Improvements introduced in radial fiber tne. (Machine-translation by Google Translate, not legally binding)

(74) Agent: Plasseraud, Devant, Gutmann, Jacquelin, Lemoine.

@ Polyvinyl alcohol fiber with excellent properties at high temperatures and radial tire containing such fibers.

72) Invention of:

33) (32) (31

Conventional priority: Patent applicati ons filed in Japan ie November 25, 1969, n. 94.790 / 1969 and April 30, 1970, n. 37.354 / 1970 in t he name of the plaintiff, then named Kurashiki Rayon Co., Ltd.

Sale of booklets at IMPRIMERIE NATIONALE, 27, rue de la Convention - PARIS (15^e)

42369

The invention relates to a polyvinyl alcohol fiber which exhibits, at high temperatures, excellent properties such as toughness, initial modulus and wire routing; it also relates to a radial tire, the dividing fabric of which is made of a cord formed of this fiber, by wiring or twisting under predetermined conditions of torsion.

In general, polyvinyl alcohol fiber (PVA) outweighs other synthetic fibers in terms of their breaking strength and initial modulus, and has been widely used in various fields for some time. . It is a well-known fact that PVA fibers which have been stretched to the limit and then reduced to a minimum length by heat shrinkage have remarkable properties of breaking streng th and initial modulus. However, PVA fibers, like other synthetic fibers, show a tendency to a stro ng degradation of the above-mentioned properties at elevated temperatures, as a function of the rise in temperature.

The main object of the invention is to avoid the above-mentioned drawbacks of synthetic fibers, so as to provide a new PVA fiber having excellent properties at high temperatures and to provide a radial tire which uses such a fiber in the cord of his dividing web. More specifically, the synthetic fiber according to the present invention is superior to conventional PVA fibers with regard to the toughness, the initial modulus and the routing of the wire. The radial tire which uses the PVA fiber of the invention in the cord of its dividing fabric has, as will be demonstrated in the description which follows, excellent results on the test with the compression piston, '' high speed test, cornering power test, tread wear resistance test and durability test.

Synthetic PVA fiber and radial tire will be described separately.

The synthetic PVA fiber according to the present invention has a high crystallinity and a strong molecular orientation, and it is characterized by its properties at high temperatures, as indicated below, and by its boric acid content (E ^ BO ^ ) or borate (the following description relating to boric acid), the properties at elevated temperatures being as follows:

42369 wire tenacity at 120 ° C initial wire nodule at 120 ° C wire routing at 135 ° C boric acid content

7.5 g / d or more 100 g / d or more 2 # maximum

0.2 to 0.9% by weight relative to PVÀ

As a general rule, the extensibility of synthetic fibers increases as the temperature rises, while the resistance and the initial modulus of the wire can decrease. It can easily be assumed that this phenomenon occurs because the movement of molecular chains is triggered by heating in the fiber, where the molecular orientation is less marked, this movement soon reaching the area where the molecular orientation is intense. To improve the properties of a synthetic fiber at high temperatures, it is therefore important to suppress as much as possible the movement of molecular chains. This can be done either (1) by intensifying the orientation of the molecular chains to the point of removing all possibility of movement, or (2) by adding to the polymers a certain substance which hinders the movement of the molecular chains. However, these two remedies do not make it possible to achieve the aims of the present invention, namely the improvement of the properties at high temperatures, such as the toughness, the initial modulus and the routing of the wire, when they are applied independently. For example, an improvement in the initial modulus of the wire can be expected by applying a method according to which a conventional PVA fiber is subjected to a post-treatment with boric acid, while this same method will give rise to a reduction. notable for the tenacity of the thread. Various researches made by the applicant have arrived at this conclusion that the essential factor which satisfies the main aim of the invention is a fibrous structure in which the orientation of the molecular chains is very marked overall, but which contains a substance intended to prevent the movement of molecular chains, where the molecular orientation is relatively weak. This means that some or all of the boric acid contained in the fiber must be combined with PVA in the zones with a relatively weak orientation, in order to oppose the movement of the molecular chains resulting from the heating. If the boric acid content does not reach $ 0.2 of the weight of PVA, this proportion is insufficient to slow the movement of the chains, while a content exceeding the proportion of $ 0.9 will prevent

42369 molecular chains to be strongly oriented, ee which will result in a reduction in the resistance of the wire.

the PVA fiber of the present invention is produced according to the process comprising the following steps: preparation of an aqueous solution of PVA containing boric acid or borate (spinning solution); spinning in a coagulation bath essentially composed of water containing sodium or potassium hydroxide and sodium sulfate, these elements being in a predetermined proportion; stretching between rollers; acid neutralization of alkalis which adhere to the fiber; wet heat stretching; rinsing with water to adjust, within a predetermined range, the proportion of boric acid which remains in the PVA fiber; dehydration and drying; and stretching with dry heat.

To go into detail about the composition of the coagulation bath, the concentration of it, which was used in the conventional wet spinning process to produce PVA fibers containing neither boric acid nor borate, was almost saturated with sodium sulfate. sodium, just in case. sodium sulfate, which is a dehydrating salt, was used for the bath. If this was so, it is because the fibers would have remained stuck to each other due to insufficient coagulation, in the event that the concentration of said bath was less than 300 g / l. This is why the coagulation bath used in the context of the present invention is additionally supplemented with sodium hydroxide or potassium hydroxide in a predetermined proportion, which facilitates the spinning of the spinning solution containing boric acid or borate. Furthermore, the properties of the PVA fiber thus produced hardly depend on the temperature. It has often been observed that when the sodium sulphate content is high in the coagulation bath, the stretchability of the product tends to decrease. the synthetic PVA fiber produced according to the invention has a higher drawing capacity and less temperature dependence, compared to conventional PVA fibers which do not contain boric acid.

the inventors carried out various researches and repeated experiments on the coagulation ability of the aqueous PVA solution containing boric acid or borate, as well as on the properties of the product thus obtained, and they discovered a process and conditions for the production of a synthetic PVA fiber, including the toughness, the initial modulus and the path of the dependent wire

<img file="FR2072392A5_D0001.tif" />

42369 tooth barely at temperature, the process consists in spinning an aqueous solution of PVA containing boric acid or borate in a coagulation bath maintained strongly alkaline by the addition of 10 to 100 g / l of sodium hydroxide or potassium hydroxide and 100 to 330 g / l of sodium sulphate, the wire then being subjected to subsequent treatments such as drawing on a roller, neutralization of its alkalis, rinsing with water to adjust the residual content of boric acid in the fiber in a range of 0.2 to 0.9 $ by weight of PVA, dehydration and drying, then drawing with dry heat.

