JP7198633B2 - Tire and tire manufacturing method - Google Patents

Description

The present invention relates to tires and methods of manufacturing tires.

Conventionally, vehicle tires, particularly trucks or buses including small trucks, or tires used for vehicles with a relatively heavy total vehicle weight such as off-road wheels for construction vehicles and mining vehicles, etc. The sidewall rubber of the sidewall portion of the tire may come into contact with an obstacle or the like and wear out early.
For example, city buses make frequent stops at closely spaced bus stops throughout the city to pick up and drop off passengers. In recent years, due to the trend toward barrier-free access to such buses, the gap between the boarding gate and the sidewalk has been eliminated by bringing the bus body closer to the curb, making it easier for elderly people, wheelchair users, and stroller users to get on and off. Experiments have been carried out to reduce the burden on the patient. In order to eliminate the gap between the bus body and the curb, it is necessary to move the sidewall of the bus tire as close to the curb as possible. Friction due to contact causes the sidewall rubber to wear prematurely, shortening the life of the tire.

JP-A-10-195249

As a countermeasure against wear of the sidewall rubber of the tire, there is a method of increasing the thickness of the sidewall rubber, but this method increases the weight of the tire and is not preferable from the viewpoint of fuel consumption. In addition, there is also a measure to change the compounding agent blended in the rubber composition used for the sidewall rubber (Patent Document 1). was not sufficient and further improvement was required.

Accordingly, it is an object of the present invention to provide a tire in which the wear resistance of the sidewall portion is improved and the state of wear can be easily recognized, and a tire manufacturing method for manufacturing such a tire. aim.

The tire of the present invention has a structure having a vulcanized rubber layer and a polyurethane foam layer on the surface of the sidewall rubber of the tire body,
The structure is characterized by having portions with different colors in the thickness direction of the structure.
According to this configuration, it is possible to easily recognize the state of wear while improving the wear resistance of the sidewall portion.

In the tire of the present invention, the polyurethane foam layer preferably contains a binder. Further, in the tire of the present invention, it is also preferable that the polyurethane foam layer contains a design substance. According to these configurations, it is possible to recognize the state of wear more easily.

In the tire of the present invention, the structure preferably has a barrier layer formed from a rubber composition containing butyl rubber as the rubber component (A) on the side of the surface to be adhered to the sidewall rubber. According to this configuration, when the wear of the structure progresses, the structure can be easily replaced.
Further, in this case, in the tire of the present invention, it is preferable that the polyurethane foam layer includes a first polyurethane foam layer positioned adjacent to the barrier layer on the opposite side of the barrier layer from the adhesive surface. . According to this configuration, it is possible to more easily recognize the state of wear. Also, discoloration of the polyurethane foam layer due to the antioxidant can be avoided.

In the tire of the present invention, it is preferable that the polyurethane foam layer has a second polyurethane foam layer, at least a part of which is present on the outer surface of the structure on the side opposite to the surface bonded to the sidewall rubber. . According to this configuration, it is possible to more easily recognize the state of wear.
Further, in this case, in the tire of the present invention, a portion of the second polyurethane foam layer present on the outer surface of the structure and a portion of the second polyurethane foam layer present on the outer surface of the structure are positioned around each other, A pattern is preferably formed by the vulcanized rubber layer present on the outer surface of the structure. According to this configuration, it is possible to improve the design of the tire and to recognize the wear condition more easily.

In the tire of the present invention, the polyurethane foam layer is two or more layers,
a second polyurethane foam layer, at least a portion of which is present on the outer surface of the structure on the side opposite to the surface to which the sidewall rubber is adhered; and a color of the second polyurethane foam layer. Differently, a third polyurethane foam layer located on the adhesive surface side with respect to the second polyurethane foam.
According to this configuration, it is possible to more easily recognize the state of wear.

In the tire of the present invention, the polyurethane foam layer has a third polyurethane foam layer present in the structure or present on the side of the structure to be bonded to the sidewall rubber,
It is preferable that the vulcanized rubber layer is positioned on the outer surface side opposite to the bonding surface of the structure to the sidewall rubber with respect to the third polyurethane foam layer.
According to this configuration, it is possible to more easily recognize the state of wear while improving the wear resistance of the sidewall portion.

In the tire according to the present invention, the rubber composition of the barrier layer comprises a layered or plate-like clay mineral (B), at least one of a processability improver (C) and a metal salt of an unsaturated carboxylic acid (E), including
The rubber composition of the barrier layer does not contain stearic acid (D), or the content of stearic acid (D) is 0.1 parts by mass or less per 100 parts by mass of the rubber component (A). is preferred.
As a result, the polyurethane foam layer can be further prevented from discoloring to brown, has low adhesion to metal parts, and facilitates adhesion of the barrier layer to the sidewall rubber.

In the tire according to the present invention, the rubber composition of the barrier layer preferably contains the processability improver (C) and the unsaturated carboxylic acid metal salt (E).
Thereby, the adhesion of the rubber composition to metal parts can be further suppressed.

In the tire according to the present invention, the rubber composition of the barrier layer contains a processability improver (C),
The processability improver (C) is preferably at least one selected from glycerin fatty acid ester compositions and stearylamine derivatives.
Thereby, the adhesion of the rubber composition to metal parts can be further suppressed.

In the tire according to the present invention, the rubber composition of the barrier layer contains a metal salt of unsaturated carboxylic acid (E),
The unsaturated carboxylic acid metal salt (E) is preferably at least one selected from metal acrylates and metal methacrylates.
Thereby, it can suppress more that a polyurethane-foam layer discolors to brown.

The tire manufacturing method of the present invention uses a vulcanized tire body, the vulcanized rubber layer before or after vulcanization, and the polyurethane foam layer to manufacture the tire according to any one of the above. characterized by
According to this configuration, even with a used tire, the abrasion resistance of the sidewall portion can be improved, and the wear condition can be easily recognized.

In the tire manufacturing method of the present invention, the tire according to any one of the above is manufactured by using the tire main body before vulcanization, the vulcanized rubber layer before vulcanization or vulcanization, and the polyurethane foam layer. characterized by
According to this configuration, when a new tire is manufactured, it is possible to easily recognize the wear state while improving the wear resistance of the sidewall portion.

ADVANTAGE OF THE INVENTION According to the present invention, it is possible to provide a tire in which the wear resistance of the sidewall portion is improved and the state of wear can be easily recognized, and a tire manufacturing method for manufacturing such a tire. can.

It is a side view showing a tire concerning one embodiment of the present invention. FIG. 2 is a cross-sectional view showing an enlarged cross-section of a structure in the tire of FIG. 1; 3 is a cross-sectional view showing an enlarged cross-section of a first modified example of the structure shown in FIG. 2; FIG. FIG. 4 is a cross-sectional view showing an enlarged cross-section of a first modification of the structure shown in FIG. 2 or the structure shown in FIG. 3 in a state where wear of the structure progresses; 3 is a cross-sectional view showing an enlarged cross-section of a second modification of the structure shown in FIG. 2; FIG. 6 is a cross-sectional view showing an enlarged cross-section of a modification of the structure shown in FIG. 5; FIG. 3 is a cross-sectional view showing an enlarged cross-section of a third modification of the structure shown in FIG. 2; FIG.

An embodiment of the present invention will be described below. These descriptions are intended to be illustrative of the invention and are not intended to limit the invention in any way.

A tire according to one embodiment is a tire having a structure having a vulcanized rubber layer and a polyurethane foam layer on the surface of a sidewall rubber of a tire body, wherein the structure extends in the thickness direction of the structure. and having portions with mutually different colors.
The tire of the present embodiment is not particularly limited, but for example, it is used for trucks including small trucks, buses, or vehicles with a relatively heavy gross vehicle weight such as off-road vehicles such as construction vehicles and mining vehicles. be able to. Moreover, in this embodiment, the tire is preferably used for an urban bus.

<Tire body>
The tire body portion of the tire of the present embodiment is not particularly limited, but has, for example, a tread portion, a pair of sidewall portions continuing to both sides of the tread portion, and a bead portion continuing to each sidewall portion. Further, the tire main body portion includes a carcass extending in a toroidal shape over the tread portion, the sidewall portion and the bead portion, a sidewall rubber disposed outside the carcass in the tire width direction and constituting the sidewall portion, and the carcass. It has a belt and a tread rubber that are arranged radially outward of the tire and constitute a tread portion.
In the present embodiment, a tire having the structure will be referred to as a tire, and regardless of whether the tire has a structure, a portion other than the structure of the tire will be referred to as a tire main body. .

<Structure>
In this embodiment, as shown in FIG. 1, the tire 1 has a structure 4, which will be described later, on at least one of the tire body 2, preferably on the surface of the sidewall rubber 3 of a pair of sidewalls. there is In particular, of the surface of the sidewall rubber 3, the structure 4 is provided on a portion that may come into contact with curbs on the road, obstacles on the ground, etc. when the vehicle is running or when the vehicle is stopped or started. ing.
In addition, the structure 4 may be arranged on the surface of the sidewall rubber 3 in a part of the tire radial direction and the entire tire circumferential direction (that is, in this case, the structure 4 may be an annular ), which is a partial range in the tire radial direction of the sidewall rubber 3, and may be arranged on the surface of a partial range in the tire circumferential direction. (That is, in this case, one structure 4 has a shape in which a rectangle is curved into an arc, an ellipse, or an elongated ellipse). Specifically, in the latter case, as shown in the side view of the sidewall portion of the tire 1 in FIG. (pieces) are provided.

Further, the structure 4 may have various configurations as described later, but only one of the configurations of the structure described later may be provided on the surface of the sidewall rubber 3, or the structure described later may be provided on the surface of the sidewall rubber 3. may be provided on the surface of the sidewall rubber 3 by combining a plurality of forms among the forms of (for example, in the example of FIG. may be combined, or each structure 4 may be one type of the structure described later, and the tire 1 as a whole may combine a plurality of types).
In addition, the position of the surface of the sidewall rubber 3 in the tire radial direction where the structure 4 is provided may change depending on the type of the tire 1, so the type of the tire 1, etc. can be changed as appropriate. For example, in the case of a tire used for a city bus, the structure can be provided on the surface of the sidewall rubber at a position in the tire radial direction so as to match the shape of the curb of the road.

As shown in FIGS. 2 to 7, the structure in the tire of the present embodiment has a vulcanized rubber layer 41 and a polyurethane foam layer 42, and further, the structure 4 has a thickness of , has portions that are different in color from each other.
Since the tire 1 has such a structure 4, the sidewall rubber 3 can be protected by the vulcanized rubber layer 41, and the wear resistance of the sidewall portion can be improved. In addition, since the structure 4 has portions with different colors in the thickness direction of the structure 4, the color that can be visually recognized from the outside varies depending on the state of wear of the structure 4. It becomes easy to recognize the wear condition of a certain structure 4, and the user of the tire 1 can replace the structure 4 at an appropriate time. Therefore, the tire 1 can be effectively used for a long period of time.

The structure used in the present embodiment may vary in shape depending on the type of tire and the extent to which the sidewall rubber is to be protected. is preferred, and the width is preferably 30 to 80 mm.
In addition, the thickness of the structure refers to the average thickness, and when the structure is provided with an adhesive layer and adhered to the tire, the thickness includes the adhesive layer. Further, the width of the structure refers to the average width of the widths measured along the surface of the sidewall rubber from the tire radially inner side to the tire radially outer side in a state where the tire has the structure.
By setting the thickness of the structure to 1.0 mm or more, the wear resistance of the structure can be improved. The effect on resistance can be suppressed. Also, by setting the width to 30 mm or more, it becomes easier to properly protect the sidewall rubber, and by setting the width to 80 mm or less, it is possible to suppress the increase in tire weight and the impact on tire rolling resistance. can.

<<Structure configuration>>
The structure 4 of this embodiment has a vulcanized rubber layer 41 and a polyurethane foam layer 42, as shown in FIG. have different colored parts.
Specifically, in the example of FIG. 2, the structural body 4 is composed of three layers in the thickness direction of the structural body 4, the barrier layer 43, the first polyurethane foam layer 421, and the vulcanized rubber layer 41. configured in order. Also, the first polyurethane foam layer 421 and the vulcanized rubber layer 41 have different colors.
In the present invention, the "bonding surface" refers to the bonding surface of the structure 4 to the sidewall rubber 3, and the "outer surface" of the structure 4 refers to the sidewall rubber 3. The adhesive surface means the surface on the opposite side of the adhesive surface, and may be abbreviated as "adhesive surface" or "outer surface" hereinafter.
Further, the portions having different colors in the thickness direction of the structure 4 are portions where the color difference ΔE00 of the CIE2000 color difference formula satisfies ΔE00≧10, preferably ΔE00≧30.

