JP2021094963A - tire - Google Patents

Abstract

To provide a tire which uses a reinforcement cord including a polyamide multifilament as a reinforcement cord of a tire reinforcement member and has improved endurance and low rolling resistance.SOLUTION: In a tire 10 provided with a belt 2 composed of at least one belt layer outside in a tire radial direction of a carcass 1 and at least one belt reinforcement layer 3 in a tire radial direction of the belt 2, at least either the carcass 1 or the belt reinforcement layer 3 has as a structural element a rubber-cord composite composed of a reinforcement cord which contains a semiaromatic polyamide multifilament composed of condensation polymer of dicarboxylic acid and non-aromatic diamine containing aromatic dicarboxylic acid or diamine condensation polymer containing non-aromatic dicarboxylic acid and aromatic diamine, and rupture strength per filament composing the multifilament is 15 cN or larger.SELECTED DRAWING: Figure 1

Description

The present invention relates to a tire, and more particularly to a tire having improved performance by using a cord using a polyamide fiber having a predetermined molecular structure as a reinforcing cord of a tire reinforcing member.

In recent years, environmental problems such as global warming due to an increase in _{CO 2 emissions and resource depletion problems have become more serious.} For this reason, tires are required to be lightweight and have low fuel consumption. Conventionally, tires have been actively improved and developed in terms of shape, structure, rubber characteristics such as tread, etc., and the weight has been reduced by reducing the amount of rubber used and the rolling resistance of the tire. , Fuel efficiency has been improved. Since the rubber member is greatly involved in rolling resistance, for example, the loss of the rubber member itself such as tread rubber, bead filler rubber, belt coating rubber, and bead filler rubber can be reduced, and the shape and structure of the rubber member can be adjusted. Low distortion has been studied and optimized.

Recently, with the progress of lowering the loss of the rubber member itself, the involvement of the loss in the rolling resistance due to the dynamic repetitive strain of the members other than the rubber member cannot be ignored. Members other than the rubber member include a carcass ply layer, a belt layer, a belt reinforcing layer, etc. Among these, the belt reinforcing layer has a large strain fluctuation at the time of rolling contact, so that the loss of the belt reinforcing layer is reduced. Technology is desired. Under such circumstances, in Patent Document 1, it can be suitably used as a cap ply layer (belt reinforcing layer) in a tire, has excellent mechanical characteristics such as rigidity, thermal characteristics, etc., and reinforcement with reduced loss only. Cord materials have been proposed.

JP-A-2002-103913

Currently, organic fibers such as polyester, rayon, and nylon are used for reinforcing members of tires. Among these, nylon fiber, which is a polyamide fiber, has an advantage that it has excellent adhesiveness to rubber and also has excellent fatigue resistance as compared with other fiber types. However, fuel efficiency is not always sufficient, and the current situation is that rolling resistance is required to be further improved.

Therefore, an object of the present invention is to use a reinforcing cord containing a polyamide multifilament as a reinforcing cord for a tire reinforcing member as a reinforcing cord for a tire reinforcing member to improve durability and low rolling resistance. To provide.

As a result of diligent studies to solve the above problems, the present inventor has obtained a cord using a multifilament of a filament having a predetermined breaking strength, which is made of a polyamide having a predetermined structure, at least among the carcass and the belt reinforcing layer. We have found that the above problems can be solved by using it as one of the reinforcing cords, and have completed the present invention.

That is, the tire of the present invention is a tire provided with a belt composed of at least one belt layer on the outer side in the radial direction of the carcass tire and at least one layer of a belt reinforcing layer on the outer side in the radial direction of the tire of the belt. ,
At least one of the carcass and the belt reinforcing layer is a rubber and a polycondensate of a dicarboxylic acid containing an aromatic dicarboxylic acid and a non-aromatic diamine or a polycondensate of a diamine containing a non-aromatic dicarboxylic acid and an aromatic diamine. It has a reinforcing cord containing a multi-filament of a semi-aromatic polyamide composed of, and a rubber-cord composite composed of a rubber-cord composite as a constituent element.
The breaking strength per filament constituting the multifilament is 15 cN or more. Here, the breaking strength is a value obtained as a tensile load when the filament constituting the multifilament is broken, and the tensile load is the tensile strength and the elongation rate of JIS-L1013 "Chemical fiber filament yarn test method". It was measured according to the test of.

In the tire of the present invention, the fineness of the filaments constituting the multifilament is preferably 4 dtex or more. Further, in the tire of the present invention, the semi-aromatic polyamide is preferably a polycondensate of an aromatic dicarboxylic acid and a non-aromatic diamine, and the non-aromatic diamine is an aliphatic diamine and an aliphatic diamine. It is preferably at least one of the diamines. Further, in the tire of the present invention, the glass transition temperature of the reinforcing cord taken out from the tire is preferably 80 to 230 ° C. Further, in the tire of the present invention, the ratio of the dynamic elastic modulus E'(100 ° C.) of the reinforcing cord taken out from the tire at 100 ° C. to the dynamic elastic modulus E'(25 ° C.) at 25 ° C., E'. The value of (100 ° C.) / E'(25 ° C.) is preferably 0.7 to 1.0. Furthermore, in the tire of the present invention, the moisture content of the reinforcing cord taken out from the tire is preferably 0.1 to 2.0% by mass.