It is preferable to add boric acid or borate to the spinning solution in an amount between 1 and 5% of the weight of PVA. the solution is kept weakly acidic, between a pH of 3 and a pH of 5 to clarify. The acid which should be added to the solution can be an inorganic acid such as sulfuric acid, nitric acid or hydrochloric acid, an organic acid such as aetic acid, tartaric aid, etc. . or a combination of an organic acid and an organic acid salt, for example citric acid and sodium citrate, acetic acid and sodium acetate, tartaric acid and potassium tartrate , tartaric acid and sodium citrate, etc.

If the spinning solution has a pH lower than 3, the coagulation speed in the bath will be slowed down and corrosion of the apparatus will appear due to the too high acidity. On the other hand, if the pH is greater than 5, the solution will become unstable, with an increase in viscosity, which greatly affects the spinning conditions.

The concentration of PVA in the spinning solution is preferably in a range between 10 and 30% by weight; preferably, its degree of polymerization will be greater than 500. The solution thus defined is spun in a strongly alkaline coagulation bath, containing mainly water, sodium or potassium hydroxide in a range between 10 and 100 g / l and sodium sulfate in a range of 100 to 330 g / l. A sodium or potassium hydroxide content of less than 10 g / l gives rise to undesirable effects, in particular a slowing down of the coagulation speed and a reduction in the ability to stretch at the time of spinning. A dose greater than 100 g / l of these additives is undesirable, because the gelling effect due to alkalis becomes sufficiently intense that properties such as tenacity, bad original

42369 the initial modulus and the path of the wire are more dependent on the temperature. On the one hand, if the concentration of sodium sulphate is less than 100 g / l, the gelling effect due to alkalis outweighs the dehydrating and coagulating effect of sodium sulphate. This will cause the fiber to swell when it coagulates, giving rise to detrimental effects on product quality. On the other hand, a concentration of sodium sulfate greater than 330 g / l produces a deformation of the fiber section which takes on the appearance of a cocoon, because the dehydrating and coagulating effect outweighs the other actions. . The deformed section of the fiber is a cause of reduction in the drawing capacity.

According to the invention, the PVA fiber thus spun is subjected to subsequent treatments such as stretching on a roller, neutralization of the alkalies by means of acid, stretching with moist heat and rinsing with water to adjust the proportion of l boric acid which remains in the fiber in a range of 0.2 to 0.9% by weight of PVA. the residual amount of boric acid after rinsing with water must be greater than 0.2% of the weight of PVA, because swelling of the fiber can occur during rinsing when this acid is present in a proportion lower than the given figure, the swelling of the fiber is at the origin of a slackening of this which will then be seized in the rollers, which will give rise to an unstable operation, from where an alteration of properties such as tenacity, the initial module and the path of the wire.

These drawbacks are not observed with the present invention because the boric acid residue present in the fiber can react with PVA, hence inter- or intramolecular crosslinking, cling to PVA chains or not react . This is one of the typical characteristics of the present invention, when the content of boric acid exceeds 0.9% by weight, the ability to stretch decreases. The consequence is a lowering of the absolute values ​​of the tenacity and of the initial modulus of the wire.

It can therefore be said that by choosing the optimum conditions for coagulation, the treatment will be stabilized with a view to producing a predictable fiber endowed with a high drawing capacity. In addition, by determining the conditions for rinsing with water so as to maintain the boric acid residue in a range of 0.2 to 0.9 by weight, a product is obtained having properties hardly dependent on temperature. , without reducing its ability to stretch in dry heat.

BAD ORIGINAL

42369

According to the invention, it is necessary to draw the PVA fiber to dry heat following rinsing with water, dehydration and drying, in order to achieve the total drawing ratio of more than 1300%. If the total draw ratio is less than 1300 it is difficult to obtain the PVA fiber having the above properties. According to the invention, the PVA fiber can be stretched to a total ratio of 1800 the properties of the PVA fiber thus obtained are as follows: tenacity of the wire at 120^at0 greater than 7.5 g / d; initial modulus of the wire at 120®C greater than 100 g / d; and wire routing at 135 ° C less than 2% (rate of elongation under load of 1 g / d for 60 min). It contains 0.2 to 0.9% boric acid, the fiber is superior to conventional PVA fibers containing no boric acid or borate, in terms of its properties at high temperatures.

the determination of the boric acid which remains in the synthetic fiber is carried out by the following method.

A fiber, weighing approximately 2 g as regards the PVA, is placed in a crucible into which an aqueous solution of sodium hydroxide at 0.1 mol / liter is introduced, so as to cover the fiber. After an overnight stay in a dryer at 105 ° C, it is heated in an electric oven at 400 ° -500 ° C for 60 min. the fiber contained in the ereuset is then placed in a hot filtration vase, to which is added water exchanging air and which is maintained in the state for 60 min. Then 0.1 mol / liter hydrochloric acid is added until the color turns from red to yellow by the dropwise introduction of phenolphthalein, serving as a colored indicator. After boiling for 30 to 60 minutes, the mixture is cooled and neutralized to pH 7 with sodium hydroxide or hydrochloric acid, to which mannite is added, and again neutralized at pH 7 by titration with hydroxide 0.1 mole sodium / liter. the titration volume (cnr) is measured, the amount of boric acid that remains in the fiber is calculated by the following equation, in which V (g) is the weight of PVA in the sample, measured from the process indicated above, and * 3Ç f and v (cnr) are respectively the strength and the volume of titration of the aqueous solution containing 0.1 mol of sodium hydroxide ï

0.62 xfxv ¥

synthetic PVA fiber produced according to the invention and

BAD ORIGINAL

- Ή,

42369 having excellent properties at high temperatures, best deploys its characteristics when used in a radial tire.