Thus, in the present embodiment, by having the barrier layer 43 on the adhesive surface side of the structure 4, the barrier layer 43 is adjacent to the sidewall rubber 3, and the barrier layer 43 serves as an adhesive for the sidewall rubber 3. As a result, when the wear of the vulcanized rubber layer 41 of the structure 4 progresses, it can be easily replaced with a new structure 4 .
In the present embodiment, as the polyurethane foam layer 42, there is a first polyurethane foam layer 421 located adjacent to the barrier layer 43 on the outer surface side of the barrier layer 43 in the structure 4 (polyurethane foam layer 421). layer 42 includes the first polyurethane foam layer 421), it is possible to prevent migration of the anti-aging agent from the sidewall rubber 3 to the polyurethane foam layer 42; to avoid discoloration.
Furthermore, the first polyurethane foam layer 421 is present in the structure 4 (the polyurethane foam layer 42 is present in the structure 4, or is present on the side of the structure 4 bonded to the sidewall rubber 3, The side wall rubber 3 is protected by the vulcanized rubber layer 41 because the vulcanized rubber layer 41 is positioned on the outer surface side of the first polyurethane foam layer 421 . As the wear of the vulcanized rubber layer 41 progresses, the polyurethane foam layer 42 located on the adhesive surface side of the vulcanized rubber layer 41 becomes visible to the user, making it easy to recognize the wear condition of the structure. can.
Furthermore, since the first polyurethane foam layer 421 in the structure 4 covers the sidewall rubber 3, it also functions to impart ozone crack resistance to the tire body.

In the illustrated example, each of the vulcanized rubber layer 41 and the polyurethane foam layer 42 is one layer, but in the present embodiment, the structure 4 includes two or more polyurethane foam layers 42 and vulcanized rubber layers 41. can also be For example, in the illustrated example, the polyurethane foam layer 42 is one layer, but an additional polyurethane foam layer 42 may be provided. In the illustrated example, the vulcanized rubber layer 41 exists on the outermost surface side of the structure 4 , but a polyurethane foam layer 42 may be further provided on the surface of the vulcanized rubber layer 41 .
Further, in the present embodiment, the structure 4 has the barrier layer 43 as shown, but the polyurethane foam layer 42 and the vulcanized rubber layer 41 can be laminated as described above without providing the barrier layer 43. .

In this embodiment, the state in which a plurality of polyurethane foam layers 42 or vulcanized rubber layers 41 are present in the laminate means that different polyurethane foam layers 42 or vulcanized rubber layers 41 differ from each other in thickness of the structure 4. In addition to the state in which they are arranged and laminated so as to overlap in the width direction (the direction perpendicular to the surface of the sidewall rubber 3 when the structure 4 is provided on the sidewall rubber 3), the thickness of the structure 4 A state in which the directions do not overlap and are arranged and combined in a direction along the outer surface of the structure 4 is also included.
In the present embodiment, the structure 4 is a portion in which the polyurethane foam layer 42 and the vulcanized rubber layer 41 are arranged in this order from the adhesive surface side toward the outer surface side in the thickness direction of the structure 4. or the structure 4 has at least a portion in which the vulcanized rubber layer 41 and the polyurethane foam layer 42 are present in the structure 4 in the direction along the outer surface of the structure 4 is preferred.

- First modified example of structure -
Next, a first modified example of the structure of this embodiment will be described.
A first modification of the structure 4 of the present embodiment, as shown in FIG. 4, the barrier layer 43, the first polyurethane foam layer 421 adjacent (laminated) to the barrier layer 43, and the first polyurethane foam layer 421 adjacent (laminated) ) is composed of a vulcanized rubber layer 41 and a second polyurethane foam layer 422 forming the outer surface of the structure 4 . Also, the first polyurethane foam layer 421 and the second polyurethane foam layer 422 have different colors. Furthermore, the vulcanized rubber layer 41 and the second polyurethane foam layer 422 are positioned at the same position when viewed in the thickness direction of the structure 4 and are adjacent to each other in the direction along the outer surface of the structure 4 . In the illustrated example, the vulcanized rubber layers 41 are positioned on the left and right sides of the drawing, and the second polyurethane foam layer 422 is positioned in the center. Although not shown, patterns (characters, drawings, etc.) are formed in the structure 4 in plan view.

In the first modified example, the structure 4 has the structure described above, so that in addition to the effects of the structure 4 of the present embodiment illustrated in FIG. 2, the following effects are obtained.
That is, in the first modification, the polyurethane foam layer 42 is a second polyurethane foam layer 422 that is at least partially present on the outer surface of the structure 4 (in the illustrated example, the second polyurethane foam layer 422 is entirely outside). located on the surface), the visibility of the structure can be improved. In addition, since the pattern is formed by the portion present on the outer surface of the second polyurethane foam layer 422 and the vulcanized rubber layer 41 present on the outer surface of the structure 4 and positioned around the portion. , can further improve the appearance.
In addition, the second polyurethane foam layer 422 (all of the second polyurethane foam layer 422 in the illustrated example), which is present at least partially on the outer surface of the structure 4, has a different color from the second polyurethane foam layer 422. , the first polyurethane foam layer 421 (in the illustrated example, the first polyurethane foam layer 422 is also the third polyurethane foam layer) located on the adhesive surface side of the second polyurethane foam, so the vulcanized rubber layer 41 and the second polyurethane foam layer 422 wear, the color changes from the vulcanized rubber layer 41 to the different colored first polyurethane foam layer 421 and further from the second polyurethane foam layer 422 to the different colored first polyurethane foam layer. Since the color of 421 also changes more clearly, the wear condition can be more easily recognized, so that the user can effectively recognize the replacement timing of the structure 4. FIG. Further, when the second polyurethane foam layer 422 forms a pattern, the pattern due to the second polyurethane foam layer 422 disappears as the wear progresses, which also makes it easier for the user to recognize when to replace the structure 4. Become.

The combination of colors of the first polyurethane foam layer 421 and the second polyurethane foam layer 422 can be arbitrary as long as they develop mutually different colors. The first polyurethane foam layer 421 is made black by containing carbon black (the blackened polyurethane foam layer 42 and the vulcanized rubber layer 41 are different in color to the extent that they can be distinguished), and the first polyurethane foam layer 421 contains a predetermined pigment. It can be made orange by Also, the second polyurethane foam layer 422 can be made white by containing a predetermined pigment.

In the illustrated example, the polyurethane foam layer 42 has two layers, but the polyurethane foam layer 42 may have three or more layers (when the polyurethane foam layer has three or more layers, the barrier layer 43 The polyurethane foam layer adjacent to is the first polyurethane foam layer, and the polyurethane foam layer forming the outer surface of the structure 4 is the second polyurethane foam layer 422, which is positioned on the adhesive surface side with respect to the second polyurethane foam. The polyurethane foam layer becomes the third polyurethane foam layer).
Furthermore, in the illustrated example, one layer of the second polyurethane foam layer 422 exists on the outer surface of the structure 4, but another second polyurethane foam layer 422 having a different color is arranged along the outer surface of the structure 4. , and the second polyurethane foam layer 422 , another second polyurethane foam layer, and the vulcanized rubber layer 41 can form a pattern in plan view of the structure 4 . In this case, the first polyurethane foam layer (bonded to the second polyurethane foam layer 422) which has a color different from that of the second polyurethane foam layer and is located on the adhesive surface side of the second polyurethane foam There may be a first polyurethane foam layer 421 located on the face side, a separate first polyurethane foam layer, or a combination thereof).
Furthermore, in the first modified example, the structure 4 has the barrier layer 43 as shown, but the first polyurethane foam layer 421, the second polyurethane foam layer 422, the first polyurethane foam layer 422, the second polyurethane foam layer 422, and the vulcanized rubber layer 41 can be laminated and combined.

Furthermore, in the structure 4 of the first modified example illustrated in FIG. 3 and the structure 4 of the present embodiment illustrated in FIG. (For example, when a hole is formed in a part of the vulcanized rubber layer 41, or when the second polyurethane foam layer 422 disappears in the case of the first modification). In such a state where wear progresses, at least a part of the polyurethane foam layer 42 exists on the outer surface of the structure 4, so that it is easy for the user to recognize the existence of the structure 4. can.

- Second modification of structure -
Next, a second modification of the structure of this embodiment will be described.
As shown in FIG. 5, a second modification of the structure 4 of the present embodiment has at least two layers and at least three layers (in the illustrated example, two layers) when viewed in the thickness direction of the structure 4. A layer portion and a three-layer portion), and from the adhesive surface side of the structure 4 toward the outer surface side, a barrier layer 43 and adjacent (laminated) layers to the barrier layer 43 and the structure 4 a vulcanized rubber layer 41 forming the outer surface of the vulcanized rubber layer 41, and a polyurethane foam layer 42 having a recess formed in a part of the outer surface of the vulcanized rubber layer 41 and fitted into the recess. The polyurethane foam layer 42 forms the outer surface of the structure 4 together with the vulcanized rubber layer 41 by being fitted into the recesses of the vulcanized rubber layer 41 . In the illustrated example, the vulcanized rubber layers 41 are positioned on the left and right sides of the drawing, the polyurethane foam layer 42 is positioned in the center, and the polyurethane foam layer 42 and the vulcanized rubber positioned around the polyurethane foam layer 42 A pattern is formed by the layer 41 in plan view of the structure 4 .

In the second modification, the structure 4 has the above-described configuration, so that in addition to the effects of the structure 4 of the present embodiment and the first modification illustrated in FIGS. 2 and 3, the following effects are obtained. .
That is, in the second modified example, the vulcanized rubber layer 41 having a recessed portion on the outer surface side is present on the outer surface of the structure 4, and the polyurethane foam layer 42 is fitted into the recessed portion to form the Since the outer surface of the structure 4 is formed together with the vulcanized rubber layer 41, when the vulcanized rubber layer 41 and the polyurethane foam layer 42 wear, the polyurethane foam layer 42 disappears first. The absence of layer 42 makes it possible to recognize the wear situation and also when it is time to replace structure 4 . Moreover, since the vulcanized rubber layer 41 can be made relatively thick, the vulcanized rubber layer 41 can also contribute to the protection of the sidewall rubber 3 .

In the example of FIG. 5, the vulcanized rubber layer 41 and the polyurethane foam layer 42 are each one layer, but the polyurethane foam layer 42 and the vulcanized rubber layer 41 may be two or more layers. A foam layer 42 may also be provided between the barrier layer 43 and the vulcanized rubber layer 41 . Furthermore, although the structure 4 has the barrier layer 43 as shown, the vulcanized rubber layer 41 can be adhered onto the surface of the sidewall rubber 3 without providing the barrier layer 43 .
Specifically, in the second modified example illustrated in FIG. 5, the barrier layer 43 can be removed from the structure 4 of the second modified example, as shown in FIG. Alternatively, in the second modification illustrated in FIG. 5, as shown in FIG. 6, the polyurethane foam layer 42 can be two layers (or two layers or more). By forming the polyurethane foam layer 42 into two or more layers adjacent to each other in the thickness direction, when the vulcanized rubber layer 41 and the polyurethane foam layer 42 wear, the polyurethane foam layer 42 on the outer surface side disappears first, and then the polyurethane foam layer 42 wears away. Since the polyurethane foam layer 42 on the adhesive surface side of the polyurethane foam layer 42 disappears, it is possible to more easily recognize the state of wear and to gradually recognize the replacement timing of the structure 4 . In the example shown in FIG. 6, one layer of vulcanized rubber layer 41 and two layers of polyurethane foam layer 42 which are mutually laminated and which are fitted with recessed portions on the outer surface side thereof. It is composed of (a first polyurethane foam layer 421 and a second polyurethane foam layer 422). The polyurethane foam layer 42 forms the outer surface of the structure 4 together with the vulcanized rubber layer 41 by being fitted into the recesses of the vulcanized rubber layer 41 . In the illustrated example, the vulcanized rubber layers 41 are positioned on the left and right sides of the drawing, the polyurethane foam layer 42 is positioned in the center, and the polyurethane foam layer 42 and the vulcanized rubber positioned around the polyurethane foam layer 42 A pattern is formed by the layer 41 in plan view of the structure 4 .
In addition, in the second modification illustrated in FIG. 5, the polyurethane foam layer 42 can be two layers (or two or more layers) adjacent to each other in the thickness direction (in the example illustrated in FIG. 6, the structure 4 A barrier layer 43 can also be added to the adhesive surface of the .