Further, in the tire of the present invention, the ratio of the loss tangent tan δ (25 ° C.) at 25 ° C. to the loss tangent tan δ (100 ° C.) at 100 ° C. of the reinforcing cord taken out from the tire, tan δ (25 ° C.) / tan δ ( The value of (100 ° C.) is preferably 0.7 to 1.0. Further, in the tire of the present invention, the loss tangent tan δ (25 ° C.) of the reinforcing cord taken out from the tire at 25 ° C. is preferably 0.01 to 0.06. Furthermore, in the tire of the present invention, the ratio of the aromatic dicarboxylic acid to the dicarboxylic acid of the reinforcing cord is preferably 50 mol% or more. Further, in the tire of the present invention, the ratio of the dicarboxylic acid having one aromatic ring to the aromatic dicarboxylic acid is 20 mol% or more, and the dicarboxylic acid having two aromatic rings to the aromatic dicarboxylic acid. The ratio of the dicarboxylic acid having three aromatic rings to the aromatic dicarboxylic acid is 20 mol% or more, and the ratio of the dicarboxylic acid having three aromatic rings is 20 mol% or more. Further, in the tire of the present invention, the ratio of the diamine having 7 to 12 carbon atoms to the diamine is preferably 20 mol% or more. Furthermore, in the tire of the present invention, the reinforcing cord is the multifilament of the polyamide, polyester fiber, nylon fiber, aramid fiber, polyketone fiber, glass fiber, carbon fiber, polyparaphenylene benzobisoxazole fiber and polyallylate. It is preferably a hybrid cord of at least one fiber selected from the group consisting of fibers.

Further, in the tire of the present invention, the reinforcing cord taken out from the tire is the following formulas (1) and (2).
α1 = N1 × √ (0.125 × D1 / ρ) × 10 ^-3 (1)
α2 = N2 × √ (0.125 × D2 / ρ) × 10 ^-3 (2)
(N1 is the number of lower twists [times / 10 cm], D1 is the fineness of one lower twist yarn [dtex], N2 is the number of upper twists [times / 10 cm], D2 is the total fineness of the cord [dtex], and ρ is the reinforcing cord. The lower twist coefficient α1 represented by the density [g / cm ³ ]) is preferably 0.1 to 0.9, and the upper twist coefficient α2 is preferably 0.1 to 1.2. Further, in the tire of the present invention, it is preferable that the α1 is 0.1 to 0.5 and the α2 is 0.1 to 0.7. Furthermore, in the tire of the present invention, the number of lower twists N1 of the reinforcing cord is preferably 10 to 30 times / 10 cm. Further, in the tire of the present invention, the number of upper twists N2 of the reinforcing cord is preferably 10 to 30 times / 10 cm.

The tire of the present invention is suitable for a passenger car tire.

Here, the tan δ of the reinforcing cord is a leolograph solid, a leovibron, a spectrometer, under the conditions of a predetermined temperature, a measurement frequency of 10 Hz, a static tension of 100 g, and a dynamic repeating strain of 1000 μm, with the reinforcing cord having a length of 5 cm. It is a value measured using metravib or the like. The glass transition temperature (Tg) is a value measured by differential scanning calorimetry (DSC). Further, the dynamic elastic modulus E'of the reinforcing cord can be measured under the same conditions as the measurement of tan δ of the reinforcing cord. Furthermore, "the ratio of the dicarboxylic acid having one aromatic ring to the aromatic dicarboxylic acid is 20 mol% or more" means that "the ratio of the structural unit derived from the aromatic dicarboxylic acid to the structural unit derived from the raw material monomer component is 10 mol". It means "% or more". "The ratio of a dicarboxylic acid having two aromatic rings to an aromatic dicarboxylic acid is 20 mol% or more", "the ratio of a dicarboxylic acid having three aromatic rings to an aromatic dicarboxylic acid is 20 mol% or more" and "diamine". The ratio of diamine having 7 to 12 carbon atoms to 20 mol% or more is the same.

According to the present invention, it is possible to provide a tire having improved durability and low rolling resistance by using a reinforcing cord containing a polyamide multifilament as a reinforcing cord of a tire reinforcing member.

It is the schematic sectional drawing in the tire width direction of the tire which concerns on one preferred embodiment of this invention.

Hereinafter, the tire of the present invention will be described in detail with reference to the drawings.
FIG. 1 is a schematic cross-sectional view of a tire according to a preferred embodiment of the present invention in the tire width direction. The tire 10 of the present invention includes a belt 2 composed of at least one belt layer on the outer side of the carcass 1 in the radial direction of the tire, and at least one layer of the belt reinforcing layer 3 on the outer side in the radial direction of the tire of the belt 2. It is a tire. In the illustrated example, the carcass 1 straddling the pair of bead cores 4 is composed of one layer of carcass ply, the belt 2 is composed of two layers of belt layers 2a and 2b, and the bead core 4 is outside in the tire radial direction. A bead filler 5 is arranged in the bead filler 5.

In the illustrated example, the belt reinforcing layer 3 is composed of a cap layer 3a arranged so as to cover the entire belt 2 and a pair of layer layers 3b arranged so as to cover only both ends of the cap layer 3a. The cap layer 3a is arranged so as to intersect and continue with the tire equatorial plane E from one tire half to the other tire half, whereas the layer layer 3b does not intersect with the tire equatorial plane E, respectively. The tire is composed of a pair arranged so as to cover only the end portion of the cap layer 3a in the half portion of the tire. In the tire 10 of the present invention, the belt reinforcing layer 3 may include both the cap layer 3a and the layer layer 3b, or may be only the cap layer 3a. Further, the cap layer 3a may be two or more layers, or may be a combination with two or more layer layers 3b. The belt reinforcing layer 3 is usually composed of a rubberized layer of cords arranged substantially parallel to the tire circumferential direction.