In the sense of adapting to the ever increasing speed of automobiles in recent years, a tire has quickly been adopted with improved qualities such as high speed performance and handling ability. This tire is commonly called a radial tire.

the radial tire comprises a carcass made of cord which is arranged parallel to the cutting axis of the tire and of a dividing fabric provided with a belt layer in which the tire cord is arranged in a direction substantially parallel to the circumference of the tire and the outer side of the careasse, in order to reinforce the tread, the radial tire has a structure very different from that of the traditional bias ply tire in which the cord, woven into a rope fabric, is cut at an angle and forms an angle of 40 to 60 ° relative to the circumferential direction of the carcass, the most particular characteristic of the radial tire is the arrangement of the belt layer, the structure having the characteristics mentioned above in the radial tire offer numerous advantages from the point of view of performance if it is accompanied by the use, for the dividing fabric, a tire cord which has properties corresponding to this structure.

the inventors carried out studies on the radial tire, and in particular on the cord used in the dividing fabric, before leading to the production of a new radial tire using the synthetic PVA fiber of the invention.

In the radial tire of the invention, the cord is made of synthetic PVA fiber containing boric acid or borate in a proportion of 0.2 to 0.9% by weight of PVA and having a wire tenacity more than 7.2 g / d at 120 ° G, an initial wire module of more than 100 g / d at 120 ° C and a wire path less than 2% (under the load of 1 g / d for 60 mn). the twist constant of the strands of this PVA wire in the rope is from 800 to 1300. The cable twist (turns / 10 cm) is carried out in a ratio of 80 to 100% of the strand twist (turns / 10 cm).

In short, the dividing canvas is what the circle is in the barrel. the basic functions that the tire cord material used in the dividing fabric must therefore have

42369 high tenacity and a high modulus, and the synthetic fibers of P7A are generally known for their high tenacity and their high modulus. However, the conventional PVA fiber has defects in that it exhibits a noticeable drop in toughness and modulus when the temperature rises, as do other synthetic thermoplastic fibers such as polyesters and polyamides . In addition, the interior of a tire in service is normally at high temperature, of the order of 100 ° C., due to the heat accumulation due to the rolling of the tire, a phenomenon which necessarily occurs also in the tire. radial and, consequently, the tire cord used for the dividing fabric is also affected by such a rise in temperature. A radial tire using conventional IVA fiber, whose properties at high temperature are highly dependent on temperature, will not be able to manifest the main function of its robust and non-stretching dividing fabric, which is to oppose tire deformation. Obviously, it is perfectly possible to overcome this lack of resistance and modulus in conventional PVA fiber by increasing the number of fibers used in a tire. But this causes this great difficulty that the durability of the tire is greatly reduced, since the accumulation of heat increases in proportion to the increase in the number of fibers used, which decreases the grip and the resistance to fatigue.

In view of the above, the applicant proposes a radial tire using the ETA fiber according to the invention, which exhibits excellent properties at high temperatures. The inventors have discovered that a radial tire will not be able to have its advantages if the PVA fiber to be used does not contain boric acid or borate within the limits of 0.2 to 0.9% by weight and does not have a wire tenacity greater than 7.5 g / d at 120 ° C, an initial wire modulus of more than 100 g / d at 120 ° G and a wire path of less than 2 / at 135 ®C · 0e fact remains valid, whatever the conditions applied during the manufacture of the cord and the heat treatment thereof, or the structure of the tire.

One of the factors that must be taken into serious consideration is the method of making the rope and, in particular, the number of twists exerts a strong influence on the performance of the final product. There is no general number of twists suitable for any material. Ge number is inseparably in original bad

42369 relationship with the properties of the material. It is therefore impossible to apply to the PVA fiber of the invention the number of twists which is suitable for conventional PVA fiber or for other fibers, the inventors have carried out repeated tests by actually rolling the tire containing the PVA fiber of the invention with various numbers of twists, to determine the optimal twist for the chord of the dividing fabric.

What complicates matters is that the properties of a tire are both in direct proportion and in inverse proportion to the number of twists. For example, the fatigue strength is improved in direct proportion to the increase in the number of twists, while the properties related to the modulus, in particular the rolling resistance, the cornering characteristics and the wear resistance of the tread are inversely proportional to it.

For any kind of tire, and not only for the radial tire, it is necessary to satisfy the various requirements concerning it, the results of the tests mentioned above have shown that there are very strict limits as to the appropriate number of twists of the synthetic PVA fiber of the invention for manufacturing the cord of the dividing fabric in the radial tire, namely that the twist constant of the strand must be between 800 and 1500 and the cable twist (turns / 10 cm) must be equal to 80-100% of the twist of the strand (turns / 10 cm), the constant term of torsion used in this memo corresponds to the symbol K in the following equation, where D is the penny and T is the number of twists (number / 10 cm):

K = VS x T the number of twists increases as the value of K. increases.

On the one hand, when the twist constant of the strand is less than 800, not only (1) the cord takes a very uneven shape and the performance of the tire is reduced, but also (2) the fatigue resistance of the cord becomes insufficient, to the point that there are breaks in the cord before the tread is completely worn, which shortens the life of the tire, the number of twists of the cable (turns / 10 cm) exerts a much greater influence on the resistance to fatigue than the twist of the strand (turns / 10 cm), the durability of the tire is also reduced when the twist of the cable (turns / 10 cm) is less than 80 7 °

<img file="FR2072392A5_D0002.tif" />

BAD ORIGIN?

42369 the twist of the strand (turns / 10 cm).

On the other hand, if the twist constant of the strand exceeds 1300, the properties of the PVA fiber, such as high toughness and modulus, are lost, so that the advantages of the radial tire with regard to rolling resistance disappear. , the wear resistance of the tread and the bend characteristics® It is also undesirable that the cable twist (turns / 10 cm) exceeds the limit specified above, i.e. 100% twist of the strand (turns / 10 cm), because not only does it reduce the toughness and modulus of the rope to a noticeable extent, but it also causes twisting of the rope upon loosening and difficulties in handling.