-Third modification of structure-
Next, a third modified example of the structure of this embodiment will be described.
As shown in FIG. 7, a third modified example of the structure 4 of the present embodiment includes a portion made of a single vulcanized rubber layer 41 and a barrier layer extending from the adhesive surface side of the structure 4 toward the outer surface side. a laminate portion having a layer 43, a first polyurethane foam layer 421, and a second polyurethane foam layer 422 different in color from the first polyurethane foam layer 421 and forming the outer surface of the structure 4; . Further, the barrier layer 43 extends between the portion made of the vulcanized rubber layer 41 and the laminated portion. The vulcanized rubber layer 41 and the second polyurethane foam layer 422 are adjacent to each other with the barrier layer 43 interposed therebetween in the direction along the outer surface of the structure 4 . In the illustrated example, the vulcanized rubber layers 41 are positioned on the left and right sides of the figure, and the second polyurethane foam layer 422 is positioned in the center. A pattern is formed by the vulcanized rubber layer 41 and the barrier layer 43 located at the position of the structure 4 in a plan view.

In the third modification, the structure 4 is configured as described above. Therefore, in addition to the effects of the first and second modifications of the structure 4 of the present embodiment illustrated in FIGS. , the following effects are obtained.
That is, in the third modification, since the structure 4 is composed of a portion made of the vulcanized rubber layer 41 and a laminated portion of the polyurethane foam layer 42, the vulcanized rubber layer 41 is formed separately from the laminated portion. can be made easier. Also, uneven wear of the polyurethane foam layer 42 can be suppressed.

In the illustrated example, the number of layers of the vulcanized rubber layer 41 and the polyurethane foam layer 42 can be changed. Furthermore, although the structure 4 has a barrier layer 43 as shown, the barrier layer 43 may be omitted, or the barrier layer 43 may be interposed between the vulcanized rubber layer 41 and the laminate. It doesn't have to be.

<Tire manufacturing method (tire manufacturing method using vulcanized tire body)>
In the tire manufacturing method of the present embodiment, the vulcanized tire main body 2, the vulcanized rubber layer 41 before or after vulcanization, and the polyurethane foam layer 42 are used to produce the above-described embodiment according to the present invention. of tires. That is, in the tire manufacturing method of the present embodiment, the vulcanized tire body portion 2, for example, the used tire body portion 2 is used to manufacture a tire having the structure 4, so the tire body that has started to be used The part 2 can be reinforced by the structure 4 described above.

In the tire manufacturing method of the present embodiment, the structure 4 is formed on the surface of the sidewall rubber 3 by, for example, attaching the vulcanized structure 4 using a known adhesive, or Using adhesion by vulcanization, the structure 4 before vulcanization can be attached by arranging it on the surface of the sidewall rubber 3 and vulcanizing it. Also, the structure 4 can be formed by arranging and adhering each layer of the structure 4 step by step, or a part of the structure 4 consisting of a part of the layers, on the surface of the sidewall rubber 3 . . Furthermore, the rubber layer of the structure 4 and the polyurethane foam layer 42 can be bonded together using an adhesive or by vulcanizing the rubber layer. Further, the polyurethane foam layers 42 can be adhered to each other by using an adhesive or by pressure bonding by vulcanizing the rubber layers.
Specifically, although not particularly limited, it can be carried out, for example, by the following method.
(i) The vulcanized rubber layer 41 before vulcanization, the polyurethane foam layer 42, and the barrier layer 43 before vulcanization are laminated and combined so as to have a desired configuration, and then vulcanized in advance. , onto the surface of the vulcanized sidewall rubber 3 using a known adhesive.
(ii) After laminating and combining the vulcanized rubber layer 41 before vulcanization, the polyurethane foam layer 42, and the barrier layer 43 before vulcanization so as to have a desired configuration, the vulcanized sidewall rubber 3 is formed. Placed on a surface and then vulcanized. It should be noted that the structure 4 may be arranged on the sidewall rubber 3 with a known adhesive interposed therebetween.
(iii) The vulcanized rubber layer 41 before vulcanization and the polyurethane foam layer 42 are laminated and combined so as to have a desired configuration and then vulcanized, and the barrier layer 43 before vulcanization is also separately vulcanized. Then, after laminating and combining them so as to have a desired configuration to form a structure 4, the structure 4 is pasted on the surface of the vulcanized sidewall rubber 3 using a known adhesive.
(iv) The vulcanized rubber layer 41 before vulcanization and the polyurethane foam layer 42 are laminated and combined so as to have a desired configuration, and then vulcanized. After lamination and combination to form the structure 4, the structure 4 is placed on the surface of the vulcanized sidewall rubber 3 and vulcanized. It should be noted that the structure 4 may be arranged on the sidewall rubber 3 with a known adhesive interposed therebetween.
(v) Vulcanize the barrier layer 43 before vulcanization, and then laminate and combine the barrier layer 43, the vulcanized rubber layer 41 before vulcanization, and the polyurethane foam layer 42 so as to have a desired configuration. After forming the structure 4, the structure 4 is placed on the surface of the vulcanized sidewall rubber 3 and vulcanized. It should be noted that the structure 4 may be arranged on the sidewall rubber 3 with a known adhesive interposed therebetween.

In the tire manufacturing method of the present embodiment, the structure 4 obtained by vulcanizing the pre-vulcanization structure 4 having the vulcanized rubber layer 41, the polyurethane foam layer 42, and the optional barrier layer 43 before vulcanization. is preferably adhered to the surface of the sidewall rubber 3 of the vulcanized tire main body 2 using an adhesive. Thereby, the vulcanized tire body portion 2 (for example, the used tire body portion) can be more easily reinforced by the structure 4 .

In the tire manufacturing method of the present embodiment, for example, when the used tire body portion is used as the vulcanized tire body portion 2, the sidewall rubber 3 of the vulcanized tire body portion 2 is prepared in advance. It is preferable to arrange the surface flat. Specifically, when the used structure 4 is provided on the surface of the sidewall rubber 3 of the tire main body 2, the residue of the used structure 4 is removed from the sidewall rubber 3. It can be removed from the surface and then manufactured.
Further, when the used tire body portion is used as the vulcanized tire body portion 2, the sidewall rubber 3 of the tire body portion 2 is supplemented with the sidewall rubber 3 before vulcanization, and then the structure 4 is formed. can also be formed.

<Tire manufacturing method (tire manufacturing method using tire body before vulcanization)>
In the tire manufacturing method of the present embodiment, the tire body portion 2 of pre-vulcanized rubber, the pre-vulcanized or vulcanized vulcanized rubber layer 41, and the polyurethane foam layer 42 are used. Manufacture tires in the form. That is, in the tire manufacturing method of the present embodiment, a tire having the structure 4 is manufactured using the tire body 2 before vulcanization. can be manufactured in a reinforced state.

In the tire manufacturing method of the present embodiment, the structure 4 is formed on the surface of the sidewall rubber 3 by, for example, using a known adhesive to attach the vulcanized structure 4, or Utilizing adhesion due to vulcanization of rubber, the structure 4 before vulcanization or vulcanization can be placed on the surface of the sidewall rubber 3 and vulcanized to attach it. Also, the structure 4 can be formed by arranging and adhering each layer of the structure 4 step by step, or a part of the structure 4 consisting of a part of the layers, on the surface of the sidewall rubber 3 . . Furthermore, the rubber layer of the structure 4 and the polyurethane foam layer 42 can be bonded together using an adhesive or by vulcanizing the rubber layer/rubber member. Further, the polyurethane foam layers 42 can be adhered to each other by using an adhesive or by pressure bonding by vulcanizing the rubber layers.
Specifically, although not particularly limited, it can be carried out, for example, by the following method.
(i) The vulcanized rubber layer 41 before vulcanization, the polyurethane foam layer 42, and the barrier layer 43 before vulcanization are laminated and combined so as to have a desired configuration, and then vulcanized in advance. , on the surface of the sidewall rubber 3 before vulcanization, using a known adhesive. Then, the sidewall rubber 3 before vulcanization (tire before vulcanization) is vulcanized.
(ii) After laminating and combining the vulcanized rubber layer 41 before vulcanization, the polyurethane foam layer 42, and the barrier layer 43 before vulcanization so as to have a desired configuration, before vulcanization, or after vulcanization separately. It is placed on the surface of the sidewall rubber 3 which has been cured, and then vulcanized. It should be noted that the structure 4 may be arranged on the sidewall rubber 3 with a known adhesive interposed therebetween.
(iii) The vulcanized rubber layer 41 before vulcanization and the polyurethane foam layer 42 are laminated and combined so as to have a desired configuration and then vulcanized, and the barrier layer 43 before vulcanization is also separately vulcanized. Then, after laminating and combining them so as to have a desired configuration to form a structure 4, the structure 4 is pasted on the surface of the sidewall rubber 3 before vulcanization using a known adhesive. . Then, the sidewall rubber 3 before vulcanization (tire before vulcanization) is vulcanized.
(iv) The vulcanized rubber layer 41 before vulcanization and the polyurethane foam layer 42 are laminated and combined so as to have a desired configuration, and then vulcanized. After lamination and combination to form the structure 4, the structure 4 is placed on the surface of the sidewall rubber 3 before vulcanization or before vulcanization and vulcanized. It should be noted that the structure 4 may be arranged on the sidewall rubber 3 with a known adhesive interposed therebetween. Then, the sidewall rubber 3 before vulcanization (tire before vulcanization) is vulcanized.
(v) Vulcanize the barrier layer 43 before vulcanization, and then laminate and combine the barrier layer 43, the vulcanized rubber layer 41 before vulcanization, and the polyurethane foam layer 42 so as to have a desired configuration. After forming the structure 4, the structure 4 is placed on the surface of the sidewall rubber 3 before vulcanization and vulcanized. It should be noted that the structure 4 may be arranged on the sidewall rubber 3 with a known adhesive interposed therebetween.

In the tire manufacturing method of the present embodiment, formation of the structure 4 on the surface of the sidewall rubber 3 is not particularly limited. The barrier layer 43 before vulcanization is arranged on the surface of the sidewall rubber 3 of the tire body 2 before vulcanization so as to form a predetermined laminated/combined state, and the tire body 2 before vulcanization is vulcanized. (that is, vulcanization of the raw tire) to bond the structure 4 to the tire body 2 . Since the structure 4 is vulcanized and adhered together with the vulcanization of the tire main body 2 before vulcanization, the structure 4 can be easily formed on the surface of the sidewall rubber 3 .
However, it is also possible to bond the rubber layers together using a known adhesive. Also, the rubber layer and the polyurethane foam layer 42 can be bonded using an adhesive or by vulcanization. Further, the adhesion of the polyurethane foam layers 42 to each other can also be performed by using an adhesive or by pressure bonding by vulcanization.

〈〈Vulcanized rubber layer〉〉
In the present embodiment, the vulcanized rubber layer is obtained, for example, by vulcanizing a rubber composition described later, and the structure having the vulcanized rubber layer can protect the sidewall rubber.
The rubber component of the rubber composition preferably contains 60 to 100% by mass, more preferably 80 to 100% by mass, and still more preferably 100% by mass of the diene rubber with respect to 100% by mass of the rubber component. be. By setting the content within this range, the vulcanized rubber layer has high strength and excellent abrasion resistance.
Moreover, the rubber component of the rubber composition preferably contains natural rubber and polybutadiene rubber, and more preferably consists of natural rubber and polybutadiene rubber. The mass ratio of natural rubber and polybutadiene rubber (natural rubber/polybutadiene rubber) in the rubber component is preferably 50/50 to 10/90, more preferably 45/55 to 10/90, and 45/ More preferably 55 to 15/85. By adjusting the mass ratio of the natural rubber and the polybutadiene rubber to the above range, the size of the abrasion powder can be reduced, large "flakes" and "chipping" can be suppressed, and the wear resistance is improved.
Synthetic polyisoprene rubber (IR) may be included in the rubber component according to necessity such as workability in manufacturing the rubber composition before vulcanization. Also, the rubber component may be one type of rubber, or may contain two or more types as described above.