In the tire 10 of the present invention, at least one of the carcass 1 and the belt reinforcing layer 3 is a polycondensate of rubber and a dicarboxylic acid containing an aromatic dicarboxylic acid and a non-aromatic diamine, or a non-aromatic dicarboxylic acid and an aromatic. It has a reinforcing cord containing a multi-filament of a semi-aromatic polyamide composed of a polycondensate of diamine containing a diamine, and a rubber-cord composite composed of a rubber-cord composite as a constituent element. The reinforcing cord made of a multifilament of a semi-aromatic polyamide may have a dicarboxylic acid containing an aromatic dicarboxylic acid or a diamine containing an aromatic diamine, and in particular, the dicarboxylic acid is aromatic. It is preferable that the code uses a multifilament containing a group dicarboxylic acid and the diamine is made of a polyamide using at least one of an aliphatic diamine and an alicyclic diamine. Nylon 66 is generally used as the reinforcing cord of the belt reinforcing layer 3, but since such a reinforcing cord has a low glass transition temperature Tg (50 ° C.), it has low rigidity at high temperature and excellent steering stability. Absent. On the other hand, the reinforcing cord using aramid fiber can secure the rigidity at high temperature, but has a problem that the rigidity is too high and the tire manufacturability is remarkably poor.

On the other hand, the semi-aromatic polyamide has a high Tg due to intermolecular interaction and has an appropriate rigidity. Therefore, by using it as a reinforcing cord for the carcass 1 and the belt reinforcing layer 3, the productivity of the tire is not impaired. , Durability and steering stability at high speeds can be improved. In addition, the loss tangent tan δ in the tire use range is small, which is advantageous for reducing the rolling of the tire. Further, the polyamide fiber composed of an alicyclic dicarboxylic acid and an aliphatic diamine has high water absorption and low physical stability. On the other hand, since the semi-aromatic polyamide fiber has low water absorption, it is possible to secure the stability of physical properties.

Further, in the tire 10 of the present invention, the breaking strength per filament constituting the multifilament is 15 cN or more. If the breaking strength per filament is less than 15 cN, the filament may break ahead and peel off from the viewpoint of rubber-cord adhesion, which is not preferable from the viewpoint of tire durability. In order to secure sufficient strength of the reinforcing member, the breaking strength per filament constituting the multifilament is preferably 15 cN or more.

In the tire 10 of the present invention, the fineness of the filaments constituting the multifilament is preferably 4 dtex or more. In the case of the same fiber, the breaking strength of the filament increases as the fineness increases. That is, the breaking strength of the filament can be adjusted by adjusting the fineness of the filament. However, when the fineness of the filament is increased, adhesive fracture is likely to occur, and the thickness of the coated rubber is increased, which is not preferable from the viewpoint of light weight. The fineness of the filament constituting the multifilament is preferably 15 dtex or less, preferably 5 dtex to 12 dtex.

The breaking strength and fineness of the filaments constituting the multifilament of the semi-aromatic polyamide according to the tire 10 of the present invention are the chemical composition of the semi-aromatic polyamide and the melt spinning in producing the multifilament of the semi-aromatic polyamide. It can be adjusted by appropriately changing the manufacturing conditions such as speed and temperature.

In the tire 10 of the present invention, the Tg of the reinforcing cord taken out from the tire 10 is preferably 80 to 230 ° C. As described above, by using the cord having a high Tg as the reinforcing cord of the carcass 1 and the belt reinforcing layer 3, the loss tangent tan δ in the tire use area can be reduced, and the rolling resistance of the tire 10 can be improved. Further, since the rigidity can be ensured even at a high temperature, the steering stability at a high speed can be improved. Preferably, the Tg is 100-160 ° C.

Further, in the tire 10 of the present invention, the ratio of the loss tangent tan δ (25 ° C.) at 25 ° C. and the loss tangent tan δ (100 ° C.) at 100 ° C. of the reinforcing cord taken out from the tire 10 is tan δ (25 ° C.) / tan δ. The value of (100 ° C.) is preferably 0.7 to 1.0. In particular, the tangent tan δ (25 ° C.) at 25 ° C. of the reinforcing cord taken out from the tire is preferably 0.01 to 0.06. Since such a reinforcing cord has a low tan δ at high temperatures, it is possible to suppress heat generation and improve the durability of the tire at high speeds. Preferably, the value of tan δ (25 ° C.) / tan δ (100 ° C.) is 0.85 to 1.0.

Further, in the tire 10 of the present invention, the ratio of the dynamic elastic modulus E'(25 ° C.) of the reinforcing cord taken out from the tire 10 at 25 ° C. to the dynamic elastic modulus E'(100 ° C.) at 100 ° C., E. The value of'(100 ° C.) / E'(25 ° C.) is preferably 0.7 to 1.0. By setting the value of E'(100 ° C.) / E'(25 ° C.) in the above range, the steering stability at high temperature can be made better. In particular, the reinforcing cord taken out from the tire preferably has a dynamic elastic modulus E'(25 ° C.) at 25 ° C. of 0.7 to 0.8.

Furthermore, in the tire 10 of the present invention, the moisture content of the reinforcing cord taken out from the tire 10 is preferably 0.1 to 2.0% by mass. As described above, the reinforcing cord according to the tire 10 of the present invention, particularly the semi-aromatic polyamide fiber, has low water absorption, so that the stability of the cord physical properties can be ensured. In particular, those having a water content of 0.1 to 2.0% by mass can satisfactorily obtain the effects of the present invention.