The tire cord is usually subjected to an immersion treatment in order to give it adhesion to the rubber. The adhesive used in the context of the present invention is not limited to particular types: any known adhesive used in the rubber industry can be used, the preferred product being REL (mixture of a condensation product alkaline initial of resorcinol and formalin with a latex), or one which is used at the same time as a latex, containing polyvinyl-pyridine. The conditions of the immersion treatment can be similar to those applied in the process for the cord of the conventional bias ply tire. Drying, cooking, stretching and heat treatment are carried out at a temperature above 200 ° 0.

In the practice of the invention, any material used in the ordinary tire with bias plies can be used in the carcass

The invention is applicable to the manufacture of a bias ply tire with a belt, provided with a layer of tire cord belt, disposed parallel to the circumference of the tire and situated outside the carcass to reinforce the tread, like that of the radial tire, but whose carcass has the same structure as the ordinary tire with bias plies.

Before coming to the description of the examples illustrating the invention, it is necessary to describe the various tests relating to the properties of a radial tire, as well as the elements evaluated.

A - Compression piston test the result is evaluated in the form of the energy (kg.cm) absorbed before the tire breaks, by slow penetration of a compression piston. The internal tire pressure here is equal to

BAD ORIGINAL

<img file="FR2072392A5_D0003.tif" />

42369 p

1.7 kg / cm. The higher the value, the more robust the tire.

B - High speed test

In accordance with standard MVSS n ° 109 (ASÏM), one begins to roll the tire, the air of which is adjusted to 1.7 kg / cm, at 80 km / h on a test drum. The speed is gradually increased in the event that no fault has appeared in the tire after it has been driven for a predetermined time. The result is evaluated in the form of the maximum speed (km / h) at breakage of the tire and the rolling time (min) at this same speed. The higher the numerical value, the greater the endurance at high speed.

C - Turnover

The turning force (kg) of a tire with an air pressure p

set at 1.7 kg / cm is measured at a speed of 30 km / h, with a load of 125 kg and a sliding angle of 10 °. The value obtained by dividing this turning force by the sliding angle constitutes the turning steepness (kg /⁰). The higher this value, the better the turning characteristic.

D - Resistance to wear of the tread

A car fitted with tires with an air pressure set at 1.7 kg / cm is driven on a test route.

After the automobile has traveled 20,000 km at a speed of approximately 80 to 100 km / h, the degree of wear of the tread in contact with the ground is measured. The wear resistance of the tread is expressed by the distance traveled by the tire until the tread has a wear of 1 mm. The higher this value, the higher the wear resistance of the tread.

E - Sustainability

A car fitted with tires with an air pressure set at 1.7 kg / cm is driven on a test course for 20,000 km at a speed of around 80 to 100 km / h. By sampling the tire cord of the dividing fabric before and after the test run, the resistance of the cord is measured. It is expressed in residual resistance (%) of the tire cord compared to the original cord. The higher this value, the greater the durability.

We can add to this description that the synthetic PVA fiber whose properties at high temperatures are improved is applicable to the tension element of a V-belt or to the reinforcement of flexible pipes. A high module and a low original chebad ^

42369 ornamentation at high temperatures make it possible to produce a V-belt whose dimensional stability is fixed when in service. High pressure hoses, intended for use in pressurized oil machines and tools, can benefit from the use of PVA fiber, since the expansion of the hose under the effect of internal pressure is very limited thanks to the high module at high temperature. Example 1

10 kg of an aqueous PVA solution containing 1.7 kg of PVA are prepared (degree of polymerization, 1750; degree of saponification,

99.5 mol%), 34 g of boric acid and a small amount of nitric acid to adjust the pH to 4.3. The spinning solution is passed through a die having 600 spin holes of 0.08 mm in diameter, to the coagulation bath which contains 30 g / l of sodium hydroxide and 230 g / l of sodium sulfate. The fiber thus spun is then extracted from the bath at a rate of 10 m / min, to be subjected to subsequent treatments such as: drawing by roller with 100 neutralization in a bath containing 70 g / l of sulfuric acid and 300 g / l sodium sulfate; 150% wet heat stretching; rinsing with water to set the boric acid content to 0.45%; dehydration and drying; and drawing with dry heat at 220%. The final product obtained is drawn at a total drawing ratio of 1500%.

The product thus obtained has a wire tenacity of 9.3 g / d at 120 ° C, an initial modulus of wire of 135 g / d at 120 ° C and a wire path of 1.4% at 135 ° C.

When manufacturing a radial tire for passenger cars, of dimensions 165-13, using the synthetic PVA fiber of the invention, the PVA fiber of 1200 d / 600 f (f being the number of filaments) is used for the division fabric, while a super tenacity 1650 d / 1100 f rayon is used at the carcass. The two threads are wired and woven into a cord fabric, the characteristics of which are given in Table 1.

BAD ORIGINAL

7Q 42369

Table 1

<td></td><td>Classification</td><td>Material A</td><td>Material B</td>

<td></td><td>Manufacturing method</td><td>1200d / l / 3</td><td>l650d / l / 2</td>

<td></td><td>Number of) strands itr / 10 cm)</td><td> 30</td><td> 50</td>

<td></td><td>twists) cable ()</td><td> 25</td><td> 50</td>

<td>Rope</td><td>Strand twist constant</td><td> 1039</td><td> 2031</td>

<td></td><td>Cable twist / strand twist x 100 (%)</td><td> 83</td><td> 100</td>

<td></td><td>Meaning of) strand twist</td><td>Z</td><td>Z</td>

<td></td><td>cable)</td><td>S</td><td>s</td>

<td>Rope fabric</td><td>Density (strands / 5 cm)</td><td> 32</td><td> 49</td>

<td>the</td><td>two rope fabrics A and B are</td><td>subject to</td><td>treatment</td>

normal immersion, using a BEL solution. On the one hand, the rope fabric  is then treated with dry heat for 3 min at 200 ° C, with stretching at 2.5 &amp; On the other hand, the rope fabric B is dried at 150 ° C while retaining its original length.

the tire of the invention is obtained by using the specified cord fabrics ei-dessas in the dividing fabric and in the carcass, by applying methods such as making the blank, shaping the tire, vulcanization and heat treatment post-vulcanization.

