JPH08108492A - Highly rigid aromatic polyamide cord for reinforcing rubber and pneumatic tire using the cord - Google Patents

Abstract

PURPOSE: To provide a rubber reinforcing highly rigid aromatic polyamide cord having high cord rigidity and a pneumatic tire having excellent durability, riding comfort, and steering stability made of the polyamide cord. CONSTITUTION: An aromatic polyamide cord consists of a cord consisting of aromatic polyamide fibers treated in sequence with a first treating liquid which contains a urethane resin, a second treating liquid which contains a polyisocyanate compound, and a third treating liquid which contains an adhesive. The rigidity of the cord is within a range of 200-600g.m.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rubber-reinforced high-rigidity aromatic polyamide cord for use in a belt material or a bead portion of a pneumatic tire and having high strength and rigidity, and a tire using the cord. It is a thing.

[0002]

2. Description of the Related Art Conventionally, a steel cord has been mainly used as a cord for reinforcing a bead portion of a pneumatic tire.

However, with the recent trend toward weight reduction of automobiles, the demand for weight reduction of tires is also increasing. As a means for reducing the weight of tires, a reinforcing cord made of steel having a large specific gravity is used instead. The mainstream is to switch to organic fiber cords with low specific gravity.

Among the rubber-reinforcing organic fibers,
In particular, aromatic polyamide fibers have characteristics of high strength and high Young's modulus, and cords composed of the aromatic polyamide fibers are considered to be promising as a substitute for steel cords, particularly in tire applications.

However, since the aromatic polyamide fiber cord is poor in adhesiveness to rubber, various methods for improving the adhesiveness between the aromatic polyamide fiber cord and rubber have been conventionally studied.

That is, as a typical conventional example for improving the adhesion of aromatic polyamide fiber cord to rubber, aromatic polyamide fiber is treated with an epoxy compound having two or more epoxy groups in the molecule. Then, a method of treating with resorcin / formaldehyde / rubber latex (JP-A-2-202569), and treating an aromatic polyamide fiber with a mixture of polyepoxy compound / blocked isocyanate compound / rubber latex, and then resorcin / formaldehyde / Examples thereof include a method of treating with a treatment liquid in which a special chlorophenol compound is mixed with rubber latex (Japanese Patent Laid-Open No. 3-40875).

However, although these methods are almost satisfactory in improving the adhesion between the aromatic polyamide fiber cord and the rubber, for example, when the treated cord is used to reinforce a tire belt material or a bead portion, it is treated. There was a problem that the rigidity of the cord was insufficient.

As a means for improving the problem of insufficient rigidity,
A method of treating an aromatic polyamide fiber cord with a first treatment liquid in which a compound having a urethane group and a substance having an epoxy group are mixed, and further treating it in a second treatment consisting of a mixed liquid of resorcinol / formaldehyde / rubber latex (special Kaihei 5-195358) has been proposed, but the aromatic polyamide fiber cord obtained by this method has a high rigidity but a strength of 12.5-16.0.
It is about g / d, and when the treated cord is used for reinforcing the tire belt material or the bead portion, there is a problem that the treated cord has low strength and poor durability.

[0009]

DISCLOSURE OF INVENTION Problems to be Solved by the Invention The present invention has been studied in order to solve the above-mentioned problems in the prior art.
It has been achieved.

Therefore, an object of the present invention is to provide a rubber having high strength and excellent adhesiveness with rubber, and also having a high cord rigidity such that the shape is stable when the cord is looped like a steel wire cord. It is intended to provide a high-rigidity aromatic polyamide cord for reinforcement and a pneumatic tire using the polyamide cord, which is excellent in durability, riding comfort and steering stability .

[0011]

In order to achieve the above object, the rubber-reinforced high-rigidity aromatic polyamide cord of the present invention comprises a cord made of an aromatic polyamide fiber and a urethane resin. First treatment liquid, second treatment liquid containing polyisocyanate compound, and third treatment liquid containing adhesive
It is an aromatic polyamide cord which is sequentially treated with a treatment liquid, and is characterized in that the cord rigidity is in the range of 200 to 600 g · cm.

