example 16) In FIG.
Consists of a thermoreversible crosslinked polymer composition B, and the adhesive layer 31 consists of a thermoreversible crosslinked polymer composition C. In this tire, the thermoreversible crosslinked polymer composition B of the adhesive layer 30 used had a lower flow start temperature than the thermoreversible crosslinked polymer composition C of the adhesive layer 31. At first, the flow start temperature of the thermoreversible crosslinked polymer composition B of the adhesive layer 30 is higher than 151 ° C., and the flow start temperature of the thermoreversible crosslinked polymer composition C of the adhesive layer 31 is lower than 185 ° C. 170
By heating to ° C., only the adhesive layer 30 was dissolved, and the tread portion could be disassembled and corrected. After disassembling and correcting the tread portion, and once cooling, the adhesive layers 30 and 31 are melted by heating to 190 ° C., which is higher than the flow start temperature of the thermoreversible crosslinked polymer composition C of the adhesive layer 31 at 185 ° C. Was dismantled, and the new tread, sidewalls and belt were glued together and corrected.

(Example 17) In FIG. 9 (a) and its enlarged view (b), the thermoreversible crosslinked polymer composition coating layer 5
2 was made of the thermoreversible crosslinked polymer composition C, and a tire was manufactured in which the belt cord 51 was a steel cord. In this tire, the coating layer 52 was melted by heating, and the belt cord 51 could be collected, reused, and recycled.

Example 18 In FIG. 9 (a) and its enlarged view (c), the thermoreversible crosslinked polymer composition coating layer 5
2 comprises a thermoreversible crosslinked polymer composition C, a rubber composition coating layer 53 comprises a rubber composition A, and a belt cord 51.
Manufactured tires that are steel cords. In this tire, the coating layer 52 is melted by heating, and the belt cord 51 is melted.
In addition, the rubber composition coating layer 53 could be recovered and reused, and a conventional metal-rubber bonding technique could be used for the production of this tire.

Example 19 In FIG. 10 (a), a tire in which the adhesive layer 32 is made of a thermoreversible crosslinked polymer composition C, and the tread 2 and all other components are made of a pre-vulcanized rubber composition Was manufactured. Specifically, the thermoreversible crosslinked polymer composition is bonded to a pre-vulcanized tread member on a rigid support, and further bonded to a separately vulcanized casing portion on the rigid support, followed by heating. And integrated. Each member of the tread member and the casing portion was vulcanized under optimum conditions in advance. This tire had high productivity because the integral vulcanization step could be omitted. In addition, the adhesive layer 32 was easily peeled off by heating and could be recycled.

Example 20 In FIG. 10 (b), the adhesive layer 33 was made of the thermoreversible crosslinked polymer composition D, the tread 2 was made of the unvulcanized rubber composition, and all the components other than the tread 2 were used. Manufactured a tire comprising a rubber composition which had been vulcanized in advance. Specifically, the thermoreversible crosslinked polymer composition is bonded to an unvulcanized tread member, and further bonded to a separately vulcanized casing portion, and then heated using a vulcanizing mold for a tread portion. It was obtained by integrating the whole together with the vulcanization of the member. Since the thickness of the rubber to be vulcanized was small, the tire could be vulcanized in a short vulcanization time, and the vulcanization productivity was high. In addition, the adhesive layer 33 was easily peeled off by heating and could be recycled.

[0247]

According to the present invention, when a part of the tire is worn or damaged, only the part can be easily replaced. Further, the tire of the present invention can be easily disassembled for each constituent member during or after use. Therefore, the reuse and recycling of the tire components can be easily performed, which is extremely useful.

[Brief description of the drawings]

FIGS. 1A to 1C are partial cross-sectional views of an example of the tire of the present invention.

FIGS. 2A and 2B are partial cross-sectional views of an example of the tire of the present invention.

FIGS. 3A to 3C are partial cross-sectional views of an example of the tire of the present invention.

FIGS. 4A and 4B are partial cross-sectional views of an example of the tire of the present invention.

FIGS. 5A to 5C are partial cross-sectional views of an example of the tire of the present invention.

FIGS. 6A and 6B are partial cross-sectional views of an example of the tire of the present invention.

FIG. 7 is a partial sectional view of an example of the tire of the present invention.

FIG. 8 is a partial sectional view of an example of the tire of the present invention.

FIG. 9A is a partial cross-sectional view of an example of the tire of the present invention. (B) is a schematic diagram showing an example of the belt of the tire shown in (a). (C) is a schematic diagram showing another example of the belt of the tire shown in (a).