However, the tire consisted of four plies in the dividing fabric and two plies in the carcass.

the results of the various tests on the performance of the tire are reported in table 2. In this table, the comparative examples relate to radial tires which are identical to the tire of the invention with regard to their structure and their dimensions, but in the division web of which a PVA fiber which has not satisfied was used not to certain of the manufacturing conditions and to certain properties of the invention, the results of the tests carried out on the comparative examples have also been reported in the table.

42369 i fi

β] Ο ft ra Srlt&gt; O 05 O ri o

ua

VS-

AU in

CM

O * KA * **

K- NV

O ka

CM o

to o

KA oo

U laughed^- ί ** ri o

Ot 02 S ri LO o ri O ri

<td>o</td><td>m</td><td>L © * O</td><td></td><td></td><td></td><td></td><td>O</td>

<td>LfA</td><td> ·»</td><td>r.</td><td></td><td></td><td></td><td></td><td>O</td>

<td>Ο-</td><td>in</td><td>00 SM 'xf</td><td>o</td><td>o</td><td>O</td><td>o</td><td>CM</td>

<td></td><td>in</td><td></td><td></td><td>CM</td><td>it</td><td>CM</td><td></td>

<td>χ—</td><td></td><td></td><td></td><td>CM</td><td></td><td>KA</td><td>X ~</td>

oo

O CM isjOA i ri os o ft ma ri mo ri O ri

<td>o</td><td>m</td><td>M3 * O</td><td></td><td></td><td></td><td></td><td>O</td><td></td><td></td><td></td>

<td>tn</td><td>• S</td><td>· »* K</td><td></td><td></td><td></td><td></td><td>O</td><td></td><td></td><td></td>

<td>h—</td><td>&lt;n</td><td>œ o »m-</td><td>o</td><td>o</td><td>O</td><td>o</td><td>AU</td><td>o</td><td>O</td><td>o</td>

<td></td><td>in</td><td>T ~</td><td></td><td>CM</td><td>co</td><td>CM</td><td></td><td>o</td><td>tn</td><td>CM</td>

<td> *-</td><td></td><td></td><td></td><td>CM</td><td></td><td>KA</td><td>x-</td><td>at ”</td><td>T-</td><td>CM</td>

ά o ft sa a ή rio ri o ri

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>8 § i ©</td>

<td>O</td><td>m</td><td>CM</td><td></td><td></td><td></td><td>o ·</td><td>d fi a »60</td>

<td>AU</td><td>9k</td><td>· »9k</td><td></td><td></td><td></td><td>O</td><td>gp- ri</td>

<td>t-</td><td>in</td><td>£ * - CM</td><td>AU O</td><td>O</td><td>O</td><td>o</td><td>§Ώ H ri</td>

<td></td><td>in</td><td>v</td><td>x— LO</td><td>VS-</td><td>O</td><td></td><td>3 ft laughed</td>

<td></td><td></td><td></td><td>KA</td><td></td><td>KA</td><td>x—</td><td>see cf zri-p</td>

i ri ri o ft 02 a ή ka o ri O ri

O UA UA t&gt; OA

OA

CM «- t- CM oo CO OA r

ri ® o ft-ri 80 ri ri O ri H Sî H ri • HP ft

CM ί

β r-1 ri

Ε4 i ri ri o ft æ a -h &lt;mo ri O ri

Where in

CM -r * x · &lt;

t— CM -Μo or · AU

O c— o

o

KA

<img file="FR2072392A5_D0004.tif" />

1ϊ^Λ3 &lt;- s ri ft i if ri o ft œ a -Ho ri O ri o

AU c—

LfA

*.

in in

ΙΑ! xt- cm vr oo ο o

MD C—

CM

O o

KA ri ri 1 ® a cfzri-p ©

&amp;

s · φ

K ft o

AU

It’s “A

OA

OA

O KA. " M

C— CM χφ

O

KA &amp;

CM

O c— here

Where

&lt;!

ft ft g Æj g

Ή • P ri ®

Ή ri &lt;H 'ri ri a

ft O fi o

laughed

-P ri o

laughed

S g

·· ft ri ri 80 ri ft ri ft "." Riri ri Ό ri ri '©' © â if "" η nt} ri

-P

H ri • rl O ft ri • P ri ri ri ri ri ri oo • HO

-g fi ri o ri O o 02

AS.

'ri fi o

• n laughed

g.