The rubber-reinforced high-rigidity aromatic polyamide cord of the present invention preferably has a twist coefficient (TM) represented by the following formula in the range of 1.1 to 5.7.

TM = T × D ^1/2 /287.4 [T: number of twists (t / 10 cm), D: original yarn fineness × number of combined yarns] And the high rigidity aromatic polyamide cord for rubber reinforcement of the present invention Indicates that the first treatment liquid containing a urethane-based resin uses an organic solvent as a solvent, and the amount of the urethane-based resin attached is 3.0 to 14.0% by weight with respect to the cord weight. The adhesion amount of the polyisocyanate compound in the second treatment liquid is 0.5 to 5.0% by weight with respect to the cord weight, and the adhesive of the third treatment liquid is resorcin / formaldehyde / rubber latex (RFL). A desirable condition is that the amount of RFL attached is 2.0 to 7.0 wt% with respect to the cord weight.

Further, in the rubber-reinforced high-rigidity aromatic polyamide cord of the present invention, the treated cord has a strength of 16.0-2.
It is characterized by being in the range of 1.0 g / d.

Further, the pneumatic tire of the present invention is characterized in that the above-mentioned high-rigidity aromatic polyamide cord for rubber reinforcement is used as a reinforcement cord, particularly at least in the bead portion of the tire.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The constitution and effects of the present invention will be specifically described below.

First, the aromatic polyamide used in the present invention means aromatic poly-p-phenylene terephthalamide and poly-p-phenylene.3-4 'diphenyl ether terephthalamide, and the aromatic polyamide cord. , A fiber obtained from the aromatic polyamide,
It can be obtained as a twisted structure, for example, a single-twisted twisted structure or a ply-twisted structure by an ordinary method.

The aromatic polyamide cord used in the present invention has a twist coefficient (TM) represented by the following formula of 1.1 to 5.
It is desirable that the twist is in the range of 7, especially in the range of 2 to 5.

TM = T × D ^1/2 /287.4 [T: twist number (t / 10 cm), D: original yarn fineness × number of combined yarns] When the twist coefficient of the aromatic polyamide cord exceeds 5.7. ,
Not only is it easy to creep, but the strength of the cord is reduced, which is not preferable.

When the twisting coefficient of the aromatic polyamide cord is 1.1 or less, the single fibers in the cord are poor in the bundle concentrating property and the adhesiveness with the rubber is deteriorated, and the cord is flattened and vulcanized. It is not preferable because troubles are likely to occur in the molding process.

In the present invention, the aromatic polyamide cord is first treated with a first treatment liquid containing a urethane resin, then with a second treatment liquid containing a polyisocyanate compound, and then a third treatment containing an adhesive. It is obtained by treating with a treatment liquid.

As the urethane resin contained in the first treatment liquid used in the present invention, polyethylene adipate, polypropylene adipate, polyethylene phthalate, polyester polyols such as polycaprolactone glycol, polyethylene glycol, polypropylene glycol, polyethylene propylene glycol, poly Examples include reaction products of polyether polyols such as tetramethylene glycol and polyisocyanates such as tolylene diisocyanate, 4-4 ′ diphenylmethane diisocyanate, 1-5-naphthalene diisocyanate, hexamethylene diisocyanate and xylene diisocyanate. However, especially polyester and 4-
A reaction product of 4'diphenylmethane diisocyanate is preferably used.

The first treatment liquid is used in the form of a polyurethane resin dissolved in an organic solvent such as methyl ethyl ketone, toluene, tetrahydrofuran and methyleneformamide.

By using an organic solvent as the solvent for the polyurethane resin, the polyurethane resin is uniformly and evenly impregnated into the aromatic polyamide cord bundle, so that the single yarns can be bonded and solidified. As a result, the rigidity of the processing cord can be sufficiently maintained.