The value of tan δ (25 ° C.) / tan δ (100 ° C.) and the value of E'(100 ° C.) / E'(25 ° C.) of the reinforcing cord are determined by the type of reinforcing cord, the number of twists, and the surface of the reinforcing cord. It can be adjusted by appropriately selecting the immersion conditions when immersing in the adhesive to be applied, the type of adhesive, and the heat treatment conditions after the adhesive treatment. Further, in the tire 10 of the present invention, the number of reinforcing cords driven in the carcass 1 and the belt reinforcing layer 3 can be appropriately set according to the strength of the reinforcing cords, and is set to, for example, 20 to 100/50 mm. be able to.

In the tire 10 of the present invention, the reinforcing cords taken out from the tire are represented by the following equations (1) and (2).
α1 = N1 × √ (0.125 × D1 / ρ) × 10 ^-3 (1)
α2 = N2 × √ (0.125 × D2 / ρ) × 10 ^-3 (2)
The lower twist coefficient α1 represented by is preferably 0.1 to 0.9, and the upper twist coefficient α2 is preferably 0.1 to 1.2. Here, N1 is the number of lower twists [times / 10 cm], D1 is the fineness of one lower twist yarn [dtex], N2 is the number of upper twists [times / 10 cm], D2 is the total fineness of the cord [dtex], and ρ is reinforcement. The density of the cord [g / cm ³ ]. By twisting the multifilament of the semi-aromatic polyamide according to the present invention, the strong utilization rate is averaged and the fatigue property is improved. In particular, by satisfying the above conditions, it is possible to achieve both rigidity and fatigue of the reinforcing cord. The tension at the time of twisting is preferably 0.01 to 0.2 cN / dtex.

Further, in the tire 10 of the present invention, it is preferable that α1 is 0.1 to 0.5 and α2 is 0.1 to 0.7. By satisfying these conditions, the rigidity and fatigue of the reinforcing cord can be highly compatible with each other. In particular, the lower twist number N1 of the reinforcing cord is preferably 10 to 30 times / 10 cm, and the upper twist number N2 is preferably 10 to 30 times / 10 cm.

In the tire 10 of the present invention, as the reinforcing cord of the carcass ply and the belt reinforcing layer 3, a cord composed of only the above-mentioned semi-aromatic polyamide multifilament may be used, but a so-called hybrid cord in which other fibers are used in combination is used. May be used. Examples of other fibers include at least one fiber selected from the group consisting of polyester fiber, nylon fiber, aramid fiber, polyketone fiber, glass fiber, carbon fiber, polyparaphenylene benzobisoxazole fiber and polyallylate fiber. be able to.

Next, the material and manufacturing method of the cord using the multi-filament of the semi-aromatic polyamide according to the tire 10 of the present invention will be described in detail. The semi-aromatic polyamide multifilament is a polyamide multifilament composed of a polycondensate of an aromatic dicarboxylic acid and a non-aromatic diamine or a polycondensate of a non-aromatic dicarboxylic acid and an aromatic diamine. The dicarboxylic acid may contain an aromatic dicarboxylic acid, and the diamine may contain an aromatic diamine, but in particular, the dicarboxylic acid contains an aromatic dicarboxylic acid, and the diamine is an aliphatic diamine and a fat. A multifilament made of a polyamide containing at least one of the cyclic diamines is preferable.

<Dicarboxylic acid>
The multifilament of the semi-aromatic polyamide according to the tire 10 of the present invention preferably has a ratio of aromatic dicarboxylic acid to dicarboxylic acid of at least 50 mol% or more, more preferably 60 mol% or more, still more preferably 70 mol% or more. .. Thereby, a multifilament of semi-aromatic polyamide having high Tg, excellent fiber strength and spinnability can be obtained.

The aromatic dicarboxylic acid is not particularly limited and may be appropriately selected depending on the intended purpose. For example, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methyl Examples thereof include aromatic dicarboxylic acids having 8 to 20 carbon atoms, which are unsubstituted or substituted with various substituents such as isophthalic acid and 5-sodium sulfoisophthalic acid. These may be used alone or in combination of two or more.

The semi-aromatic polyamide multifilament used for the reinforcing cord according to the tire 10 of the present invention is an alicyclic dicarboxylic acid having an alicyclic structure having 3 to 10 carbon atoms, as a dicarboxylic acid other than the aromatic dicarboxylic acid. An acid, a linear or branched aliphatic dicarboxylic acid having 3 to 20 carbon atoms, or the like can be used.

Specific examples of the alicyclic dicarboxylic acid having 3 to 10 carbon atoms in the alicyclic structure include 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,3-cyclopentanedicarboxylic acid. And so on. In the reinforcing cord used for the tire 10 of the present invention, the alicyclic dicarboxylic acid may be unsubstituted or have a substituent. Examples of the substituent include an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group and a tert-butyl group. However, it is not limited to this. Among these, 1,4-cyclohexanedicarboxylic acid is preferable from the viewpoint of heat resistance, dimensional stability, strength and the like of the reinforcing cord. As the alicyclic dicarboxylic acid, one type may be used alone, or two or more types may be used in combination.

In addition, the cyclic dicarboxylic acid has geometric isomers of trans form and cis form. For example, 1,4-cyclohexanedicarboxylic acid as a raw material monomer may be used as either a trans form or a cis form, or may be used as a mixture of various ratios of the trans form and the cis form.