• r) laugh

O

P ri ri ri d

laugh laugh

• H £

O ft

O ri o

laugh laugh

laughed

Ή ri ri ri - * ·&gt; H ri O&gt; ® 60 ri o

laughed

-P ri ri ri - · ri ri H

-P 60 ri - * Φ o © ©

ri a en O CM HW ri ri ri ri ft ft ri ft ft ri ri ft ri

O in

CM îri ri ·

O ©

Μ M cm ri ri ri ft ri -P ft

<td>O</td><td></td><td></td><td></td>

<td>tn</td><td>O</td><td>O</td><td>O</td>

<td></td><td>O</td><td>AU</td><td>CM</td>

<td></td><td></td><td></td><td>CM</td>

<td></td><td></td><td></td><td></td>

<td></td><td></td><td>AS</td><td>AS</td>

<td></td><td></td><td>Z</td><td></td>

<td></td><td>X '·' *,</td><td> ©</td><td></td>

<td></td><td>AS</td><td>laughed</td><td> ©</td>

<td>X - »*</td><td></td><td>laughed</td><td>ft</td>

<td></td><td></td><td>at</td><td>O</td>

<td> ©</td><td></td><td>fi</td><td>Z ©</td>

<td rowspan="2">£ laughed</td><td></td><td>ft</td><td>m</td>

<td></td><td>laughed</td><td>laughed</td>

<td>laughed</td><td>fi</td><td>fi</td><td>fi</td>

<td>-P</td><td>laughed</td><td> ©</td><td> ©</td>

<td>'laughed</td><td> © _|</td><td>d</td><td>d</td>

<td>laughed</td><td> 3</td><td>K ft</td><td>CO ft</td>

<td></td><td>o</td><td>O</td><td>o</td>

<td>laughed</td><td>laughed</td><td></td><td></td>

<td>d</td><td></td><td>laughed</td><td>laughed</td>

<td>-P</td><td>laughed</td><td>laughed</td><td>laughed</td>

<td>o</td><td>laughed</td><td></td><td></td>

<td> +»</td><td>ft</td><td>zri</td><td>zri</td>

<td> £</td><td> © 60</td><td> « 60</td><td rowspan="2">© 60 laughed</td>

<td>o</td><td> &amp;</td><td>laughed</td>

<td>ft</td><td>laughed</td><td>laughed</td><td>laughed</td>

<td>ft</td><td>laughed</td><td>laughed</td><td>laughed</td>

<td>laughed</td><td>-P</td><td>-P</td><td>-P</td>

<td>ft</td><td>ft</td><td>ft</td><td>ft</td>

xioxq.'eoTjq'Bj ep Βποτ ^ τρποο

42369

<td> 1 ^Λmo</td><td> 46</td><td>the</td><td>pa</td><td>IA</td><td>o CM</td><td>h-</td><td>O</td>

<td>p ©</td><td>• k</td><td>© k</td><td>"K</td><td> 00</td><td>• k</td><td>• k</td><td>H</td>

<td>S πιτ-</td><td>O</td><td>CO</td><td>CO CM</td><td>Η-</td><td>CM</td><td>PA</td><td>x- in</td>

<td>ο this</td><td></td><td></td><td>σ "</td><td>ΡΑ</td><td>σ "</td><td>PA</td><td> 00 00</td>

<td>O fl</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>ia</td><td>o</td><td></td><td></td><td></td><td>H-</td><td></td><td></td>

<td>(fl o</td><td>o</td><td>O</td><td>H ·</td><td> 00</td><td>CM</td><td>IA</td><td>o</td>

<td>P ©</td><td> ·*</td><td>"K</td><td>• k</td><td>in</td><td> *-</td><td>"K</td><td>CO</td>

<td>a aco</td><td></td><td>vs-</td><td>CM CM</td><td>CM</td><td>H-</td><td>CM</td><td>m cm</td>

<td>o fl</td><td></td><td></td><td>co</td><td>H ·</td><td> 00</td><td>PA</td><td>t- co</td>

<td>o fl</td><td></td><td></td><td></td><td></td><td> ·“</td><td></td><td></td>

<td>i fl</td><td>m</td><td></td><td></td><td></td><td>PA</td><td></td><td></td>

<td>as o</td><td></td><td>PA</td><td>pa</td><td>CM</td><td>CM</td><td>E—</td><td>S</td>

<td>P ©</td><td>"K</td><td>• k</td><td>• k</td><td>PA</td><td> —</td><td>"K</td><td>PA</td>

<td>â h la</td><td>o</td><td></td><td>V- CM</td><td>CO</td><td>OO</td><td>Q</td><td>O CO</td>

<td>o fl</td><td></td><td></td><td>in</td><td>Η-</td><td>o</td><td>PA</td><td> 00 00</td>

<td>o fl</td><td></td><td></td><td></td><td></td><td>CM</td><td></td><td></td>

<td>I fl</td><td>œ</td><td></td><td></td><td></td><td>O</td><td></td><td></td>

<td>fl o</td><td>M-</td><td></td><td></td><td>ΡΑ</td><td>H-</td><td>CM</td><td>o</td>

<td>Pim</td><td>• k</td><td>* k</td><td>• k</td><td>H-</td><td>• k</td><td>• k</td><td>PA</td>

<td>â a h-</td><td>o</td><td>tn</td><td>DAD</td><td>CO</td><td>o</td><td>o</td><td>co O</td>

<td>O fl</td><td></td><td></td><td>CO</td><td>CM</td><td>CO</td><td>PA</td><td>E- E—</td>

<td>o fl</td><td></td><td></td><td></td><td></td><td> ·*-</td><td></td><td></td>

<td>I fl</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>fl o</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>Folds</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>aa pa</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>o fl</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>O fl</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>1 fl</td><td>CM</td><td></td><td></td><td></td><td>IA</td><td></td><td></td>

<td>do</td><td>tn</td><td>o</td><td>CM</td><td>IA</td><td>CM</td><td> 00</td><td>O</td>

<td>Pim</td><td>"K</td><td></td><td>• k</td><td>t—</td><td> ·*</td><td>© k</td><td>in</td>

<td>a to CM</td><td>o</td><td></td><td>CM CM</td><td>X—</td><td>CM</td><td>CM</td><td>CM CO</td>

<td>O fl</td><td></td><td></td><td> &lt;0</td><td>H-</td><td>we</td><td>PA</td><td>co c-</td>

<td>O fl</td><td></td><td></td><td></td><td></td><td> *-</td><td></td><td></td>

<td>1 fl</td><td></td><td></td><td></td><td></td><td>o</td><td></td><td></td>

<td>fl o</td><td>m</td><td>CM</td><td>IA</td><td>H-</td><td>T—</td><td>in</td><td>o</td>

<td>Plia</td><td>"K</td><td>• k</td><td>• k</td><td>CM</td><td> ·*</td><td>• k</td><td>τ—</td>

<td>ah -ί-</td><td>o</td><td>CO</td><td>CM CM</td><td>IA</td><td>H ·</td><td>T-</td><td>t- PA</td>

<td>ο fl</td><td></td><td></td><td>vs-</td><td>PA</td><td>OO</td><td>tn</td><td>E— E-</td>

<td>a fl</td><td></td><td></td><td></td><td></td><td>X—</td><td></td><td></td>

<td> ©</td><td>ia</td><td></td><td></td><td></td><td>O</td><td></td><td></td>

<td>Γί</td><td>h-</td><td>pa</td><td>H</td><td>PA</td><td>CM</td><td>ITk</td><td>O</td>

<td>P</td><td>• k</td><td> ·»</td><td>• k</td><td>CO</td><td> «.</td><td>• k</td><td>CM</td>