When the first treatment liquid is formed by using an aqueous resin solution (for example, RFL or urethane aqueous solution) instead of the above organic solvent, the first treatment liquid composed of the aqueous resin solution is an aromatic polyamide. It is not preferable because it is difficult for the cord to permeate the inside of the cord bundle and the polyurethane resin tends to exist only on the cord surface.

The above-mentioned first treatment liquid is prepared so that the total solid content concentration of the urethane resin in this treatment liquid is 5 to 20% by weight, preferably 10 to 15% by weight, and the solid content in the cord is adjusted. Adhesion amount is 3.0 to 14.0% by weight, preferably 8 to
It is added so as to be in the range of 12% by weight.

When the amount of the polyurethane-based resin adhered to the cord is 3.0% by weight or less, the rigidity of the cord is lowered and the shape retention of the cord when looped is deteriorated. If it exceeds 0%, the rigidity of the cord increases, but the strength of the cord decreases, which is not preferable.

In the present invention, after immersing the aromatic polyamide cord in the first treatment liquid, at a temperature of 110 to 150 ° C., preferably at a temperature of 120 to 130 ° C., 0.1 to 0.3 g / d for 360 seconds. Dry under tension of.

At a drying temperature of 110 ° C. or lower after application of the first treatment liquid, the treatment liquid does not solidify sufficiently and adheres to the roller, which reduces the amount of adhesion to the cord and reduces the rigidity of the cord. Become.

Further, if the treatment tension is 0.3 g / d or more, the cord bundle is tightened, the permeation of the first treatment liquid into the cord layer is suppressed, and the rigidity of the treatment cord tends to decrease, which is not preferable. . In order to promote the permeation and diffusion of the first treatment liquid to the inner layer of the cord and to coat the surface of the single yarn with the polyurethane resin, a low tension treatment of 0.2 g / d or less is particularly desirable.

Examples of the polyisocyanate compound contained in the second treatment liquid used in the present invention include tolylene diisocyanate, metaphenylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, polymethylene polyphenyl isocyanate,
And triphenylmethane triisocyanate are used, and among them, polyfunctional polyisocyanate of polymethylene polyphenyl isocyanate is preferably used.

The second treatment liquid is prepared by dissolving the polyisocyanate compound in an organic solvent such as toluene so that the total solid concentration of the polyisocyanate compound becomes 5 to 20% by weight, preferably 10 to 15% by weight. The amount of solids deposited on the outer periphery of the aromatic polyamide cord of the polyisocyanate compound is 0.5 to 5.0% by weight, especially 2.0 to
It is added so as to be in the range of 4.0% by weight.

When the amount of the polyisocyanate compound applied to the aromatic polyamide cord is 0.5% by weight or less, the adhesion between the treated cord and the rubber is lowered, and the weight is 5.0% by weight.
If it exceeds, the adhesiveness to rubber is saturated and, on the contrary, the adhesiveness tends to be lowered, which is not preferable.

In the present invention, treatment with the first treatment liquid
The dried aromatic polyamide cord is then dipped in the second treatment liquid to obtain a temperature of 200 to 250 ° C., preferably 2
0.1 to 0.5 g / for 60 seconds at a temperature of 20 to 230 ° C
The heat treatment is performed under a tension of d, preferably a tension of 0.2 to 0.4 g / d.

If the drying temperature after application of the second treatment liquid is too harsh at 250 ° C. or higher, the polyurethane resin is deteriorated and the rigidity of the treatment cord tends to be lowered, which is not preferable. .

Further, in order to promote penetration and diffusion of the second treatment liquid into the inner layer of the cord and to coat the surface of the single yarn with the polyisocyanate compound, a low tension treatment of 0.4 g / d or less is particularly desirable.

Examples of the adhesive used in the third treatment liquid used in the present invention include resorcinol / formaldehyde / rubber latex, rubber paste, and adhesives that adhere to rubber such as Chemloc. However, resorcin / formaldehyde / rubber latex is preferably used.