Examples of the linear or branched aliphatic dicarboxylic acid having 3 to 20 carbon atoms include malonic acid, dimethylmalonic acid, succinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylglutaric acid, and 2,2. -Diethylsuccinic acid, 2,3-diethylglutaric acid, glutaric acid, 2,2-dimethylglutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecane Examples thereof include, but are not limited to, diacid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, eicosandioic acid, and diglycolic acid.

In general, when the number of aromatic rings contained in the dicarboxylic acid constituting the multifilament of polyamide is increased, the binding force due to the interaction between the aromatic rings between the molecules is increased, and the Tg is increased. Therefore, the aromatic ring contained in the dicarboxylic acid may be adjusted according to the required durability at high speed and steering stability. For example, the ratio of a dicarboxylic acid having one aromatic ring to an aromatic dicarboxylic acid is 20 mol% or more, and the ratio of a dicarboxylic acid having two aromatic rings to an aromatic dicarboxylic acid is 20 mol% or more. , And those in which the ratio of the dicarboxylic acid having three aromatic rings to the aromatic dicarboxylic acid is 20 mol% or more can be appropriately used. When the number of aromatic rings contained in the dicarboxylic acid increases, the melting point (Tm) also rises at the same time, so that the spinning workability of the fiber decreases, but the Tm can be lowered by increasing the number of carbon atoms of the diamine component. It is possible.

<Diamine>
The semi-aromatic polyamide multifilament according to the tire 10 of the present invention has a diamine ratio of 7 to 12 carbon atoms to diamine of 20 mol% or more from the viewpoint of spinning stability, heat resistance, and low water absorption. Is preferable. It is more preferably 30 mol% or more and 80 mol% or less, further preferably 40 mol% or more and 75 mol% or less, and particularly preferably 45 mol% or more and 70 mol% or less.

Generally, a polymer having a high Tg tends to have a high Tm. If the Tm is too high, the polyamide is thermally decomposed at the time of melting, the molecular weight and strength are lowered, coloring and decomposition gas are mixed, and the spinnability is deteriorated. However, by containing 20 mol% or more of diamine having 7 to 12 carbon atoms, it is possible to suppress the Tm to be suitable for melt spinning while maintaining a high Tg. Further, since the polyamide containing a diamine having 7 to 12 carbon atoms has high thermal stability at the time of melting, it is possible to obtain a multifilament having excellent spinning stability and good uniformity. Furthermore, by reducing the concentration of amide groups in the polyamide, it is possible to obtain a multifilament having excellent dimensional stability during water absorption. In particular, 1,9-nonanediamine and 1,10-decamethylenediamine are preferable from the viewpoint of achieving both spinning stability and strength.

The diamine other than 1,9-nonanediamine and 1,10-decamethylenediamine is not particularly limited, and even an unsubstituted linear aliphatic diamine is branched having a substituent such as an alkyl group having 1 to 4 carbon atoms. It may be an aliphatic diamine or an alicyclic diamine. Here, examples of the substituent include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group and the like. Examples of diamines other than 1,9-nonandamine and 1,10-decamethylenediamine include ethylenediamine, propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, and undecamethylenediamine. , Dodecamethylenediamine, Linear aliphatic diamines such as tridecamethylenediamine, 2-methylpentamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2-methyloctamethylenediamine, 2,4-dimethyloctamethylenediamine , 1,4-Cyclohexanediamine, 1,3-cyclohexanediamine, 1,3-cyclopentanediamine and the like.

Further, in the semi-aromatic polyamide multifilament according to the tire 10 of the present invention, aromatic diamine may be added to the diamine as long as the fluidity of the polyamide is not impaired. The aromatic diamine is a diamine containing an aromatic, and examples thereof include, but are not limited to, metaxylylenediamine, orthoxylylenediamine, and paraxylylenediamine.

As the diamine other than 1,9-nonanediamine and 1,10-decamethylenediamine, it is more preferable that the diamine contains 5 to 6 carbon atoms and the ratio of the diamine having 5 to 6 carbon atoms is 20 mol% or more. By copolymerizing a diamine having 5 to 6 carbon atoms in addition to 1,9-nonanediamine and 1,10-decamethylenediamine, a polymer having high crystallinity can be obtained while maintaining an appropriate melting point suitable for spinning. be able to. Examples of the diamine having 5 to 6 carbon atoms include pentamethylenediamine, hexamethylenediamine, 2-methylpentamethylenediamine, 2,5-dimethylhexanediamine, 2,2,4-trimethylhexamethylenediamine and the like. ..

Among diamines having 5 to 6 carbon atoms, 2-methylpentamethylenediamine is preferable from the viewpoint of spinnability, fluidity and strength. If the ratio of 2-methylpentamethylenediamine is too high, 2-methylpentamethylenediamine self-cyclizes and decomposes at the time of melting, causing a decrease in molecular weight, resulting in deterioration of spinnability and strength. The ratio of 2-methylpentamethylenediamine in the diamine needs to be set within a range in which decomposition does not occur at the time of melting while ensuring fluidity, and is preferably 20 mol% or more and 70 mol% or less, more preferably 20 mol%. It is 60 mol% or more, more preferably 20 mol% or more and 55 mol% or less.

Among diamines having 5 to 6 carbon atoms, hexamethylenediamine is preferable from the viewpoint of heat resistance of the reinforcing cord according to the tire 10 of the present invention. If the ratio of hexamethylenediamine is too high, the melting point becomes too high and spinning becomes difficult. Therefore, the ratio of hexamethylenediamine in the diamine is preferably 20 mol% or more and 60 mol% or less, more preferably 20 mol% or more and 50 mol. % Or less, more preferably 20 mol% or more and 45 mol% or less.