In this embodiment, the rubber composition may contain fatty acid amides. As a result, the fatty acid amide migrates (blooms) to the outer surface of the structure, lubricates the outer surface of the structure, and makes the structure less likely to wear.
The content of the fatty acid amide in the rubber composition is preferably 1 part by mass or more, more preferably 1.5 parts by mass or more, and still more preferably 2 parts by mass or more with respect to 100 parts by mass of the rubber component. and particularly preferably 2.5 parts by mass or more. By setting the content to 1 part by mass or more, the fatty acid amide can easily migrate (bloom) to the outer surface of the structure. On the other hand, the content of the fatty acid amide is preferably 25 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 15 parts by mass or less with respect to 100 parts by mass of the rubber component. By setting the content to 25 parts by mass or less, a large amount of blooming occurs from the rubber composition during processing of the rubber composition before vulcanization, causing molding defects (bonding defects of rubber members) with other members during molding. can be avoided.

Although the fatty acid amide is not particularly limited, for example, fatty acid amides having 8 to 22 carbon atoms are preferable. Examples of such fatty acid amides are, but not particularly limited to, caprylic acid amide, lauric acid amide, myristic acid amide, and palmitic acid. Examples include amide, stearic acid amide, behenic acid amide, erucic acid amide, oleic acid amide, linoleic acid amide, and linoleic acid amide. Among these fatty acid amides, oleic acid amide is preferable from the viewpoint of the balance between compatibility with rubber and migration to the surface.

The rubber composition can contain carbon black as a filler. Thereby, the tensile elastic modulus of the vulcanized rubber layer can be improved.
The content of carbon black in the rubber composition is preferably 30 parts by mass or more, more preferably 35 parts by mass or more, and still more preferably 40 parts by mass or more with respect to 100 parts by mass of the rubber component. . By setting the content to 30 parts by mass or more, the tensile elastic modulus of the vulcanized rubber layer can be further improved, and the structure is less likely to wear. On the other hand, the content of carbon black is preferably 70 parts by mass or less, more preferably 65 parts by mass or less, still more preferably 60 parts by mass or less, and particularly preferably 100 parts by mass of the rubber component. is 55 parts by mass or less. By setting the content to 70 parts by mass or less, it is possible to ensure the dispersibility of carbon black and prevent the coefficient of friction of the vulcanized rubber layer from increasing.

Carbon black preferably has a nitrogen adsorption specific surface area (N ₂ SA) of 110 m ² /g or more, more preferably 120 m ² /g or more, still more preferably 130 m ² /g or more, and particularly preferably 135 m ² /g or more. From the viewpoint of suppressing wear of the vulcanized rubber layer, carbon black having a fine particle size is preferable to carbon black having a large particle size, and from this point of view, the higher the nitrogen adsorption specific surface area, the better. On the other hand, the nitrogen adsorption specific surface area is preferably 180 m ² /g or less from the viewpoint of securing workability during production of the rubber composition before vulcanization. The nitrogen adsorption specific surface area of carbon black is measured according to JIS K 6217-2:2001.

Carbon black preferably has a dibutyl phthalate absorption (DBP absorption) of 110 cm ³ /100 g or more, more preferably 115 cm ³ /100 g or more, still more preferably 120 cm ³ /100 g or more, and particularly preferably 125 cm ³ /100 g or more. The higher the dibutyl phthalate absorption amount, the more excellent the abrasion resistance of the vulcanized rubber layer. Generally, from the viewpoint of ease of production, it is preferably 170 cm ³ /100 g or less. When the dibutyl phthalate absorption amount is 110 cm ³ /100 g or more, the carbon black has a high structure and the vulcanized rubber layer has excellent abrasion resistance. The dibutyl phthalate absorption amount of carbon black is measured according to JIS K 6217-4:2008.

In the present embodiment, suitable carbon black includes, for example, N-135 (ASTM rubber carbon black representative value (D1765-93), N ₂ SA: 145 m ² /g, element adsorption amount (IA): 151 g/kg , DBP absorption: 135 cm ³ /100 g); SAF-HS (manufactured by CABOT, trade name “VULCAN 10H”, N ₂ SA: 148 m ² /g, IA: 137 g/kg, DBP absorption: 127 cm ³ /100 g) etc.
One type of carbon black may be used, or two or more types may be used in combination.

In this embodiment, when the rubber composition contains a fatty acid amide, it is preferred that it does not substantially contain silica. Specifically, the rubber composition does not contain silica, or even if it does contain silica, the content is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the rubber component, and is preferably 5 parts by mass. It is more preferably less than 1 part. This is because silica may adsorb fatty acid amides and prevent migration of fatty acid amides to the outer surface of the structure.
In the present embodiment, it is particularly preferable that the rubber composition contains only carbon black as a filler from the viewpoint of enhancing the effect of the fatty acid amide.

In the present embodiment, the rubber composition may optionally contain compounding agents commonly used in the rubber industry, such as vulcanizing agents, vulcanization accelerators, process oils, anti-aging agents, as long as the object of the present invention is not impaired. Anti-scorch agents, zinc white, stearic acid and the like may be included.

In the present embodiment, the rubber composition is obtained by kneading each raw material using a kneader such as a Banbury mixer, a roll, or an internal mixer.
Further, in the present embodiment, the vulcanized rubber layer can be obtained by molding a rubber composition obtained by kneading to obtain a vulcanized rubber layer before vulcanization, and then vulcanizing the vulcanized rubber layer.

<<Polyurethane foam layer>>
In this embodiment, the polyurethane foam layer is a layer containing polyurethane foam. Since the polyurethane foam layer can be distinguished from the vulcanized rubber layer, it is possible to easily recognize when the structure, which is a protective member, needs to be replaced. In addition, since urethane in polyurethane foam does not have unsaturated bonds in its molecular chain, the polyurethane foam layer also functions to impart ozone crack resistance to the tire.

－Polyurethane foam－
The polyurethane foam is not particularly limited, and known polyurethane foams can be used. As for the polyurethane foam, for example, one obtained by foaming a polyurethane resin with a foaming agent or the like can be used.

Examples of polyurethane resins include urethane resins formed from polyol and polyisocyanate.

Examples of polyols include low-molecular-weight polyols and high-molecular-weight polyols. A polyol may be used individually by 1 type, and may be used in combination of 2 or more type.
Examples of low-molecular-weight polyols include ethylene glycol, propylene glycol, 1,4-butanediol, glycerol, trimethylolpropane, 1,2,6-hexanetriol, erythritol and sorbitol.
Examples of polymer polyols include polyether-based polyols and polyester-based polyols.

Examples of polyether-based polyols include polyoxyethylene glycol, polyoxyethylene glyceryl ether, polyoxyethylene trimethylolpropane ether, polyoxyethylene sorbitol ether, polyoxypropylene bisphenol A ether, polyoxypropylene glycol, and polyoxypropylene glyceryl. Ether, polyoxypropylene trimethylolpropane ether, polyoxypropylene sorbitol ether, polyoxyethylene-polyoxypropylene glycol, polyoxyethylene-polyoxypropylene glyceryl ether, polyoxyethylene-polyoxypropylene trimethylolpropane ether, polyoxyethylene -polyoxyalkylene-polyol such as polyoxypropylene sorbitol ether, polyoxyethylene-polyoxypropylene bisphenol A ether, and the like.

Polyester-based polyols include, for example, polyethylene adipate polyol, polybutylene adipate polyol, polyethylene-butylene adipate polyol, and polyethylene terephthalate polyol.

Examples of polyisocyanates include 4,4′-diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), dicyclohexylmethane diisocyanate, xylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, o-toluidine diisocyanate, naphthylene diisocyanate, xylylene diisocyanate, isocyanate, lysine diisocyanate, polymethylene polyphenylene polyisocyanate, and the like. One type of polyisocyanate may be used alone, or two or more types may be used in combination.

Polyurethane foams may be flexible, semi-rigid or rigid foams.

The cell structure of the polyurethane foam is not particularly limited, and may be a closed cell structure, an open cell structure, or a cell structure in which a closed cell structure and an open cell structure are mixed (hereinafter simply referred to as "mixed cell structure"). good. The cell structure of the polyurethane foam is preferably a closed cell structure from the viewpoint of impregnating properties such as binder and carbon black.

The cell diameter of the polyurethane foam may be appropriately adjusted, and is, for example, 250 μm or more and 10 mm or less. The cell diameter is calculated after measuring the number of cells (cells/25 mm) in accordance with JIS K6400-1:2004 Annex 1.

The cell diameter of the polyurethane foam is 10 mm or less, 5 mm or less, 3 mm or less, 1 mm or less, 900 μm or less, 800 μm or less, 700 μm or less, 600 μm or less, 500 μm or less, 450 μm or less, 400 μm or less, 350 μm or less, 300 μm or less, 250 μm or less, and 200 μm. 150 μm or less, or 100 μm or less. The cell diameter of the polyurethane foam can be 250 μm or more, 300 μm or more, 350 μm or more, 400 μm or more, 500 μm or more, 600 μm or more, 700 μm or more, 800 μm or more, 900 μm or more, 1 mm or more, 3 mm or more, or 5 mm or more.

^The ventilation rate of the ^{polyurethane foam} may be adjusted as appropriate. is. Also, the measurement of the ventilation rate is performed according to JIS K6400-7:2012. In one embodiment, the air permeability (cc/cm ² /sec) of the polyurethane foam is 30 or more, or 60 or more, and 500 or less, 200 or less, 150 or less, or 100 or less.

The polyurethane foam preferably has an air permeability of 30 to 500 cc/cm ² /sec at a thickness of 2 mm.
When the air flow rate is 30 cc/cm ² /sec or more, the impregnability of the binder and particles is enhanced, while when the air flow rate is 500 cc/cm ² /sec or less, the crack resistance as a tire is well balanced. improves.

The thickness of the polyurethane foam is typically substantially the same or the same as the thickness of the polyurethane foam layer. The thickness of the polyurethane foam may be appropriately adjusted, and is, for example, 0.5 to 50 mm, preferably 1 to 20 mm.

A commercially available product may be used as the polyurethane foam. Commercially available products of polyurethane foam include, for example, trade names "Everlight (registered trademark) HZCD", "Everlight (registered trademark) HZ", "Everlight (registered trademark) CD" and "Everlight (registered trademark)" manufactured by Bridgestone Chemitech. (registered trademark) HR", "Everlight (registered trademark)" series such as "Everlight (registered trademark) ZC", and the like.

-binder-
In this embodiment, the polyurethane foam layer preferably contains a binder (preferably, the binder is bound to the polyurethane foam).
As a result, the resistance to moist heat of the polyurethane foam layer is improved, the gloss of the tire is maintained, and it is possible to make it easier to recognize when the structural body needs to be replaced.

The binder is not particularly limited, and known binders can be used. Examples of binders include acrylic resins, urethane resins, fluorine resins, polyvinyl alcohol, polyacrylamide, polyvinyl chloride resins, vinyl acetate resins, butadiene resins, epoxy resins, alkyd resins, melamine resins, chloroprene rubbers, and the like. be done. A binder may be used individually by 1 type, and may be used in combination of 2 or more type.

Examples of acrylic resins include acrylic resins, polyacrylic acid ester resins, acrylic acid-styrene copolymer resins, acrylic acid-vinyl acetate copolymer resins, and the like.

In this embodiment, the binder is one or more selected from the group consisting of urethane-based resins, acrylic resins and fluorine-based resins. More preferably, it is one or more selected from the group consisting of urethane resins and acrylic resins. This improves the appearance and makes it easier to recognize when the structure should be replaced.

When a binder is used, a material obtained by combining a binder solution with a design substance described later, such as an acrylic resin-based paint, may be used.

The amount of the binder is not particularly limited and may be adjusted as appropriate. For example, the amount of binder is 12 to 90 parts by weight with respect to 100 parts by weight of polyurethane foam.

The method for binding the binder to the polyurethane foam is not particularly limited, and may be selected as appropriate. The binder may be mixed with the foaming stock solution before foam molding of the polyurethane foam, and the binder may be bound to the polyurethane foam by foam molding. may be combined.