The above-mentioned resorcinol-formaldehyde-rubber latex is obtained by aging a mixture of an initial condensate of resorcinol-formaldehyde under an alkali catalyst and a rubber latex, generally at a temperature of 20 to 30 ° C. for 24 hours or more, It is usually called RFL.

Examples of the rubber latex as used herein include natural rubber latex, styrene / butadiene / copolymer latex, and vinylpyridine / styrene / butadiene / terpolymer latex. Among them, vinylpyridine / styrene / butadiene is particularly preferable. -The terpolymer latex is preferably used alone or in combination with another rubber latex.

A mixture of a halogen latex such as 2-6 bis (2,4-dihydroxyphenylmethyl) -4-chlorophenol and an initial condensate of resorcin-formaldehyde and a rubber latex is used. May be.

The third treatment liquid containing the RFL is prepared so that the total solid content concentration is 10 to 25% by weight, preferably 15 to 20% by weight, and the solid content deposition amount on the outer circumference of the RFL cord is 2%. 0.0 to 7.0% by weight, preferably 4 to 6% by weight.

If the adhesion amount of RFL to the aromatic polyamide cord is less than 2.0% by weight, the adhesion between the treated cord and the rubber is insufficient, and if it exceeds 7.0% by weight.
It is not preferable because the adhesion of the treated cord to the rubber tends to be saturated or lowered.

The aromatic polyamide cord applied with the second treatment liquid and dried is then dipped in the third treatment liquid to obtain 10
Dry at a temperature of 0 to 150 ° C for 150 seconds, and further 200 to 2
At a temperature of 50 ° C., preferably 220-240 ° C.,
Tension of 0.1 to 1.5 g / d for 60 seconds, preferably 0.1.
The tension heat treatment is performed under a tension of 5 to 1.0 g / d.

When the drying condition after applying the third treatment liquid is 100 ° C. or lower, the resorcinol / formaldehyde / rubber latex adheres to the roller without solidifying, so that the adhered amount to the cord is reduced and further the adhesion unevenness is caused to cause the rubber. Adhesiveness with will tend to decrease.

On the other hand, if the heat treatment condition is severer than 250 ° C., the polyurethane resin and the resorcin / formaldehyde / rubber latex previously applied are deteriorated, and the rigidity of the cord and the adhesiveness with the rubber are deteriorated, which is not preferable.

On the other hand, if the heat treatment condition is too low, that is, less than 200 ° C., the rigidity of the treated cord and the adhesiveness with the rubber are poor and it cannot be put to practical use, which is not preferable.

Further, if the treatment tension after application of the third treatment liquid is too low at 0.2 g / d or less, the single fibers of the treatment cord are poor in the focusing property and the aligning effect, and some of the single fibers are stressed. Are concentrated and the strength of the cord is reduced, which is not preferable.

Therefore, the treatment tension in this case is preferably high tension treatment, but even if a high tension of 1.5 g / d or more is applied, the effect of improving the strength of the treatment cord is small, which is not preferable. .

The thus-obtained high-rigidity aromatic polyamide cord for rubber reinforcement of the present invention has high strength and excellent adhesiveness to rubber, and has a form when the cord is looped like a steel wire cord. It has a high level of cord rigidity to be stable, and is extremely useful as a reinforcing material for high-grade reinforced rubber products such as rubber products such as tires, conveyor belts and hoses. Pneumatic tires made from group III polyamide cords offer durability, ride comfort and handling
It has excellent characteristics such as qualitative properties.

That is, the pneumatic tire of the present invention uses the above-mentioned high-rigidity aromatic polyamide cord for rubber reinforcement as a reinforcement cord for carcass plies, belt layers, auxiliary belt layers, and the like, and particularly for the bead portion. As a result, it is less likely to break the cord ply and separate from the rubber, and is excellent in durability, especially high-speed durability, and also excellent in various characteristics such as riding comfort and steering stability. It exhibits excellent performance.

[0051]

EXAMPLES The present invention will now be described in more detail with reference to examples.