The amount of the dicarboxylic acid added and the amount of the diamine added are preferably around the same mol amount in order to increase the molecular weight. Considering the amount of diamine escaping to the outside of the reaction system during the polymerization reaction in the mol ratio, the mol amount of the entire diamine is 0.99 to 1.20 with respect to the mol amount of 1.00 of the entire dicarboxylic acid. It is preferably 0.95 to 1.10, and even more preferably 0.98 to 1.05.

When polymerizing a polyamide from a dicarboxylic acid and a diamine, a known end-capping agent can be further added to control the molecular weight. Examples of the terminal encapsulant include acid anhydrides such as monocarboxylic acid, monoamine and phthalic anhydride, monoisocyanate, monoacid halides, monoesters and monoalcohols, and from the viewpoint of thermal stability. , Monocarboxylic acid, monoamine are preferable. The end sealant may be used alone or in combination of two or more.

In the multifilament of the semi-aromatic polyamide of the reinforcing cord according to the tire 10 of the present invention, the cross ratio is preferably 1.7 or less. The cross ratio is a value obtained by dividing the maximum diameter in the multifilament by the minimum diameter, and is a measure of uniformity between single yarns. Since the strength of the multifilament is pulled by the low physical properties in the strength distribution of the single yarn, the strength does not appear if the variation between the single yarns is large. Therefore, in the semi-aromatic polyamide multifilament according to the tire 10 of the present invention, the cross ratio is preferably 1.7 or less, more preferably 1.6 or less, and further preferably 1.5 or less. When the cross ratio is 1.7 or less, stretching at the single yarn level is uniformly performed, there is little variation in single yarn strength, and excellent strength as a multifilament of semi-aromatic polyamide is exhibited. The lower limit of the cross ratio is 1.0.

<Manufacturing method of semi-aromatic polyamide>
Examples of the method for producing a semi-aromatic polyamide include (1) a method in which an aqueous solution of a dicarboxylic acid / diamine salt or a mixture thereof or a suspension of water is heated and polymerized while maintaining a molten state (thermal melt polymerization method). , (2) A method of increasing the degree of polymerization of the polyamide obtained by the hot melt polymerization method while maintaining the solid state at a temperature below the melting point (hot melt polymerization / solid phase polymerization method), (3) Diamine dicarboxylate. Alternatively, a method of heating an aqueous solution or a suspension of water of the mixture and further melting the precipitated prepolymer with an extruder such as a kneader to increase the degree of polymerization (prepolymer / extrusion polymerization method), (4). A method of heating a suspension of an aqueous solution or water of a diamine / dicarboxylate or a mixture thereof to increase the degree of polymerization of the precipitated prepolymer while maintaining the solid state at a temperature below the melting point of the polyamide (prepolymer / solid). (Phase polymerization method), (5) A method of polymerizing a diamine dicarboxylate or a mixture thereof while maintaining a solid state (solid phase polymerization method), (6) A dicarboxylic acid halide component and a diamine component equivalent to the dicarboxylic acid. Examples thereof include a method of polymerizing using the method (solution method).

As a method for producing a semi-aromatic polyamide, since it is easy to maintain the trans isomer ratio at 85% or less and the color tone of the obtained polyamide is excellent, (1) Fused Deposition Modeling Method or (1) 2) It is preferable to produce the polyamide by the hot melt polymerization / solid phase polymerization method. The polymerization form may be a batch type or a continuous type. The polymerization apparatus is not particularly limited, and examples thereof include known apparatus such as an autoclave type reactor, a tumbler type reactor, and an extruder type reactor such as a kneader.

<Multifilament of semi-aromatic polyamide>
The semi-aromatic polyamide multifilament according to the tire 10 of the present invention is a fibrous version of the above-mentioned semi-aromatic polyamide. Various methods can be used for producing the multi-filament of the semi-aromatic polyamide, but melt spinning is usually used, and it is preferable to use a screw type melt extruder. The spinning temperature (melting temperature) of the polyamide is preferably 300 ° C. or higher and 360 ° C. or lower. If the temperature is 300 ° C. or higher, it is possible to suppress the mixing of undissolved substances due to insufficient heat. When the temperature is 360 ° C. or lower, the thermal decomposition of the polymer and the generation of decomposed gas are significantly reduced, and the spinnability is improved. In the tire of the present invention, the breaking strength of the filament constituting the multifilament of the semi-aromatic polyamide is 15 cN or more, but the breaking strength of the filament is not only the chemical composition of the semi-aromatic polyamide but also the melt spinning. It can be adjusted by appropriately changing the manufacturing conditions such as speed and temperature.

For the semi-aromatic polyamide multifilament cord according to the tire 10 of the present invention, it is preferable to use an adhesive for adhering the rubber constituting the tire and the semi-aromatic polyamide multifilament cord, and this adhesive. As a solution, a resorcin-formalin-latex solution (RFL solution) is preferable.

After adhering the RFL liquid, the RFL liquid is dried, fixed and relaxed. The drying temperature of the RFL liquid is preferably 120 to 250 ° C., more preferably 140 to 200 ° C., and the drying time is preferably 10 seconds or longer, more preferably 20 to 120 seconds. After drying, the twisted material is subsequently heat-treated in the heat set zone and the normalizing zone. The temperature and time in the heat set zone and the normalizing zone are preferably 150 to 250 ° C. and 10 to 300 seconds, respectively. At this time, stretching of 2% to 10% is performed, and it is preferable that stretching of 3% to 9% is performed.