When the binder is brought into contact with the polyurethane foam after foam molding, for example, the polyurethane foam after foam molding in any shape such as sheet-like or disk-like is compressed under pressure, and the compressed polyurethane foam is added to the solution of the binder. The cells of the polyurethane foam are impregnated with the binder by immersing it in a solution of the binder, releasing the pressure in a solution of the binder to expand the polyurethane foam, and then drying to impregnate the binder into the polyurethane foam (e.g., the walls of the cells, etc.). can be bound to Alternatively, for example, a polyurethane foam having an arbitrary shape such as a sheet-like shape or a disk-like shape is immersed in a solution of a binder, pressure is arbitrarily applied and released once or multiple times to the polyurethane foam during immersion, and the cells of the polyurethane foam are can be impregnated with a binder, brought into contact, and then dried to bond the binder to the polyurethane foam (eg, cell walls, etc.).

-designable substances-
In this embodiment, the polyurethane foam layer preferably contains a designable substance. As a result, designability is improved, and it is possible to make it easier to recognize when the structure should be replaced. In addition, the designable substance means a substance that can contribute to improving the appearance or designability of the tire.

Further, "the polyurethane foam layer contains a design substance" means that the polyurethane foam layer contains the design substance. A mode in which the polyurethane foam layer obtained by molding contains a design substance in at least a part of the polyurethane foam layer (e.g., the surface of the polyurethane foam, the inside of the cells, etc.), and an embodiment in which the design substance is brought into contact with the polyurethane foam after foaming. The polyurethane foam layer includes both an embodiment in which the decorative substance is included in at least a portion of the polyurethane foam layer (for example, the surface of the polyurethane foam, the inside of the cells, etc.). Furthermore, in the latter embodiment, the design substance may be in contact with at least a portion of the polyurethane foam. For example, the design substance may be supported in the cells of the polyurethane foam via a binder, The design substance may be carried in the cells of the polyurethane foam without a binder interposed therebetween.

In this embodiment, in the polyurethane foam layer, it is preferable that the binder is bonded to the polyurethane foam, and the design substance is supported on the polyurethane foam via the binder. As a result, the excellent appearance is maintained for a longer period of time, and it is possible to sufficiently recognize when it is time to replace the structure.

In order to support the designable substance on the polyurethane foam via a binder, for example, as described above, the polyurethane foam after foam molding is compressed under pressure, and the compressed polyurethane foam is combined with the binder and the design material. A method in which the polyurethane foam is immersed in a solution containing a functional substance, the pressure is released in the solution to expand the polyurethane foam, and then dried; and drying.

In this embodiment, the design substance is preferably selected from the group consisting of carbon black, pigment, fine metal particles, phosphorescent powder, fluorescent powder, retroreflective particles, color flop particles and chromic materials. As a result, the appearance is further improved, and it is possible to fully recognize when the structure should be replaced. The design substance is not particularly limited as long as it is a component that contributes to improving the appearance or design of the tire. The design substance may be used singly or in combination of two or more.

--Carbon black--
When carbon black is used as the design substance, discoloration of the polyurethane foam layer over time, such as discoloration to yellow, can be suppressed, and the black state of the tire can be maintained for a long period of time. Even if microcracks occur in the polyurethane foam layer, the cracks are made less noticeable, so the appearance of the tire is excellent. In addition, carbon black shall not be included in a pigment in this embodiment.

Carbon black is not particularly limited, and known carbon black can be used. Examples of carbon black include FEF, SRF, HAF, ISAF and SAF grades.

In the present embodiment, carbon black is preferably one or more selected from the group consisting of furnace black. This improves the appearance of the tire while maintaining a high level of crack resistance.

When carbon black is used as the designable substance, the particle size of carbon black is not particularly limited and may be adjusted as appropriate, and is, for example, 10 to 400 nm.

When carbon black is used as the design substance, the cell diameter of the polyurethane foam is preferably 500 μm or less. Thereby, the yellowing resistance and ozone crack resistance of the polyurethane foam can be further enhanced. When carbon black is used as the design substance, the cell diameter of the polyurethane foam is more preferably 450 μm or less, 400 μm or less, or 300 μm or less.

--pigments--
When a pigment is used as the designable substance, the color of the polyurethane foam layer can be set to various colors, so that the designability of the tire is further enhanced.
The pigment is not particularly limited, and known pigments can be used. Examples of pigments include inorganic pigments and organic pigments.

Examples of inorganic pigments include zinc white, zinc dust, lead zincate, aluminum pigments, lead monoxide, mica-like iron oxide pigments, basic lead chromate, basic lead carbonate, red lead, white lead, yellow lead, Ocher, kaolin, clay, ultramarine blue, graphite, goko powder, Prussian blue, iron oxide pigment, iron oxide powder, cyanamide lead, ground calcium carbonate, zinc chromate, talc, ground powder, precipitated calcium carbonate, precipitated barium sulfate, iron yellow , iron black, tono powder, titanium dioxide, chalk, baryte powder, red iron oxide, litharge and the like.

Examples of organic pigments include azo pigments such as soluble azo red, monoazo yellow, monoazo red, disazo yellow, disazo orange, and condensed azo pigments; and phthalocyanine pigments such as copper phthalocyanine blue, copper phthalocyanine green, and cobalt phthalocyanine blue. be done.

The particle size of the pigment is not particularly limited, and may be adjusted appropriately, and is, for example, 50 to 180 nm.

--Metal Fine Particles--
When metal fine particles are used as the designable substance, for example, the polyurethane foam layer can exhibit a metallic color or change color tone depending on the thickness, thereby further enhancing the designability of the tire. In addition, it is possible to make it easier to recognize when the structure should be replaced.

Examples of metals of fine metal particles include gold, silver, copper, aluminum, chromium, molybdenum, nickel, iron, zinc, titanium, platinum, palladium, rhodium, iridium, ruthenium, and osnium.
As the metal fine particles, for example, metal nanoparticles described in JP-A-2017-128469, WO 2013/039180, etc. may be used.

--Luminescent powder--
When a phosphorescent powder is used as the designable substance, for example, a luminescence phenomenon, in which the polyurethane foam layer emits light at night, can be exhibited, thereby further enhancing the designability of the tire. In addition, it is possible to make it easier to recognize when the structure should be replaced.

The phosphorescent powder is not particularly limited, and known phosphorescent powders can be used. As the phosphorescent powder, for example, composition formula: SrAl ₂ O ₄ :Eu, Dy, Sr ₄ Al ₁₄ O ₂₅ : Eu, Dy, SrAl ₂ O ₄ : Eu, Dy+Sr ₄ Al ₁₄ O ₂₅ : Eu, Dy, Sr _{4Al 14} O ₂₅ :Eu,Dy+CaAl ₂ O ₄ :Eu,Nd, CaAl ₂ O ₄ :Eu,Nd, ZnS:Cu,Mn,Co, ZnS:Cu and the like.
Commercially available luminous powders include, for example, pale yellow-green luminous pigments such as the G series manufactured by Nemoto Special Chemical Co., Ltd., and blue-green luminous pigments such as the BG series.

--Fluorescent powder--
When a fluorescent powder is used as a designable substance, for example, a luminescence phenomenon in which the polyurethane foam layer emits light by ultraviolet rays can be exhibited, so that the designability of the tire is further enhanced. In addition, even in situations where visible light is weak, such as dawn, dusk, cloudy weather, fog, and rain, the fluorescent powder emits light in ultraviolet light, making it highly visible to pedestrians and drivers of other vehicles. It also leads to improved safety. In addition, it is possible to make it easier to recognize when the structure should be replaced.

The fluorescent powder is not particularly limited, and known fluorescent powders can be used. Examples of the fluorescent powder include fluorescent pigments described in JP-A-2011-140585 and JP-A-2005-314540.

--Retroreflective Particles--
When retroreflective particles are used as the designable substance, for example, the light incident on the polyurethane foam layer from the light source can be reflected toward the light source, thereby further enhancing the designability of the tire. In addition, it is possible to make it easier to recognize when the structure should be replaced.
The retroreflective particles are not particularly limited, and known retroreflective particles can be used. Examples of retroreflective particles include titanium barium glass.
Commercial products of retroreflective particles include, for example, the UB series manufactured by Unitika Ltd. such as trade names "UB-052NH", "UB-12NH", "UB-23NH", "UB-34NH", and "UB-45NH". etc.

--color flopping particles--
Color flop particles are particles that have the property of changing color tone depending on the angle or distance. When color flop particles are used as the design substance, the color tone changes depending on the angle at which the tire is viewed and the distance from the tire. In addition, it is possible to make it easier to recognize when the structure should be replaced.

The color flop particles are not particularly limited, and known color flop particles can be used. Examples of the color flop particles include interference metal pigments described in JP-A-2012-031232.
Commercially available color flop particles include, for example, an interference color aluminum pigment "Chromashine (registered trademark)" manufactured by Toyo Aluminum Co., Ltd., and the like.

--chromic materials--
A chromic material is a material that changes or develops a color by an external stimulus such as temperature, moisture, or light (eg, ultraviolet rays). When a chromic material is used as a designable substance, for example, the color changes or develops due to the above-described external stimulus, so the designability of the tire is further enhanced.

The chromic material is not particularly limited, and known chromic materials can be used. Examples of chromic materials include temperature indicating materials (thermochromic materials) such as reversible thermochromic microcapsule pigments described in JP-A-2009-019195, low refractive index pigments described in JP-A-2010-208040, and transparent and photochromic materials such as organic photochromic compounds described in JP-A-2004-255041.

Here, in the present embodiment, the polyurethane foam has a cell diameter of 500 μm or less, and the design substance includes carbon black, pigment, fine metal particles, phosphorescent powder, fluorescent powder, retroreflective particles, color flop particles and chromic particles. It is preferably selected from the group consisting of materials. This further improves the appearance of the tire. In addition, it is possible to make it easier to recognize when the structure should be replaced.
Alternatively, the polyurethane foam has a cell diameter of more than 500 μm, and the design substance is selected from the group consisting of pigments, fine metal particles, phosphorescent powders, fluorescent powders, retroreflective particles, color flop particles, and chromic materials. is also preferred. This further enhances the designability of the tire. In addition, it is possible to make it easier to recognize when the structure should be replaced.

In the present embodiment, the polyurethane foam layer contains a designable substance, the designable substance contains particles, and the maximum diameter of the particles is preferably 250 μm or less, more preferably 100 μm or less. This improves the appearance of the tire. In addition, it is possible to make it easier to recognize when the structure should be replaced.

Particles contained in the design substance may be one or more selected from the group consisting of carbon black, pigment, fine metal particles, phosphorescent powder, fluorescent powder, retroreflective particles, color flop particles and chromic materials. .

The amount of the design substance is not particularly limited, and may be adjusted as appropriate. For example, the amount of the design substance is 1 to 100 parts by weight, or 5 to 435 parts by weight with respect to 100 parts by weight of the binder.

-Other ingredients-
In addition to the components described above, the polyurethane foam layer may contain catalysts, antifoaming agents, foaming agents, surfactants, curing agents and the like within the scope of the present invention.

-Method for preparing polyurethane foam layer-
The method for preparing the polyurethane foam layer is not particularly limited. For example, a polyurethane foam is formed by foaming a foaming stock solution containing a polyol and a polyisocyanate, and optionally a catalyst, an antifoaming agent, a foaming agent, a design substance, a binder, and the like. can be obtained. The method for obtaining a polyurethane foam by foam-molding the foaming stock solution is not particularly limited, and for example, a known method such as the method described in JP-A-2011-079232 can be used.

Alternatively, as described above, a polyurethane foam layer may be prepared by bringing a solution containing a binder and a design substance into contact with a polyurethane foam after foam molding to bind the binder to the polyurethane foam.

〈〈Barrier layer〉〉
In this embodiment, the structure can have a barrier layer formed from a rubber composition containing butyl rubber as the rubber component (A) on the bonding surface side of the structure. As a result, if the polyurethane foam layer is positioned adjacent to the barrier layer on the outer surface side of the barrier layer in the structure (in other words, the polyurethane foam layer is adjacent to the sidewall rubber via the barrier layer). ), it is possible to prevent migration of the anti-aging agent from the sidewall rubber to the polyurethane foam layer, thus avoiding brown discoloration of the polyurethane foam layer due to the anti-aging agent. In addition, since the structure has the barrier layer, it can function as an adhesive for the sidewall rubber (after vulcanization), and as a result, the wear of the vulcanized rubber layer of the structure progresses. If so, you can replace it with a new structure.
The barrier layer is preferably positioned adjacent to the polyurethane foam layer on the outer surface side of the barrier layer in the structure, but the barrier layer does not have to be adjacent to the polyurethane foam layer in the structure. Moreover, the barrier layer can also be used in a portion other than the bonding surface side of the structure in the structure.