The strength in the examples described below,
The evaluations of the cord rigidity and the peeling force are values obtained as follows.

(1) Strength This is obtained from the maximum strength (Kg) and fineness (D) of an aromatic polyamide-treated cord using Tensilon, measured under conditions of a test length of 250 mm and a pulling speed of 100 mm / min.

(2) Cord stiffness Measured using a Taber stiffness tester, the value is g
Expressed in cm. The larger the measured value, the stiffer.

(3) Peeling force The aromatic polyamide-treated cord was embedded in a carcass compound rubber for automobile tires, pressure-vulcanized at a temperature of 150 ° C. for 30 minutes, and then the cord was pulled from the rubber at a rate of 300 mm / min. The force required for peeling is expressed in Kg / code.

[Example 1] As a polyurethane resin, "Nipporan" 2301 (4 manufactured by Nippon Polyurethane Industry Co., Ltd.)
A 0% solid content liquid) was used, and 250 g of the solution was dissolved in 750 g of methyl ethyl ketone to obtain a first treatment liquid.

The polyisocyanate compound PAPI
100 g of -135 (manufactured by Kasei Upjohn Co., Ltd.) was dissolved in 900 g of toluene to obtain a second treatment liquid.

Further, an initial condensate of 200.92 g of distilled water, 29.71 g of 1% caustic soda, 18.46 g of resorcin, and 16.87 g of 37% formaldehyde was prepared, and the condensate was converted to vinylpyridine / styrene / butadiene / taden. -Polymer latex (PYRATEX-FS40.5% solid content liquid manufactured by Sumitomo Nogatak) 30
The mixture was stirred and added to a mixed liquid of 8.64 g and 25.40 g of distilled water for aging, and this RFL liquid was further added to 250.00 g of Denabond (20% solid content liquid manufactured by Nagase Kasei Co., Ltd.).
A third treatment liquid was prepared by adding the mixture to 150.00 g of distilled water and distilled water while stirring and aging.

On the other hand, four pieces of aromatic polyamide fiber "Kevlar" 3000d-1333f manufactured by DuPont were used to combine the four.
Twist coefficient = 3.8 (twist number 10 times / 10c) using a computer treating machine (CA, manufactured by Ritzler)
m) twisted cord was obtained.

The aromatic polyamide cord was first immersed in the first treatment liquid and then dried at 125 ° C. under a tension of 0.2 g / d for 360 seconds.

The aromatic polyamide cord treated with the first treatment liquid is then immersed in the second treatment liquid and then 2
Heat treatment was performed for 60 seconds at 30 ° C. and a tension of 0.2 g / d.

Further, after the aromatic polyamide cord treated with the second treatment liquid is immersed in the third treatment liquid,
Dry at 130 ° C for 150 seconds, then 240 ° C,
A tension heat treatment was performed for 60 seconds under a tension of 0.5 g / d.

In the obtained treatment code, the first treatment liquid had a solid content of 9.0% by weight, the second treatment liquid had a solid content of 1.1% by weight, and the third treatment liquid had a solid content. 4.7% by weight was attached respectively.

With respect to the obtained treated cord, cord strength, cord rigidity, and peeling force were measured. As a result, the cord strength was 20.42 g / d and the cord rigidity was 515 g · c.
m, and the peeling force was 5.1 kg / code.

[Comparative Examples 1, 4 and 6] Using the aromatic polyamide cord of Example 1, after immersing it in the first treatment liquid of Example 1, it was heated at 125 ° C. under a tension of 0.2 g / d for 360 seconds. The evaluation results of the treated cords obtained by drying are shown in Table 1 (Comparative Example 1).

As is clear from the results of Table 1, the treated cord of this Comparative Example 1 has a higher cord strength and is better than the treated cord obtained in Example 1, but has a large cord rigidity. It is not preferable for rubber reinforcement because the width is reduced, the shape retention when the cord is formed into a loop shape is extremely poor, and the adhesiveness is also extremely poor.