<td>at ·-</td><td>o</td><td>σ "</td><td>IA T-</td><td> 00</td><td>t-</td><td>O</td><td>in the</td>

<td> «</td><td></td><td></td><td>PA</td><td>PA</td><td></td><td>M</td><td>oo in</td>

<td>M</td><td></td><td></td><td>χ—</td><td></td><td>CM</td><td></td><td></td>

<td>P4</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td> ©</td>

<td></td><td></td><td></td><td></td><td></td><td>fl</td><td></td><td>AT</td>

<td></td><td></td><td></td><td></td><td>fl</td><td>g</td><td></td><td>fl</td>

<td></td><td></td><td></td><td></td><td>Oz-&gt;</td><td></td><td></td><td>fl</td>

<td></td><td></td><td></td><td>z- ^</td><td>aa</td><td> ·*</td><td></td><td> 33</td>

<td></td><td></td><td></td><td>fl</td><td>© O</td><td> 34</td><td></td><td></td>

<td></td><td> ©</td><td></td><td></td><td> © ·</td><td></td><td></td><td>fl</td>

<td></td><td>fl</td><td></td><td> 40</td><td>© a</td><td>at</td><td>O</td><td>r — 1</td>

<td></td><td>σ '</td><td></td><td></td><td>fl Λ)</td><td></td><td></td><td></td>

<td></td><td>• H</td><td></td><td>χ — X</td><td>Pc—</td><td></td><td> 60</td><td> ©</td>

<td></td><td>fl</td><td></td><td>Z * XX</td><td>at</td><td></td><td></td><td>&gt; £ jz — x</td>

<td></td><td>o</td><td>fl</td><td>o</td><td>O</td><td> «</td><td></td><td>at</td>

<td></td><td> 32</td><td></td><td>o</td><td>O</td><td> ©</td><td></td><td>© a</td>

<td></td><td></td><td> 40</td><td>O</td><td></td><td> ©</td><td> ©</td><td>fl- · '”</td>

<td></td><td>e</td><td></td><td>CM O</td><td> ©</td><td> ©</td><td> 40</td><td>fl 4p</td>

<td></td><td>fl</td><td></td><td>x- o</td><td>fl</td><td>P</td><td>fl</td><td>a Λ4</td>

<td></td><td>AT</td><td></td><td>- IA</td><td></td><td>• rl</td><td>fl</td><td>fl ^ _x</td>

<td></td><td>O</td><td>O</td><td>PA</td><td>fl</td><td> &gt;</td><td>AT</td><td></td>

<td></td><td>flz-x</td><td>o</td><td>H -</td><td>o</td><td></td><td> !&gt;</td><td>H -P</td>

<td></td><td>- 'ïg.</td><td>O</td><td>CO</td><td> -13</td><td> ©</td><td></td><td>fl</td>

<td></td><td></td><td>CM</td><td>AT</td><td> ©</td><td>-P</td><td> ©</td><td>zfl © '-'</td>

<td></td><td></td><td>x—</td><td>-P + »</td><td>AT</td><td>fl</td><td>AT</td><td>at</td>

<td></td><td>fl H</td><td></td><td>A fl</td><td>Pi</td><td>fl</td><td></td><td>© © A</td>

<td></td><td>O ©</td><td></td><td>fl ©</td><td></td><td> 34</td><td> ©</td><td>OH -P</td>

<td></td><td>• A fl</td><td>MD</td><td>•Ha</td><td>fl</td><td></td><td>O</td><td>fl fl H</td>

<td></td><td>-P fl</td><td>• P</td><td> ©</td><td>fl</td><td>zfl</td><td>fl</td><td>fl o H</td>

<td></td><td>fl A</td><td>AT</td><td>© a</td><td></td><td></td><td>fl</td><td>-P fl H</td>

<td></td><td>where your</td><td>O</td><td>HA</td><td>• H</td><td>-H</td><td> ©</td><td> © 33</td>

<td></td><td>PXD</td><td>fl</td><td>fl a</td><td>fl</td><td>fl</td><td> ©</td><td>• H © fl</td>

<td></td><td>O fl</td><td>fl</td><td>fl ©</td><td> ©</td><td> ©</td><td>H</td><td>© fl fl</td>

<td></td><td>fl</td><td>MD</td><td>JS</td><td> ©</td><td> ©</td><td>fl</td><td> ·©</td>

<td></td><td>PM</td><td>H</td><td>go</td><td>W</td><td></td><td>ίζ</td><td>ffj -A</td>

<td></td><td colspan="2">TTJ</td><td></td><td></td><td colspan="2">neud</td><td>up</td>

<td></td><td colspan="3">np s ^^ TJdoja:</td><td colspan="4">seouemjtojaej</td>

at

<td></td><td>• rl fl O ©</td>

<td> ©</td><td>© fl © -P fl -P XD O fl H P Φ</td>

<td>fl</td><td> 5</td>

<td> &amp;</td><td>fl</td>

<td>AT</td><td>σ '</td>

<td>fl</td><td>• rl</td>

<td>P</td><td>P</td>

<td>fl</td><td> '©</td>

<td>fl</td><td>O</td>

<td>-P</td><td>fl</td>

<td> ©</td><td> ©</td>

<td>fl</td><td>fl</td>

<td>AT</td><td>• rl</td>

<td>O</td><td>O</td>

<td>fl</td><td>fl</td>

<td>β</td><td> *</td>

<td>rd</td><td>rd</td>

<td>fl</td><td>fl</td>

<td>fl</td><td>fl</td>

<td>Pt</td><td>Pi</td>

<td> '©</td><td>XD</td>

<td>H</td><td>H</td>

<td> 40</td><td> 40</td>

<td> '©</td><td>XD</td>

<td>fl</td><td>fl</td>

<td>H</td><td>W</td>

<td>Pi</td><td>Pi</td>

<td></td><td>CM</td>

<td> *</td><td> *</td>

In Example 1 and Comparative Examples up to 4, the pH is adjusted by means of nitric acid.

aS

-po

HER

42369

Example 2

A PVA fiber containing sodium borate and drawn at a total drawing ratio of 1500% is obtained in the same manner as in Example 1, except for the use of sodium borate in a proportion of 1.5 compared to PVA in place of boric acid, and tartaric acid in place of nitric acid for pH adjustment. The product obtained has a wire tenacity of 9.1 g / d at 120 ° C, an initial modulus of wire of 127 g / d at 120 ° C and a path of 1.5% at 135 ° C · the performances of radial tires, made with this wire, have been compared for different? twists of the rope for the division fabric, as indicated in table 3.