FIGS. 10A and 10B are schematic diagrams of an example of the tire of the present invention.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 Side wall 1 'Part of side wall 2 Tread 3 Cap tread 4 Under tread 5 Belt 6 Carcass 6' Carcass winding part 7 Bead filler 8 Bead core 9 Inner liner 10 Belt edge cushion 21 Thermo-reversible crosslinked polymer composition 22 Coating layer 23, 24, 25, 26, 27, 28, 29, 30, 3,
1, 32 adhesive layer 51 belt cord 52 thermoreversible crosslinked polymer composition coating layer 53 rubber composition coating layer

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) B60C 15/06 B60C 15/06 B C08L 21/00 C08L 21/00 // C08F 8/00 C08F 8/00 (72) Inventor Keisuke Chino 2-1 Oiwake, Hiratsuka-shi, Kanagawa Prefecture F-term in the Hiratsuka Works of Yokohama Rubber Co., Ltd. ER006 EU026 EU086 EU186 EU196 FD010 FD140 GN01 4J100 AA02P AA03Q AA06P AB02Q AM02Q AS02P AS03P AS07P CA01 CA04 CA23 CA31 HA53 HA55 HA57 HC28 HC63 JA29

Claims (20)

[Claims] 1. A tire comprising at least a part of a thermoreversible crosslinked polymer composition. 2. The tire according to claim 1, wherein at least one tire constituent member is a tire constituent member in which at least a part of a portion in contact with another member is made of a thermoreversible crosslinked polymer composition. 3. The tire according to claim 1, wherein at least one of the tire components has an adhesive layer made of a thermoreversible crosslinked polymer composition in at least a part between the tire and another adjacent member.
The tire described in the above. 4. The tire according to claim 2, wherein the tire constituent member is a tread member. 5. The tire according to claim 2, wherein the tire constituent member is a belt member. 6. The tire according to claim 2, wherein the tire constituent member is a side member. 7. The tire according to claim 2, wherein the tire constituent member is a bead filler member. 8. The tire according to claim 2, wherein the tire constituent member is an inner liner member. 9. The tire according to claim 1, wherein at least a part of a member covering at least one reinforcing cord is made of a thermoreversible crosslinked polymer composition. 10. The tire according to any one of claims 1 to 9, wherein at least a part of the part which comes into contact with the part made of the thermoreversible crosslinked polymer composition is made of a pre-vulcanized rubber composition. 11. The thermoreversible crosslinked polymer composition,
The thermoreversible crosslinked polymer contained in the thermoreversible crosslinked polymer composition used in at least one place is a hydroxyl group, at least one selected from the group consisting of a primary amino group and a secondary amino group, and a tertiary amino group and 2. A modified rubber having a reactive site capable of forming a hydrogen bond with at least one selected from the group consisting of carbonyl groups.
The tire according to any one of claims 10 to 10. 12. The thermoreversible crosslinked polymer composition,
The thermoreversible crosslinked polymer contained in the thermoreversible crosslinked polymer composition used in at least one place has the following formula (1) to
The tire according to claim 11, which has at least one group of (5). Embedded image 13. The thermoreversible crosslinked polymer composition,
The tire according to any one of claims 1 to 12, wherein the thermoreversible crosslinked polymer contained in the thermoreversible crosslinked polymer composition used in at least one place is a modified rubber having an organic salt structure in a side chain. 14. The thermoreversible crosslinked polymer composition,
The thermoreversible crosslinked polymer contained in the thermoreversible crosslinked polymer composition used in at least one place is a modified rubber having a crosslinked structure formed by a Diels-Alder reaction from a conjugated diene structure and a dienophile structure.
14. The tire according to any one of items 13 to 13. 15. The thermoreversible crosslinked polymer composition,
The thermoreversible crosslinked polymer contained in the thermoreversible crosslinked polymer composition used in at least one place is a modified rubber obtained by utilizing a reaction between an acid anhydride group and a hydroxyl group for a crosslink reaction. Tires. 16. The thermoreversible crosslinked polymer composition,
The thermoreversible crosslinked polymer contained in the thermoreversible crosslinked polymer composition used in at least one place is a modified rubber utilizing a reaction between a carboxyl group and a vinyl ether group for a crosslink reaction. tire. 17. The thermoreversible crosslinked polymer composition,
The thermoreversible crosslinked polymer contained in the thermoreversible crosslinked polymer composition used in at least one place is a modified rubber utilizing a reaction between an alkyl halide group and a tertiary amino group for a crosslinking reaction. The tire according to any of the above. 18. The thermoreversible crosslinked polymer composition,
The thermoreversible crosslinked polymer contained in the thermoreversible crosslinked polymer composition used in at least one place is a modified rubber utilizing a reaction between an isocyanate group and a phenolic hydroxyl group for a crosslink reaction. Tires. 19. The thermoreversible crosslinked polymer composition,
The thermoreversible crosslinked polymer contained in the thermoreversible crosslinked polymer composition used in at least one place is a modified rubber obtained by utilizing a reaction between an azlactone group and a phenolic hydroxyl group for a crosslinking reaction. Tires. 20. The thermoreversible crosslinked polymer composition,
The thermoreversible crosslinked polymer contained in the thermoreversible crosslinked polymer composition used in at least one place is a modified rubber using a dimerization reaction of a nitroso group for a crosslink reaction.
20. The tire according to any one of 19.