In Example 1, after the first treatment liquid and the third treatment liquid were not used and only the second treatment liquid was immersed,
Table 1 also shows the evaluation results of the cords obtained by heat treatment at 230 ° C. under a tension of 0.2 g / d for 60 seconds (Comparative Example 4).

As is clear from the results shown in Table 1, the treated cord of this Comparative Example 4 has higher cord strength but lower cord rigidity and adhesiveness than the treated cord obtained in Example 1. However, it is not preferable for rubber reinforcement.

Furthermore, in Example 1, the first treatment liquid and the second treatment liquid were not used, only the third treatment liquid was soaked, followed by drying at 130 ° C. for 150 seconds, and subsequently at 240 ° C.
The measurement results of the cord obtained by performing the heat treatment for tension for 60 seconds under the tension of 0.5 g / d are also shown in Table 1 (Comparative Example 6).

As is clear from the results shown in Table 1, the treated cord of this Comparative Example 6 has higher cord strength but lower cord rigidity and adhesiveness than the treated cord obtained in Example 1. However, it is not preferable for rubber reinforcement.

[0071]

[Table 1]

[Examples 2 to 10, Comparative Examples 2 to 3, Comparative Example 5 and Comparative Examples 7 to 9] Using the aromatic polyamide cord of Example 1, the first treatment liquid and the second treatment liquid in Example 1 were used. Also, the solid content concentration of the third treatment liquid was changed as shown in Table 1 and the evaluation results of the cords obtained by performing the tension heat treatment under the same conditions as in Example 1 are also shown in Table 1. Show.

As a result, when compared with the characteristics of the treatment cords obtained in the first embodiment, the characteristics of the treatment cords obtained in the present embodiments 2 to 10 are excellent as in the first embodiment, but
When the treatment liquid is not used (Comparative Example 2), the strength and the adhesiveness of the obtained treated cord are high and good, but the cord rigidity is greatly reduced, and the shape retention property when the cord is looped. Is bad.

On the other hand, by increasing the solid content concentration of the first treatment liquid,
Although the strength of the treated cord tends to decrease as the amount of the urethane resin deposited increases, the cord rigidity and the adhesiveness are excellent, and the object of the present invention can be sufficiently achieved ( Examples 2, 3 and 4).

When the solid content concentration of the first treatment liquid is increased to 25% by weight to increase the amount of the urethane resin adhered, the cord rigidity and adhesiveness of the obtained treatment cord are improved, but the cord strength is improved. It greatly decreases (Comparative Example 3).

In Example 1, when the second treatment liquid is not used, the cord strength of the obtained treatment cord is high,
The cord rigidity and the adhesiveness are reduced (Comparative Example 5).

On the other hand, in Example 1, when the solid content concentration of the second treatment liquid is increased and the amount of the polyisocyanate compound attached is increased, the cord strength of the obtained treatment cord tends to decrease. Since the rigidity is high and the adhesiveness is excellent, the object of the present invention can be sufficiently achieved (Examples 5, 6, 7, and 8).

Further, in Example 1, when the solid content concentration of the third treatment liquid was set to 5% by weight and the adhesion amount of RFL was reduced, the cord strength and the cord rigidity of the obtained treatment cord were excellent, but the adhesiveness was high. Is significantly unfavorable for rubber reinforcement (Comparative Example 7).

On the other hand, in Example 1, when the solid content concentration of the third treatment liquid was set to 10 to 20% by weight and the adhesion amount of RFL was increased, the adhesiveness of the obtained treatment cord was improved and the object of the present invention was to Sufficiently achieved (Examples 9 and 10).

On the other hand, in Example 1, the solid content concentration of the third treatment liquid was increased to 25 to 30% by weight, and the RFL
If the adhesion amount of (1) is increased too much, the adhesiveness of the obtained treated cord will be saturated, and not only a large improvement can be expected as compared with Example 1, but the improvement effect will be rather reduced. Not only that, it also tends to induce uneven adhesion of the treatment liquid and cause variations in adhesion (Comparative Examples 8 and 9).