Table 3

<td></td><td>Free 2</td><td>Compa- reason 8</td><td>Compa- reason 9</td><td>Compa- reason 10</td><td>Compa- reason 11</td>

<td colspan="2">Number of) strand (turns / 10 cm) 30</td><td> 30</td><td> 23</td><td> 18</td><td> 40</td>

<td>twists) cable ("</td><td> ) 30</td><td> 20</td><td> 11,5</td><td> 18</td><td> 40</td>

<td>Sense of the) strand</td><td>Z</td><td>Z</td><td>Z</td><td>Z</td><td>Z</td>

<td>twist) cable</td><td>s</td><td>S</td><td>s</td><td>S</td><td> 3</td>

<td colspan="2">Torsional constant of strands 1039</td><td> 1039</td><td> 797</td><td> 624</td><td> 1386</td>

<td>Cable twist / twist</td><td></td><td></td><td></td><td></td><td></td>

<td>strand x 100 (%)</td><td> 100</td><td> 67</td><td> 50</td><td> 100</td><td> 100</td>

<td></td><td>no</td><td>break</td><td>not</td><td> »</td><td>no</td>

<td></td><td colspan="2">inddent of</td><td>H</td><td>not</td><td>incident</td>

<td></td><td>after</td><td>rope</td><td>not</td><td>not</td><td>after</td>

<td></td><td> 40000</td><td>of the</td><td>not</td><td>not</td><td> 40000</td>

<td></td><td>km from</td><td>canvas</td><td>not</td><td>not</td><td>km from</td>

<td></td><td>market</td><td>division</td><td>not</td><td>H</td><td>market</td>

<td></td><td></td><td>at the end</td><td>II</td><td>not</td><td></td>

<td></td><td></td><td>of</td><td>II</td><td>not</td><td></td>

<td></td><td></td><td>30000km</td><td>24000km</td><td>12,000 km</td><td></td>

<td>Durability (% resistance</td><td></td><td></td><td></td><td></td><td></td>

<td>residual rope</td><td></td><td></td><td></td><td></td><td></td>

<td>after 20,000 km of walking)</td><td> 97</td><td> 81</td><td> 73</td><td> -</td><td> 96</td>

<td>Turning power (kg / ®)</td><td> 40,3</td><td> 39,6</td><td> 43,3</td><td> 45,6</td><td> 30,6</td>

Example 3

An aqueous solution of PVA at a concentration of 15% by weight, containing 150 g of PVA having a degree of polymerization of 2350 and a degree of saponification of 99.5 mol%, is added with 30 g of boric acid (2% in weight relative to PVA) and small amounts of aeetic aid to prepare a spinning solution

<img file="FR2072392A5_D0005.tif" />

<img file="FR2072392A5_D0006.tif" />

42369 a pH of 4.5. The spinning solution is spun in a strongly alkaline coagulation bath, composed mainly of water and containing 40 g / l of sodium hydroxide and 250 g / l of sodium sulfate. After having been extracted from the bath at a rate of 10 m / min, the wire is subjected to the following operations: drawing on a roll at 100 neutralization, drawing with moist heat at 150%, rinsing with water to adjust the amount of acid residual boric at 0.4% by weight relative to the PVA, dehydration and drying, as well as drawing with dry heat at 200%. The product (1200d / 600f) is therefore stretched at the total stretching ratio of 1400 fi. The product thus obtained has a wire tenacity of 9.2 g / d at 120 ° C, an initial modulus of 131 g / d at 120®C and a path of 1.9% at 135 ° Cj the product is superior as to its properties at high temperatures.

The wire thus obtained is used to manufacture the division fabric of a radial tire, by wiring into a cord (1200/1/3) under the following conditions:

strand twist 30 turns / 10 ca cable twist 30 direction of twist) strand Z) cable S strand twist constant 1039 cable twist / strand twist x 100 (%) 100

No damage was observed after 35,000 km of pond. The durability is 98 fi and the turning power is equal to 40.8 kg /⁰.

Example 4

An aqueous solution of PVA at 17% by weight, containing 100 kg of PVA having a degree of polymerization of 1750 and a degree of saponification of 99.9 mol%, is added with 2 kg of boric acid (2% by weight) relative to PVA) and 0.3 kg of acetic acid (0.005 g equivalent of 100 g of PVA) to prepare a spinning solution. The pH is maintained at 4.5.

The spinning solution is sent, through dies with 1000 holes of 0.15 mm in diameter, to a coagulation bath containing 50 g / l of sodium hydroxide and 200 g / l of sodium sulfate. Then the fiber is extracted from the bath at a rate of 10 m / min. In this case, the spinning conditions are very stable. During a two-week spinning, no incident was observed, such as a plugging of the die. The spun fiber is then subjected to the same

42369 treatment as in Example 3: that is to say, drawing with a roller, neutralization, drawing with moist heat, rinsing with water to adjust the proportion of residual boric acid to 0.5% by weight per PVA ratio, dehydration, drying and stretching with dry heat. the product (1800d / lC00f) thus obtained is drawn to a total ratio of 1400%. the product has a wire tenacity of 9.3 g / d at 120 ° C, an initial modulus of 154 g / d at 120 ° C and a path of 1.8% at

135 ° W.

the wire thus obtained is used vision of a radial tire, by wiring the following conditions: twist of strand cable twist direction of twist) strand) constant cable of twist of strand cable twist / twist of strand x 100 (#)

After 35,000 km of walking, durability reaches 96% and 41.2 kg /⁰.

to make the canvas of a rope (1800 d / 1/2) in turns / 10 cm 30

ZS

1272

100 no damage was observed, the turning power is equal to

42369