-Butyl Rubber-
The butyl rubber (IIR) is not particularly limited, and known butyl rubbers can be used. The butyl rubber may be unmodified butyl rubber or modified butyl rubber such as chlorinated butyl rubber and brominated butyl rubber. For example, halide and non-halide versions of butyl rubber are available under the trade name "Exxon Butyl™" (ExxonMobil Chemical Co.). A butyl rubber may be used individually by 1 type, and may be used in combination of 2 or more type.

In the present embodiment, the ratio of butyl rubber in the rubber component (A) in the rubber composition of the barrier layer can be appropriately adjusted. The ratio of the butyl rubber in the rubber component (A) is, for example, 50 parts by mass or more, 60 parts by mass or more, 70 parts by mass or more, 80 parts by mass or more, or 90 parts by mass or more with respect to 100 parts by mass of the rubber component (A). , or 100 parts by mass or more. The ratio of the butyl rubber in the rubber component (A) is, for example, 100 parts by mass or less, 90 parts by mass or less, 80 parts by mass or less, 70 parts by mass or less, or 60 parts by mass or less per 100 parts by mass of the rubber component (A). , or 50 parts by mass or less.

-Rubber components other than butyl rubber-
The rubber composition of the barrier layer may contain a rubber component other than butyl rubber. Rubber components other than butyl rubber include, for example, copolymers and terpolymers of isobutylene and at least one other comonomer. Useful comonomers include, for example, divinyl aromatic monomers, alkyl-substituted vinyl aromatic monomers, combinations thereof, and the like.

Exemplary divinyl aromatic monomers include vinyl styrene.
Exemplary alkyl-substituted vinyl aromatic monomers also include α-methylstyrene and p-methylstyrene.
Additionally, the above copolymers and terpolymers may be halogenated, such as chlorinated, brominated. Halogenated copolymers or terpolymers can also be derived from monomers such as p-bromomethylstyrene.

The rubber composition of the barrier layer includes a copolymer of isobutylene and p-methylstyrene, a terpolymer of isobutylene, isoprene and vinylstyrene, and a brominated copolymer of isobutylene and p-methylstyrene (p-bromomethylstyrene ) and one or more selected from the group consisting of these halides.

Copolymers of isobutylene and p-methylstyrene contain 0.5 to 25% by weight, or 2 to 20% by weight of p-methylstyrene, based on the total weight of the copolymer, with the remainder of the copolymer being isobutylene. good too.
Copolymers of isobutylene and p-methylstyrene may also be halogenated, such as with bromine. If halogenated, the copolymer of isobutylene and p-methylstyrene may contain greater than 0 weight percent and up to 10 weight percent halogen, or from 0.3 to 7 weight percent.

A terpolymer of isobutylene, isoprene, and vinyl styrene comprises 95 to 99 weight percent, or 96 to 98.5 weight percent isobutylene and 0.5 to 5 weight percent, or 0 weight percent, based on the total weight of the terpolymer. .8 to 2.5% by weight of isoprene, the remainder of the terpolymer being vinyl styrene.

In the case of the halide, 0.1 to 10% by weight, or 0.3 to 7% by weight, or 0.5 to 3% by weight of the halogen is contained relative to the total weight of the copolymer or terpolymer. good too.

In the present embodiment, the rubber composition preferably contains brominated isobutylene-p-methylstyrene copolymer rubber (a copolymer of isobutylene and p-methylstyrene). This increases the adhesion between the barrier layer and the sidewall rubber.

For example, halide and non-halide versions of copolymers of isobutylene and p-methylstyrene are available under the tradename "Exxpro™" (ExxonMobil Chemical Co.). Also, for example, a copolymer having p-bromomethylstyrenyl mer units is available under the tradename “Exxpro 3745” (ExxonMobil Chemical Co.). Halide and non-halide versions of terpolymers of isobutylene, isoprene and vinylstyrene, for example, are also available under the trade name “Polysar Butyl™” (Lanxess; Germany).

Copolymers of isobutylene and p-methylstyrene, terpolymers of isobutylene, isoprene and vinylstyrene, brominated copolymers of isobutylene and p-methylstyrene in the rubber component (A) in the rubber composition of the barrier layer, and these The ratio of one or more selected from the group consisting of halides may be adjusted as appropriate. The ratio in the rubber component (A) is, for example, 5 parts by mass or more, 10 parts by mass or more, 20 parts by mass or more, 30 parts by mass or more, 40 parts by mass or more with respect to 100 parts by mass of the rubber component (A), It can be 50 parts by weight or more, 60 parts by weight or more, 70 parts by weight or more, 80 parts by weight or more, or 90 parts by weight or more. The ratio in the rubber component (A) is, for example, 90 parts by mass or less, 80 parts by mass or less, 70 parts by mass or less, 60 parts by mass or less, or 50 parts by mass or less with respect to 100 parts by mass of the rubber component (A). It can be 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less.

selected from the group consisting of copolymers of isobutylene and p-methylstyrene, terpolymers of isobutylene, isoprene and vinylstyrene, bromides of copolymers of isobutylene and p-methylstyrene, and halides thereof in the rubber component (A); The ratio of the one or more types to be used can be 20 to 30 parts by mass with respect to 100 parts by mass of the rubber component (A).

The rubber component (A) other than butyl rubber may be used singly or in combination of two or more.

-Other ingredients-
In this embodiment, the rubber composition of the barrier layer may contain filler, oil, stearic acid, a cross-linking agent, a co-cross-linking agent, and the like.
The filler for the barrier layer is not particularly limited, and known fillers can be appropriately selected and used. Examples of fillers include silica, carbon black, clay, aluminum hydroxide, alumina, talc, mica, kaolin, glass balloons, glass beads, calcium carbonate, magnesium carbonate, magnesium hydroxide, magnesium oxide, titanium oxide, and potassium titanate. , barium sulfate, and the like. A filler may be used individually by 1 type, and may be used in combination of 2 or more type.

In this embodiment, the rubber composition preferably contains a layered or platy clay mineral (B). As a result, migration of the anti-aging agent from the rubber of the tire is further suppressed, and brown discoloration of the polyurethane foam layer can be further suppressed.

The layered or platy clay mineral (B) preferably has an average aspect ratio of 2-200. When the layered or plate-like clay mineral (B) has an average aspect ratio of 2 or more, the planes of the layered or plate-like clay mineral particles are oriented, which further suppresses brown discoloration of the polyurethane foam layer. Further, if the average aspect ratio of the layered or plate-like clay mineral (B) is 200 or less, the layered or plate-like clay mineral (B) will be more uniformly dispersed during kneading of the rubber composition, and the polyurethane will be produced. Discoloration of the foam layer to brown can be further suppressed. In a preferred embodiment, the average aspect ratio is 3 to 150, 5 to 100, 5 to 50, or 10 to 30 from the viewpoint of suppressing brown discoloration of the polyurethane foam layer. The average aspect ratio is obtained as x/y from the average length x and average thickness y.

In a preferred embodiment, the layered or platy clay mineral (B) has an average particle size (measured by the Malvern Method) of 50 μm or less, 0.2-30 μm, 0.2-5 μm, or 1.5-4. 5 μm. If the layered or plate-like clay mineral (B) has an average particle size of 50 µm or less, the rubber composition will have good flex resistance.

Both natural products and synthetic products can be used as the layered or plate-like clay mineral (B). Examples of layered or platy clay minerals (B) include clays such as kaolin clay, sericite clay, calcined clay, and surface-treated silane-modified clay; montmorillonite, saponite, hectorite, beidellite, steven smectite clay minerals such as site and nontronite; mica, feldspar, vermiculite, halloysite, talc and swelling mica. Among these, clay, mica, talc and feldspar are preferred, clay, mica and talc are more preferred, clay and talc are even more preferred, and clay is particularly preferred, from the viewpoint of suppressing brown discoloration of the polyurethane foam layer. . Among the above clays, kaolin clay is particularly preferred. These layered or plate-like clay minerals (B) may be used singly or in combination of two or more.

In a preferred embodiment, the content of the layered or plate-like clay mineral (B) in the rubber composition of the barrier layer is such that the polyurethane foam layer turns brown with respect to 100 parts by mass of the rubber component (A). 10 parts by mass or more, 15 parts by mass or more, 20 parts by mass or more, or 25 parts by mass or more from the viewpoint of suppressing From a viewpoint, it is 100 mass parts or less, 80 mass parts or less, or 60 mass parts or less.

The content of the filler in the rubber composition for the barrier layer of the tire of the present embodiment is not particularly limited, and may be adjusted as appropriate. can do. The amount of the filler compounded in the rubber composition of the barrier layer is preferably 30 parts by mass or more with respect to 100 parts by mass of the rubber component (A) from the viewpoint of workability and forming the rubber composition of the barrier layer into a sheet. .

The rubber composition for the barrier layer of the tire of the present embodiment may further contain a processability improver (C). The workability improver (C) is a compounding agent that has the effect of improving the workability of the rubber composition by suppressing adhesion to metal parts such as metal rotors of kneading equipment.

The processability improver (C) may be used alone or in combination of two or more.

In a preferred embodiment, the content of the processability improver (C) in the rubber composition of the barrier layer is 0.1 to 20 parts by mass, or 0.1 to 20 parts by mass with respect to 100 parts by mass of the rubber component (A). 1 to 10 parts by mass. If the content of the processability improver (C) is 0.1 parts by mass or more with respect to 100 parts by mass of the rubber component (A), the adhesion of the rubber composition to metal parts can be further suppressed. If it is not more than parts by mass, the effect on physical properties (storage modulus, etc.) of the rubber composition after vulcanization is small.

As the processability improver (C), glycerin fatty acid ester compositions and stearylamine derivatives are preferred. By using a glycerin fatty acid ester composition and/or a stearylamine derivative as the workability improver (C), adhesion of the rubber composition to metal parts can be further suppressed.

In the tire according to the present invention, the processability improver (C) is preferably at least one selected from the group consisting of glycerin fatty acid ester compositions and stearylamine derivatives.
Thereby, the adhesion of the rubber composition to metal parts can be further suppressed.

The glycerin fatty acid ester composition is a composition containing a glycerin fatty acid ester. The glycerin fatty acid ester is a compound in which at least one of the three OH groups of glycerin and a COOH group of a fatty acid are ester-bonded.

The glycerin fatty acid ester may be a glycerin fatty acid monoester (monoglyceride) obtained by esterifying one molecule of glycerin and one molecule of fatty acid, or a glycerin fatty acid diester (diglyceride) obtained by esterifying one molecule of glycerin and two molecules of fatty acid. Glycerin fatty acid triester (triglyceride) in which one molecule and three fatty acid molecules are esterified may be used, or a mixture thereof may be used. The glycerin fatty acid ester is preferably a glycerin fatty acid monoester.

As the glycerin fatty acid ester composition, 1) glycerin fatty acid monoester alone, 2) a mixture of glycerin fatty acid monoester and glycerin fatty acid diester, 3) further, 1) or 2) above, glycerin fatty acid triester or glycerin Containing is preferred.

The glycerin fatty acid ester composition preferably contains a glycerin fatty acid monoester. When the glycerin fatty acid ester composition contains a glycerin fatty acid monoester, adhesion of the rubber composition to metal parts can be further suppressed. In a preferred embodiment, the glycerin fatty acid monoester content in the glycerin fatty acid ester composition is 35 to 100% by mass, 50 to 100% by mass, 60 to 99% by mass, or 85 to 98% by mass. . When the content is 50 to 100% by mass, the processability of the rubber composition can be further improved, which is also preferable from the viewpoint of production.

In a preferred embodiment, the content of the glycerin fatty acid diester in the glycerin fatty acid ester composition reduces the unvulcanized viscosity of the rubber composition, suppresses the discoloration of the polyurethane foam layer to brown, and prevents bending. From the viewpoint of property improvement, it is 65% by mass or less, 55% by mass or less, or 50% by mass or less.

In a preferred embodiment, the content of the glycerin fatty acid triester in the glycerin fatty acid ester composition is, from the viewpoint of reducing the influence on the physical properties of the rubber composition after vulcanization (decrease in storage elastic modulus, etc.), It is 10% by mass or less, 5% by mass or less, or 3% by mass or less, and from the viewpoint of productivity, it may be 0.3% by mass or more.