[Examples 11 to 12, Comparative Examples 10 to 11]
Table 2 also shows the evaluation results of the treated cords obtained by changing the twist coefficient (TM) of the "Kevlar" raw cord as shown in Table 2 and performing the same treatment as in Example 1.

[0082]

[Table 2]

As is clear from the results shown in Table 2, when the twist coefficient of the raw cord is set higher or lower than that of Example 1, the focusing property of the cord is increased and the penetration and diffusion of the first treatment liquid into the cord is increased. Not only the cord rigidity of the treated cord tends to decrease due to the reduced amount of the first treatment liquid adhered due to alienation, but the cord strength also tends to decrease as the twist coefficient increases, but the twist coefficient is 5.7 or less. Alternatively, if it is 1.1 or more, the object of the present invention can be achieved (Examples 11 and 1).
2).

On the other hand, when the twist coefficient of the raw cord is less than 1.1, the adhesiveness of the obtained treated cord is extremely poor (Comparative Example 10).

When the twist coefficient of the raw cord exceeds 5.7, the cord strength of the obtained treated cord is extremely low (Comparative Example 11).

As is clear from the above results, the rubber-reinforcing polyamide cord of the present invention has the following properties of cord strength, cord rigidity and adhesiveness in balance, as compared with the rubber-reinforcing polyamide cord of the comparative example. It is excellent.

[Comparative Example 12] Distilled water (255 g) was added to sorbitol polyglycidyl ether (Denacol EX611 (manufactured by Nagase Kasei)) (45 g) to uniformly dissolve the sorbitol polyglycidyl ether, and the urethane-containing compound Hydran AP3 was added to the aqueous solution.
0 (Dainippon Ink and Chemicals 20% solid content liquid) 525g
And 175 g of distilled water were added and uniformly dissolved to obtain a first treatment liquid.

On the other hand, 360.48 g of distilled water, 51.0 g of 1% caustic soda, 18.9 g of resorcin, and 37%
Prepare an initial condensate of 27.67 g of formaldehyde,
This condensate is converted into vinyl pyridine / styrene / butadiene /
Terpolymer latex (PYR manufactured by Sumitomo Nogatak Co., Ltd.
ATEX-FS40.5 solid content liquid) 423.0 g,
Distilled water 99.5 g, and 28% ammonia 19.45
A second treatment liquid was prepared by adding to the mixed liquid of g with stirring and aging.

Using the aromatic polyamide cord of Example 1, after immersing it in the above-mentioned first treatment liquid, it was heated at 130 ° C. for 15 minutes.
Dry at 0 ° C for 150 seconds, then 240 ° C, 1.0 g /
A tension heat treatment was performed for 60 seconds under the tension of d.

Further, after the cord treated with the first treatment liquid is dipped in the second treatment liquid, 150 at 130 ° C.
It was dried for 2 seconds and subsequently subjected to a tension heat treatment at 240 ° C. under a tension of 1.0 g / d for 60 seconds.

The processing code thus obtained includes
The solid content of the first treatment liquid was 7.0% by weight, and the solid content of the second treatment liquid was 4.0% by weight.

The treated cord had a cord rigidity of 495 g · cm and a peeling force of 5.21 Kg / cord, but the cord strength was only 14.14 g / d, which was low.

[Example 13 and Comparative Example 13] A tire in which the treated cord obtained in Example 1 was applied as a rubber reinforcing material for a bead portion of a pneumatic tire was prepared and subjected to an actual vehicle running test. As a result of evaluating durability, riding comfort, and steering stability, all were good (Example 1
3). On the other hand, the treated cord obtained in Comparative Example 12 was applied as a reinforcing rubber layer of a bead portion of a pneumatic tire similar to the above, and the same actual vehicle running test was carried out. As a result, this pneumatic tire was reinforced. The breakage of the cord and the separation of the cord and the rubber particularly near the rim portion were likely to occur at an early stage, and the durability was extremely poor as compared with the pneumatic tire of Example 13 (Comparative Example 1).
3).