The tire 10 of the present invention includes a belt 2 composed of at least one belt layer on the outer side in the tire radial direction of the carcass 1, and at least one layer belt reinforcing layer 3 on the outer side in the tire radial direction of the belt 2. At least one of 1 and the belt reinforcing layer 3 is made of rubber and a polycondensate of a dicarboxylic acid containing an aromatic dicarboxylic acid and a non-aromatic diamine or a polycondensate of a diamine containing a non-aromatic dicarboxylic acid and an aromatic diamine. Except that it has a reinforcing cord containing a multifilament of a semi-aromatic polyamide and a rubber-cord composite composed of a rubber-cord composite as a constituent element, and the breaking strength per filament constituting the multifilament is 15 cN or more. There is no particular limitation on the above, and a known structure can be adopted. In the tire 10 of the present invention, at least one layer of the carcass ply or the belt reinforcing layer may be made of the rubber-cord composite, and the other layers may have a conventional configuration.

For example, in the example shown in FIG. 1, the carcass 1 is composed of one layer of carcass ply, but in the tire 10 of the present invention, the number of layers of the carcass ply is not limited to this, and two or more layers are used. There may be. Further, when a cord other than the above-mentioned cord made of a multi-filament of semi-aromatic polyamide is used as the reinforcing cord of the carcass 1 and the belt reinforcing layer 3, a known organic fiber cord can be used, and the angle of the cord of the carcass is , The direction substantially orthogonal to the tire circumferential direction, for example, 70 to 90 °. As the organic fiber cord, a commonly used known one can be used. For example, nylon or polyethylene terephthalate (PET) cords can also be used. Further, the locking structure of the carcass ply in the bead portion is not limited to the structure in which the carcass ply is wound and locked around the bead core 4 as shown in the figure, and the end portion of the carcass ply may be sandwiched between two layers of bead cores. (Not shown).

Further, in the illustrated tire 10, the belt 2 is composed of two layers of belt layers 2a and 2b, but in the tire 10 of the present invention, the belt layer may be three or more layers. The belt layer can be, for example, a rubberized layer of a cord extending at an inclination of ± 15 to 40 ° with respect to the tire circumferential direction, preferably a rubberized layer of a metal cord such as steel. For example, the two belt layers 2a and 2b shown in the figure may be laminated so that the metal cords constituting the respective belt layers intersect each other with the tire equatorial plane E in between. The metal cord may be a metal cord in which a plurality of metal filaments are twisted together, or may be a metal cord in which a plurality of metal filaments are bundled without being twisted. Further, a plurality of metal filaments may be arranged in parallel without being twisted, and the metal filaments at that time may be straight or molded.

The form of the metal cord in which a plurality of metal filaments are arranged in parallel without twisting is preferably 2 or more, more preferably 5 or more, preferably 20 or less, and more preferably. Examples thereof include those in which metal filaments are arranged in parallel as a bundle of 12 or less, more preferably 10 or less, and particularly preferably 9 or less.

A rubber-metal cord composite of metal cords in which a plurality of metal filaments are arranged in parallel without being twisted or bundled can be produced by a known method. For example, metal cords can be arranged in parallel at predetermined intervals, and the metal cords can be coated from both the upper and lower sides with a sheet made of an elastomer and having a thickness of about 0.5 mm. Further, the metal filament can be molded by a conventional method using a normal molding machine.

Further, in the tire 10 of the present invention, although not shown, an inner liner may be arranged in the innermost layer. In the tire 10 of the present invention, as the gas to be filled in the tire, normal or variable oxygen partial pressure air or an inert gas such as nitrogen can be used. The tire of the present invention is suitable for a passenger car tire.

Hereinafter, the tire of the present invention will be described in more detail with reference to examples.
<Examples and Comparative Examples>
The type of tire shown in FIG. 1 was manufactured with a tire size of 205 / 55R16. The carcass is composed of a single layer of carcass ply, which is arranged in a direction substantially orthogonal to the tire circumferential direction. Further, as the belt reinforcing layer, one cap layer and one layer layer were arranged so as to be substantially parallel (0 ° to 5 °) in the tire circumferential direction. The structure of the belt reinforcing layer is as shown in Table 1. In the table, the semi-aromatic polyamide mainly consists of terephthalic acid and 1,9-diaminenonane. The physical characteristics of the reinforcing cord are as follows.

The rolling resistance and durability of the obtained tires were evaluated by the following procedure. The values of Tg, tan δ (25 ° C.) / tan δ (100 ° C.), and E'(100 ° C.) / E'(25 ° C.) of the code composed of multifilaments of semi-aromatic polyamide are relative to the dicarboxylic acid. The ratio of the aromatic dicarboxylic acid, the number of twists, the dipping conditions when immersing in the adhesive, and the heat treatment conditions after the adhesive treatment were adjusted.

<Evaluation of adhesion with rubber>
A sample was cut out from the tire so that the length was about 200 mm in the cord direction and the width was 20 evaluation cords. Six cords were raised from this sample every two cords, and the resistance force when the cords were grasped together and peeled off from the sample was divided by the number of cords (6 cords) to obtain a numerical value.

<Rolling resistance>
Each tire is assembled on a regular rim specified by JATMA, the appropriate internal pressure is applied, an appropriate load is applied, and the resistance of each tire in Comparative Example 1 and Comparative Example 2 is directly applied in a drum test at a speed of 80 km / h. It was measured and evaluated by estimating the resistance of each tire based on the breaking strength and fineness of the fibers in Examples 1 to 3. The larger the exponential value, the smaller the rolling resistance and the better. The obtained results are also shown in Table 1.