In a preferred embodiment, the fatty acid constituting the glycerin fatty acid ester has 8 to 28 carbon atoms, 8 to 22 carbon atoms, 10 ~18, 12-18, 14-18, or 16-18. A fatty acid having 8 or more carbon atoms has a high affinity with the rubber component (A), and blooming of the glycerin fatty acid ester composition is less likely to occur. In addition, fatty acids having 28 or less carbon atoms can reduce the production cost of the glycerin fatty acid ester composition.

The fatty acid may be linear or branched, but preferably linear. Further, the fatty acid may be saturated fatty acid or unsaturated fatty acid. The fatty acid is preferably saturated fatty acid. The fatty acid is particularly preferably a linear saturated fatty acid.

Specific examples of the fatty acids include caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, linoleic acid, linolenic acid, araginic acid, arachidonic acid, and behenic acid. is mentioned. Preferred fatty acids are lauric acid, myristic acid, palmitic acid and stearic acid, and more preferred are palmitic acid and stearic acid.

As the glycerin fatty acid ester, specifically, lauric acid monoglyceride, myristate monoglyceride, palmitic acid monoglyceride, and stearic acid monoglyceride are preferable, and palmitic acid monoglyceride and stearic acid monoglyceride are more preferable.

Glycerin may remain as an unreacted raw material during the production of the glycerin fatty acid ester composition. In a preferred embodiment, the content of glycerin in the glycerin fatty acid ester composition is 10% by mass or less, 5% by mass or less, or 3% by mass or less from the viewpoint of suppressing deterioration of heat resistance. From the viewpoint of, it may be 0.3% by mass or more.

The glycerin fatty acid ester composition can be produced by an esterification method produced from glycerin and a fatty acid, or by an ester exchange method using oils and fats and glycerin as raw materials, and the amount of monoester in the glycerin fatty acid ester composition is Methods for producing controlled products include the following methods 1) to 3).

1) A method of controlling the equilibrium composition of esterification by changing the charging ratio of the fatty acid component and the glycerin component in the above esterification method, transesterification method, or the like. Here, glycerin can be further removed by distillation. However, in view of reaction characteristics, the upper limit of the amount of glycerin fatty acid monoester is considered to be around 65% by mass.

2) A method in which the reaction product obtained by the esterification method or the transesterification method is further fractionally distilled by molecular distillation or the like to obtain a glycerin fatty acid ester composition having a high monoester purity (usually 95% by mass or more).

3) By mixing the glycerin fatty acid ester composition obtained by the method of 2) with the glycerin fatty acid ester composition obtained by the method of 1) in an arbitrary ratio, about 65 to 95% by mass of monoester A method for obtaining a glycerin fatty acid ester composition containing

Glycerin fatty acid esters with reduced environmental load can be used by using naturally derived oils and fats, fatty acids, etc., as the raw materials.

As raw materials for fatty acids, those obtained by hydrolyzing oils such as vegetable oils and animal oils, and those obtained by hardening or unhardening these oils and fats or hydrolyzed fatty acids can be used. In addition, the oil and fat raw materials are not particularly limited, but vegetable oils and animal oils and fats are used, and specific examples include palm oil, soybean oil, olive oil, cottonseed oil, coconut oil, palm kernel oil, beef tallow, lard, fish oil, and the like. can be used.

As the glycerin fatty acid ester composition, it is possible to use a commercially available product with a controlled amount of monoester. -95 etc.).

The monoglyceride content (glycerin fatty acid monoester content) in the glycerin fatty acid ester composition is determined according to the following formula (I) by GPC analysis (gel permeation chromatography), and is glycerin, monoglyceride, diglyceride. It means the area ratio of monoglyceride to the total of (glycerin fatty acid diester) and triglyceride (glycerin fatty acid triester) in GPC analysis.
Monoglyceride content (% by area) = MG/(G + MG + DG + TG) x 100
(I)
In the above formula (I), G is the glycerol area of GPC, MG is the monoglyceride area of GPC, DG is the diglyceride area of GPC, and TG is the triglyceride area of GPC.
In addition, the measurement conditions of GPC are as follows.

<GPC measurement conditions>
GPC measurement was carried out using the following measurement apparatus, flowing THF (tetrahydrofuran) as an eluent at a flow rate of 0.6 mL/min, stabilizing the column in a constant temperature bath at 40 ° C., and dissolving 1% by mass in THF there. Measurement is performed by injecting 10 μL of the sample solution.
Standard material: Monodisperse polystyrene Detector: RI-8022 (manufactured by Tosoh Corporation)
Measuring device: HPLC-8220 GPC (manufactured by Tosoh Corporation)
Analysis column: 2 TSK-GEL SUPER H1000 and 2 TSK-GEL SUPER H2000 connected in series (manufactured by Tosoh Corporation)

Similarly, the diglyceride content in the glycerin fatty acid ester composition means the area ratio of diglyceride in GPC analysis to the total of glycerin, monoglyceride, diglyceride and triglyceride, and the triglyceride content in the glycerin fatty acid ester composition means glycerin, It means the area ratio in GPC analysis of triglycerides to the sum of monoglycerides, diglycerides and triglycerides.

Examples of the glycerin fatty acid ester composition whose monoglyceride content is controlled include, for example, a composition containing glyceryl caprylate having a fatty acid with 8 carbon atoms, a composition containing glyceryl decanoate having a fatty acid with 10 carbon atoms, and laurin having 12 carbon atoms as a fatty acid. A composition containing glyceryl acid, a composition containing glyceryl myristate having a fatty acid having 14 carbon atoms, a composition containing glyceryl palmitate having a fatty acid having 16 carbon atoms, a composition containing glyceryl stearate having a fatty acid having 18 carbon atoms, and a fatty acid having 22 carbon atoms Glyceryl behenate-containing composition, C28 fatty acid glyceryl montanate-containing composition, etc. Among these, glyceryl laurate-containing composition, glyceryl palmitate-containing composition, glyceryl stearate-containing composition preferable. One or two or more of these glycerin fatty acid ester compositions with a controlled monoester content are arbitrarily selected and blended.

The glycerin fatty acid ester composition preferably comprises a glycerin fatty acid ester, the glycerin fatty acid ester is an ester of glycerin and two or more fatty acids, and two or more fatty acids constituting the glycerin fatty acid ester. Among them, the fatty acid component in the largest amount is preferably 10 to 90% by mass based on the total fatty acid, and the monoester component is preferably included in 50 to 100% by mass based on the glycerin fatty acid ester. Here, the fatty acid component is considered to be one component for each fatty acid having the same number of alkyl carbon atoms, steric configuration and bonding state, that is, for each stereoisomer. For example, even with the same 18-carbon fatty acid, n-1-octadecanoic acid (general linear stearic acid), 2-octyl-1-decanoic acid (2-position branched stearic acid), cis-9-octadecenoic acid ( Ordinary oleic acid), cis, cis-9,12-octadecadienoic acid (ordinary linoleic acid), etc. are considered as separate components.

In a preferred embodiment, the mass ratio of the two or more kinds of fatty acids is 10 to 90% by mass in the total fatty acid even at the highest fatty acid component, and from the viewpoint of further improving the processability of the rubber composition, it is 15 to 80. % by weight, 20 to 70% by weight, or 30 to 60% by weight.

Further, among the two or more kinds of fatty acids that are raw materials for the glycerin fatty acid ester, one of the fatty acid components having the largest amount and the fatty acid component having the second largest amount is a fatty acid having 16 carbon atoms and the other is a fatty acid having 18 carbon atoms. more preferred. In a preferred embodiment, when the glycerin fatty acid ester is an ester of glycerin with a fatty acid having 16 carbon atoms and a fatty acid having 18 carbon atoms, the mass ratio of the fatty acid having 16 carbon atoms to the fatty acid having 18 carbon atoms (C16 Fatty Acid/C18 Fatty Acid) ranges from 90/10 to 10/90, from 80/20 to 20/80, or from 75/25 to 25/75. If the mass ratio of the fatty acid having 16 carbon atoms and the fatty acid having 18 carbon atoms is within this range, the processability of the rubber composition can be further improved.

The content (% by mass) of the fatty acid component is measured by subjecting the glycerin fatty acid ester to saponification and methyl esterification according to the standard method for analysis of fats and oils established by the Japan Oil Chemists' Society, followed by GPC analysis.

In addition, the glycerin fatty acid ester composition includes a glycerin fatty acid monoester and a glycerin fatty acid diester, and the content of the glycerin fatty acid monoester in the glycerin fatty acid ester composition is 35% by mass or more. It is also preferable that the content of the glycerin fatty acid diester in the ester composition is 65% by mass or less. Such a glycerin fatty acid ester composition can improve the flex resistance of the rubber composition.

In a preferred embodiment, the content of the glycerin fatty acid ester composition is such that the processability of the rubber composition (suppression of adhesion to metal parts) and the polyurethane foam layer are brown with respect to 100 parts by mass of the rubber component (A). From the viewpoint of suppressing discoloration and bending resistance, it is 0.5 parts by mass or more, 1 part by mass or more, 2 parts by mass or more, or 3 parts by mass or more, and the physical properties of the rubber composition after vulcanization (storage modulus, etc.), it is 20 parts by mass or less, 15 parts by mass or less, 12 parts by mass or less, 11 parts by mass or less, or 10 parts by mass or less. In another preferred embodiment, the content of the glycerin fatty acid ester composition is 0.5 to 20 parts by mass, 1 to 15 parts by mass, or 2 to 12 parts by mass with respect to 100 parts by mass of the rubber component (A). parts, 3 to 11 parts by mass, and 3 to 10 parts by mass.

In a preferred embodiment, the content of the glycerin fatty acid ester composition is, with respect to 100 parts by mass of the layered or plate-like clay mineral (B), from the viewpoint of workability of the rubber composition (suppression of adhesion to metal parts). is 0.1 parts by mass or more, 0.25 parts by mass or more, 0.5 parts by mass or more, or 1 part by mass or more, and the effect on physical properties (storage modulus, etc.) after vulcanization of the rubber composition is From the viewpoint of miniaturization, it is 20 parts by mass or less, 15 parts by mass or less, 12 parts by mass or less, 10 parts by mass or less, 8 parts by mass or less, or 7 parts by mass or less. In another preferred embodiment, the content of the glycerin fatty acid ester composition is 0.1 to 20 parts by mass, 0.25 to 15 parts by mass with respect to 100 parts by mass of the layered or platy clay mineral (B). 0.25 to 10 parts by weight, 0.5 to 8 parts by weight, or 1 to 7 parts by weight.

In a preferred embodiment, the content of the glycerin fatty acid triester in the rubber composition of the present invention is the rubber component ( A) With respect to 100 parts by mass, it is 0.5 parts by mass or less, 0.3 parts by mass or less, or 0.1 parts by mass or less, and from the viewpoint of productivity, even if it is 0.01 parts by mass or more good.

In a preferred embodiment, the content of glycerin in the rubber composition of the present invention is from 0.5 parts by mass or less to 0.3 parts by mass with respect to 100 parts by mass of the rubber component (A), from the viewpoint of suppressing deterioration in heat resistance. It is 0.1 part by mass or less, or 0.1 part by mass or less, and may be 0.01 part by mass or more from the viewpoint of productivity.

The stearylamine derivative is a derivative of stearylamine, preferably a compound in which the hydrogen of the amino group of stearylamine is substituted with an alkyl group. Here, the alkyl group includes a methyl group, an ethyl group, a propyl group, a butyl group and the like.

Specific examples of the stearylamine derivative include dimethylstearylamine, diethylstearylamine, dipropylstearylamine, ethylmethylstearylamine, ethylpropylstearylamine, and methylpropylstearylamine. Stearylamine is preferred.

In a preferred embodiment, the content of the stearylamine derivative is 0.1 to 10 parts by mass, 0.2 to 5 parts by mass, or 0.5 to 2 parts by mass with respect to 100 parts by mass of the rubber component (A). part by mass. If the content of the stearylamine derivative is 0.1 parts by mass or more with respect to 100 parts by mass of the rubber component (A), the adhesion of the rubber composition to metal parts can be further suppressed. If there is, the effect on physical properties (storage modulus, etc.) of the rubber composition after vulcanization is small.

In one embodiment, the rubber composition of the barrier layer does not contain stearic acid (D), or the content of stearic acid (D) is 0.1 mass parts per 100 mass parts of the rubber component (A). It is below the department. By not containing the stearic acid (D) or by setting the content to 0.1 parts by mass or less, the aggregation of the layered or plate-like clay mineral (B) can be suppressed, and the layered or plate-like clay mineral (B) can be prevented from As a result of improved dispersibility, discoloration of the polyurethane foam layer to brown is further suppressed.