[0094]

As described above, the rubber-reinforcing high-rigidity aromatic polyamide cord of the present invention has high strength and excellent adhesiveness to rubber, and has a loop-shaped cord such as a steel wire cord. It has a high cord rigidity to such an extent that its shape is stable when it is formed, and is extremely useful as a reinforcing material for high-quality reinforced rubber products, for example, rubber products such as tires, conveyor belts and hoses.

Further, the pneumatic tire of the present invention using the above-mentioned high-strength aromatic polyamide cord for rubber reinforcement as a reinforcement cord for the auxiliary belt layer and bead portion of the tire causes the cord ply to be cut and the rubber to be separated. It is excellent in durability, especially high speed durability,
It has excellent balance of various characteristics such as riding comfort, lightness and steering stability.

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Claims (12)

[Claims] 1. A cord made of an aromatic polyamide fiber impregnated with a urethane resin, having a cord rigidity of 200.
A high-rigidity aromatic polyamide cord for rubber reinforcement, which is in the range of up to 600 g · cm. 2. The high-strength aromatic fragrance for rubber reinforcement according to claim 1, wherein the twist coefficient (TM) of the aromatic polyamide cord represented by the following formula is in the range of 1.1 to 5.7. Family polyamide cord. 3. A cord made of aromatic polyamide fiber, a first treatment liquid containing a urethane resin, a second treatment liquid containing a polyisocyanate compound, and a third treatment containing an adhesive.
A highly rigid aromatic polyamide cord for rubber reinforcement, which is an aromatic polyamide cord which is sequentially treated with a treatment liquid and has a cord rigidity in a range of 200 to 600 g · cm. 4. The high rigidity aromatic fragrance for rubber reinforcement according to claim 3, wherein the twist coefficient (TM) represented by the following formula of the aromatic polyamide cord is in the range of 1.1 to 5.7. Family polyamide cord. TM = T × D ^1/2 /287.4 [T: twist number (t / 10 cm), D: original yarn fineness x number of combined yarns] 5. The rubber-reinforced high-rigidity aromatic polyamide cord according to claim 3, wherein the first treatment liquid containing a urethane resin uses an organic solvent as a solvent. 6. The rubber reinforcement according to claim 1, 2, 3, 4 or 5, wherein the amount of the urethane resin adhered is 3.0 to 14.0% by weight based on the weight of the cord. High rigidity aromatic polyamide cord for use. 7. The adhesion amount of the polyisocyanate compound in the second treatment liquid is 0.5 to 5.0 with respect to the cord weight.
The high-rigidity aromatic polyamide cord for rubber reinforcement according to claim 3, 4, 5 or 6, characterized in that the content is% by weight. 8. The high-strength aromatic fragrance for rubber reinforcement according to claim 3, 4, 5, 6 or 7, wherein the adhesive of the third treatment liquid is resorcinol-formaldehyde-rubber latex (RFL). Family polyamide cord. 9. The adhesion amount of the adhesive in the third treatment liquid is
The high rigidity aromatic polyamide cord for rubber reinforcement according to claim 3, 4, 5, 6, 7 or 8, which is 2.0 to 7.0% by weight relative to the cord weight. 10. The strength of the processing code is 16.0-2.
2. The range of 1.0 g / d.
The highly rigid aromatic polyamide cord for rubber reinforcement according to 2, 3, 4, 5, 6, 7, 8 or 9. 11. The method according to claim 1, 2, 3, 4, 5, 6, 7,
A pneumatic tire using the high-rigidity aromatic polyamide cord for rubber reinforcement according to 8, 9, or 10 as a reinforcement cord. 12. The method according to claim 1, 2, 3, 4, 5, 6, 7,
A pneumatic tire comprising the high-strength aromatic polyamide cord for rubber reinforcement according to 8, 9, 10 or 11 in at least a bead portion of the tire.