<Durability>
Assemble the obtained tire to the rim specified by JATMA, fill it with the proper internal pressure, load the proper load, start from a speed of 120 km / h with a drum tester, and step the speed by 10 km / h every 20 minutes. The high-speed durability was evaluated by running while raising the tire and measuring the speed at the time of failure. Comparative Examples 1 and 2 were actually measured, and Examples 1 to 3 were estimated based on the breaking strength and fineness of the fibers. Based on the tires of Comparative Example 1, the equivalent cases were marked with ⊚ and then with ◯. The results are also shown in Table 1.

Ｎｙ６６：ナイロン６６

Ny66: Nylon 66

From the above, it can be seen that the tire of the present invention has improved rolling resistance and durability.

10 Tires 1 Carcass 2 Belts 3 Belt Reinforcement Layer 4 Bead Core 5 Bead Filler

Claims (20)

In a tire having a belt composed of at least one belt layer on the outer side in the radial direction of the carcass tire and at least one layer of a belt reinforcing layer on the outer side in the radial direction of the tire of the belt.
At least one of the carcass and the belt reinforcing layer is a rubber and a polycondensate of a dicarboxylic acid containing an aromatic dicarboxylic acid and a non-aromatic diamine or a polycondensate of a diamine containing a non-aromatic dicarboxylic acid and an aromatic diamine. It has a reinforcing cord containing a multi-filament of a semi-aromatic polyamide composed of, and a rubber-cord composite composed of, as a constituent element,
A tire characterized in that the breaking strength per filament constituting the multifilament is 15 cN or more. The tire according to claim 1, wherein the filaments constituting the multifilament have a fineness of 4 dtex or more. The tire according to claim 1 or 2, wherein the semi-aromatic polyamide is a polycondensate of an aromatic dicarboxylic acid and a non-aromatic diamine. The tire according to any one of claims 1 to 3, wherein the diamine is at least one of an aliphatic diamine and an alicyclic diamine. The tire according to any one of claims 1 to 4, wherein the glass transition temperature of the reinforcing cord taken out from the tire is 80 to 230 ° C. The ratio of the dynamic elastic modulus E'(100 ° C.) at 100 ° C. to the dynamic elastic modulus E'(25 ° C.) at 25 ° C. of the reinforcing cord taken out from the tire, E'(100 ° C.) / E'(25 ° C.) The tire according to any one of claims 1 to 5, wherein the value of (° C.) is 0.7 to 1.0. The tire according to any one of claims 1 to 6, wherein the reinforcing cord taken out from the tire has a moisture content of 0.1 to 2.0% by mass. The ratio of the loss tangent tan δ (25 ° C.) at 25 ° C. to the loss tangent tan δ (100 ° C.) at 100 ° C., and the value of tan δ (25 ° C.) / tan δ (100 ° C.) of the reinforcing cord taken out from the tire are 0. The tire according to any one of claims 1 to 7, which is 7 to 1.0. The tire according to any one of claims 1 to 8, wherein the loss tangent tan δ (25 ° C.) of the reinforcing cord taken out from the tire at 25 ° C. is 0.01 to 0.06. The tire according to any one of claims 1 to 9, wherein the ratio of the aromatic dicarboxylic acid to the dicarboxylic acid of the reinforcing cord is 50 mol% or more. The tire according to any one of claims 1 to 10, wherein the ratio of the dicarboxylic acid having one aromatic ring to the aromatic dicarboxylic acid is 20 mol% or more. The tire according to any one of claims 1 to 10, wherein the ratio of the dicarboxylic acid having two aromatic rings to the aromatic dicarboxylic acid is 20 mol% or more. The tire according to any one of claims 1 to 10, wherein the ratio of the dicarboxylic acid having three aromatic rings to the aromatic dicarboxylic acid is 20 mol% or more. The tire according to any one of claims 1 to 13, wherein the ratio of the diamine having 7 to 12 carbon atoms to the diamine is 20 mol% or more. The reinforcing cord is at least one selected from the group consisting of the multifilament of the polyamide and the group consisting of polyester fiber, nylon fiber, aramid fiber, polyketone fiber, glass fiber, carbon fiber, polyparaphenylene benzobisoxazole fiber and polyarylate fiber. The tire according to any one of claims 1 to 14, which is a hybrid code of the fiber. The reinforcing cord taken out from the tire is the following formulas (1) and (2).
α1 = N1 × √ (0.125 × D1 / ρ) × 10 ^-3 (1)
α2 = N2 × √ (0.125 × D2 / ρ) × 10 ^-3 (2)
(N1 is the number of lower twists [times / 10 cm], D1 is the fineness of one lower twist yarn [dtex], N2 is the number of upper twists [times / 10 cm], D2 is the total fineness of the cord [dtex], and ρ is the reinforcing cord. The lower twist coefficient α1 represented by the density [g / cm ³ ]) is 0.1 to 0.9, and the upper twist coefficient α2 is 0.1 to 1.2. The tire described in item 1. The tire according to claim 16, wherein the α1 is 0.1 to 0.5 and the α2 is 0.1 to 0.7. The tire according to claim 16 or 17, wherein the number of lower twists N1 of the reinforcing cord is 10 to 30 times / 10 cm. The tire according to any one of claims 16 to 18, wherein the number of upper twists N2 of the reinforcing cord is 10 to 30 times / 10 cm. The tire according to any one of claims 1 to 19, which is for a passenger car.

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