In a preferred embodiment, the content of stearic acid (D) is 0.05 parts by mass or less, or 0.02 parts by mass or less per 100 parts by mass of the rubber component (A). In another preferred embodiment, it does not contain stearic acid (D). The smaller the content of stearic acid (D), the more the polyurethane foam layer is prevented from discoloring to brown, the barrier layer is more likely to adhere to the sidewall rubber, and the rubber composition contains stearic acid (D). If it is not contained, the brown discoloration of the polyurethane foam layer is further suppressed, and the barrier layer is more likely to adhere to the sidewall rubber. Although not wishing to be bound by theory, by not including stearic acid (D) or by making the content of stearic acid (D) 0.1 parts by mass or less, the pH of the rubber composition is increased, and the pH is increased. It is presumed that this makes it difficult for the layered or plate-like clay mineral (B) to agglomerate.

In the tire according to the present embodiment, the rubber composition further contains a layered or plate-like clay mineral (B) and at least one of a workability improver (C) and a metal salt of an unsaturated carboxylic acid (E). including
It is preferable that the stearic acid (D) is not included or the content of the stearic acid (D) is 0.1 parts by mass or less per 100 parts by mass of the rubber component (A).
As a result, the polyurethane foam layer can be further prevented from discoloring to brown, has low adhesion to metal parts, and facilitates adhesion of the barrier layer to the sidewall rubber.

The tire according to the present embodiment preferably contains the processability improver (C) and the metal salt of unsaturated carboxylic acid (E).
Thereby, the adhesion of the rubber composition to metal parts can be further suppressed.

The unsaturated carboxylic acid metal salt (E) may be used alone or in combination of two or more.

Examples of the unsaturated carboxylic acid constituting the unsaturated carboxylic acid metal salt (E) include α,β-ethylenic unsaturated acids such as acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, angelic acid, and cinnamic acid. Saturated carboxylic acid and the like can be mentioned. Among these, acrylic acid and methacrylic acid are preferable as the unsaturated carboxylic acid.

The unsaturated carboxylic acid metal salt (E) is preferably at least one selected from the group consisting of metal acrylates and metal methacrylates. Thereby, it can suppress more that a polyurethane-foam layer discolors to brown.

Examples of metals constituting the unsaturated carboxylic acid metal salt (E) include sodium, potassium, lithium, calcium, barium, magnesium, zinc, aluminum, tin, zirconium, and cadmium. Among these metals, sodium, magnesium, zinc and aluminum are preferred, and zinc is particularly preferred. That is, unsaturated carboxylic acid zinc is preferable as the unsaturated carboxylic acid metal salt (E).

Specific examples of the unsaturated carboxylic acid metal salt (E) include zinc diacrylate, zinc dimethacrylate, zinc monoacrylate, zinc monomethacrylate, magnesium diacrylate, magnesium dimethacrylate, and magnesium monoacrylate. , magnesium monomethacrylate and the like.

The unsaturated carboxylic acid metal salt (E) is preferably at least one selected from the group consisting of zinc dimethacrylate and zinc monomethacrylate. By including zinc dimethacrylate and/or zinc monomethacrylate in the rubber composition, discoloration of the polyurethane foam layer to brown can be further suppressed.

In a preferred embodiment, the content of the unsaturated carboxylic acid metal salt (E) is 0.1 to 3.8 parts by mass, 0.2 to 3 parts by mass, relative to 100 parts by mass of the rubber component (A). parts by weight, or 0.3 to 2 parts by weight. When the content is 0.1 parts by mass or more, it is possible to further suppress the polyurethane foam layer from discoloring to brown, and when the content is 3.8 parts by mass or less, rubber scorching of the rubber composition can be sufficiently suppressed.

In a preferred embodiment, the ratio of the content of the unsaturated carboxylic acid metal salt (E) to the content of the layered or plate-like clay mineral (B) is 0.1 to 38% by mass, 0.2 to 30% by mass, 0.5 to 10% by mass. When the ratio is in the range of 0.1 to 38% by mass, the layered or platy clay mineral (B) and the unsaturated carboxylic acid metal salt (E) can be efficiently coupled, and the polyurethane foam can be obtained. Discoloration of the layer to brown can be further suppressed.

-Dimensions of barrier layer-
The thickness of the barrier layer is not particularly limited, and may be adjusted as appropriate. The thickness of the barrier layer is preferably from 0.1 to 2 mm, more preferably from 0.3 to 1 mm, from the viewpoints of suppressing migration of the antioxidant to the barrier layer and reducing the weight of the barrier layer.

Although the embodiments of the present invention have been described above with reference to the drawings, the tire and tire manufacturing method of the present invention are not limited to the above examples.

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples.

As a tire of the example, a structure having the structure shown in FIG. 7 was formed on the surface of the sidewall rubber of the vulcanized tire main body. Specifically, a letter "B" hole was formed in the vulcanized rubber layer (dimensions: 100 mm x 200 mm) before vulcanization using a letter "B" type punching blade. Next, a first polyurethane foam layer (color: white, thickness: 10 mm), a second polyurethane foam layer (color: red, thickness: 2 mm), and a barrier layer ( thickness: 0.5 mm) was laminated on the cutout portion of the vulcanized rubber layer before vulcanization to obtain a structure before vulcanization. Next, the structure before vulcanization was placed on the surface of the sidewall rubber of the vulcanized tire body, and vulcanized at 160° C. for 15 minutes to obtain the tire of the example.
The composition of the vulcanized rubber layer before vulcanization is as follows.
・Rubber sheet composition (assuming sidewall rubber, which is the outer layer of the tire)
Natural rubber (NR): RSS#3, 40 parts by mass Butadiene rubber (BR): Trade name "JSR BR01" manufactured by JSR, 60 parts by mass Carbon black: N234, 27 parts by mass Silica: A product manufactured by Tosoh Silica Corporation Name “Nipsil (registered trademark) AQ”, 27 parts by mass Silane coupling agent: 2.5 parts by mass Process oil: 15 parts by mass Anti-aging agent: Trade name “Nocrac (registered trademark) 6C” manufactured by Ouchi Shinko Chemical Industry Co., Ltd. ", 3 parts by mass Stearic acid: 2 parts by mass Zinc oxide: 3 parts by mass Sulfur: 1.5 parts by mass Vulcanization accelerator (DPG): 0.8 parts by mass Vulcanization accelerator (DM): 1 part by mass Vulcanization Accelerator (NS): 1 part by mass The composition of the first polyurethane foam layer is as follows.
・Polyurethane foam, trade name “HZCD” manufactured by Bridgestone Chemitech, closed cell structure, cell diameter = 350 μm, ventilation rate at 2 mm thickness = 150 cc/cm2/sec
Binder acrylic resin: trade name "BS050301-1" manufactured by Enex, acrylic emulsion Further, the composition of the second polyurethane foam layer is as follows.
・Polyurethane foam, trade name “HZCD” manufactured by Bridgestone Chemitech, closed-cell structure, cell diameter = 350 μm, ventilation rate at 2 mm thickness = 150 cc/cm ² /sec
・ Binder fluororesin: trade name “F101” manufactured by E-Tech Co., Ltd.
・Design substance Pigment: Trade name “PSM Red” manufactured by Mikuni Color Co., Ltd., azo red pigment, nonionic surfactant content, pigment solid content = 32.0%, 25.5 per 100 parts by mass of binder Parts by Mass Furthermore, the composition of the barrier layer is as follows.
・Rubber composition material for barrier layer <rubber component (A)>
Brominated butyl rubber (Br-IIR): high viscosity butyl, trade name "Bromobutyl 2255" manufactured by Exxon, 100 parts by mass <filler>
Clay (layered or platy clay mineral (B)): J.I. M. Huber's trade name "Polyfil DL", average aspect ratio = 20, average particle size = 3.2 µm, 30 parts by mass Carbon black: Asahi Carbon Co., Ltd.'s trade name "Asahi #55", 40 parts by mass <Others>
Zinc monomethacrylate (metal salt of unsaturated carboxylic acid (E)): ZMMA manufactured by Cray Valley, trade name "Dymalink 708F", 0.8 parts by mass Sulfur: 0.68 parts by mass Vulcanization accelerator (DM) : Di-2-benzothiazolyl disulfide, trade name "Noccellar (registered trademark) DM" manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd., 1 part by mass Zinc oxide: 2 parts by mass Glycerin fatty acid ester composition (processability improver ( C)): According to the method described in Production Example 1 of International Publication No. WO 2014/185545, glycerin fatty acid prepared by synthesizing the same molar amount of palm-derived hardened fatty acid from octanoic acid and further molecularly distilling. Ester composition, glycerin fatty acid monoester content = 97% by weight, 54% by weight of the constituent fatty acids is stearic acid, 42% by weight is palmitic acid, and 4% by weight is other fatty acids. 1 part by mass.
When the tire of the above example was run for 10 km while contacting the curb so that the structure was worn, the color of the first polyurethane foam layer changed to the color of the second polyurethane foam layer, indicating that it was time to replace the structure. turned out to be

ADVANTAGE OF THE INVENTION According to this invention, the tire which can be used effectively for a long period of time, and the manufacturing method of a tire can be provided.

1: tire, 2: tire body, 3: sidewall rubber, 4: structure,
41: vulcanized rubber layer, 42: polyurethane foam layer,
421: first polyurethane foam layer, 422: second polyurethane foam layer,
43: Barrier layer

Claims (13)

Having a structure having a vulcanized rubber layer and a polyurethane foam layer on the surface of the sidewall rubber of the tire body,
The structure has portions with different colors in the thickness direction of the structure ,
A tire , wherein the polyurethane foam layer comprises a binder . 2. The tire of claim 1 , wherein said polyurethane foam layer comprises a decorative material. The tire according to claim 1 or 2 , wherein the structure has a barrier layer formed from a rubber composition containing butyl rubber as the rubber component (A) on the side of the surface to be bonded to the sidewall rubber. 4. The tire of claim 3 , wherein the polyurethane foam layer comprises a first polyurethane foam layer located adjacent to and on the opposite side of the barrier layer from the adhesive side. 5. The polyurethane foam layer has a second polyurethane foam layer, at least a part of which is present on the outer surface of the structure on the side opposite to the surface bonded to the sidewall rubber. The tires described in . A portion of the second polyurethane foam layer present on the outer surface of the structure, and a portion of the second polyurethane foam layer present on the outer surface of the structure and positioned around the portion present on the outer surface of the structure. The tire according to claim 5 , wherein a pattern is formed by said vulcanized rubber layer. The polyurethane foam layer is two or more layers,
a second polyurethane foam layer, at least a portion of which is present on the outer surface of the structure on the side opposite to the surface to which the sidewall rubber is adhered; and a color of the second polyurethane foam layer. 7. The tire according to any one of claims 1 to 6 , comprising a third polyurethane foam layer which is different and located on the adhesive surface side with respect to the second polyurethane foam. The rubber composition of the barrier layer contains a layered or platy clay mineral (B) and at least one of a processability improver (C) and a metal salt of an unsaturated carboxylic acid (E),
The rubber composition of the barrier layer does not contain stearic acid (D), or the content of stearic acid (D) is 0.1 parts by mass or less per 100 parts by mass of the rubber component (A). 4. A tire according to claim 3 . 9. The tire according to claim 8 , wherein the barrier layer rubber composition comprises the processability modifier (C) and a metal salt of an unsaturated carboxylic acid (E). The rubber composition of the barrier layer contains a processability improver (C),
The tire according to claim 8 or 9 , wherein the processability improver (C) is at least one selected from glycerin fatty acid ester compositions and stearylamine derivatives.
thing. The rubber composition of the barrier layer contains a metal salt of unsaturated carboxylic acid (E),
The tire according to any one of claims 8 to 10 , wherein the unsaturated carboxylic acid metal salt (E) is at least one selected from a metal acrylate and a metal methacrylate. The tire according to any one of claims 1 to 11 is manufactured by using a vulcanized tire body portion , a rubber layer before vulcanization or the vulcanized rubber layer that has been vulcanized, and the polyurethane foam layer. A method for manufacturing a tire, characterized by manufacturing. The tire according to any one of claims 1 to 11 is manufactured by using the tire body portion before vulcanization , the rubber layer before vulcanization or the vulcanized rubber layer that has been vulcanized, and the polyurethane foam layer. A method for manufacturing a tire, characterized by manufacturing.

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