ES414751A1

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

Abstract

Perfections introduced in radial fabric tires, characterized in that they present a protector that is made of cord which comprises polyvinyl alcohol fibers containing boric acid or a borate salt thereof in an amount of 0.2 to 0.9% by weight. Weight of polyvinyl alcohol, said fibers having the following properties at elevated temperature: yarn tenacity at 120º c, at least 7.5 g/d, initial yarn modulus at 120º c, at least 100 g/d, and yarn creep at 135º c, less than 2%, the fibers coiling under the torsional constant of the layers from 800 to 1300 and the twisting of the cable (turns/10 cm) from 80 to 100 percent of the twisting of the fabrics (turns/10) cm). (Machine-translation by Google Translate, not legally binding)

ES414751A1, drawing sheet 1 — Sheet 1 of 36

Term

Term ended

Projected expiry passed 14 May 1993, 33.4 years ago.

5 claims: 4 independent, 1 dependent

1
REIVINDICACIONES Los puntos de invención propia y nueva que se presentan para que sean objeto de esta solicitud 10 de Patente de Invención en España, por VEINTE años, son los que se recogen en las reivindicaciones siguientes:1a,- Perfeccionamientos introducidos en neumáticos de telas radiales, caracterizados por que presentan un protector que está hecho de cordoncillo que 15 comprende fibras de poli-alcohol vinílico que contienen ácido bórico o una sal borato del mismo en una cantidad de 0,2 a 0,9% en peso de poli-alcohol vinílico, presentando dichas fibras las propiedades singuientes a tempe, 19 ratura elevada: tenacidad del hilo a 1202C, al menos 6.73. 7,5 g/d, módulo inicial del hilo a 12020, al menos 100 g/d, y fluencia del hilo a 135 2 C, inferior al 2%, arrollándose las fibras bajo la constante de torsión de las capas de 800 a 1300 y la torsión del cable (vueltas/10
2
5 cm) de 80 a 100 por ciento de la torsión de las telas (vueltas/10 cm). 22,- Perfeccionamientos según la reivindicación 12, caracterizados porque la fibra de poli-aleo hol vinílico utilizada en el cordoncillo del protector es
3
10 una fibra sintética obtenida a partir de una solución de hilatura de poli-alcohol vinílico que contiene ácido bórico o borato y que se mantiene a un pil de 3 a 5, conteniente la solución de 10 a 100 g/l de hidróxido alcalino y de 100 a 33θ g/l is sulfato sódico, sometiéndose la
4
15 solución a estirado con rodillos, neutralización, estira do a calor húmedo, lavado con agua para ajustar la canti dad de ácido bórico o borato que permanece, para que sea del 0,2 al 0,9% del peso del poli-alcohol vinílico, deshidratación y secado, y estirado a calor seco para que
5
20 resulte una relación de estirado total de más del 1500%. 32.- Perfeccionamientos introducidos en neumáticos de telas radiales. Tal y como se ha descrito en la Memoria que antecede y para los fines que se han especificado. 20.6.73. 35 Esta Memoria consta de treinta y seis hojas escritas a máquina por una sola cara. G.D.S. 20.6.73. Madrid, T. A. wl ra?;Per Ped

Independent claims5

685 paragraphs in 56 sections, as filed

414 751

Ρ.- 54,476

4 / + - 94790 Div.

wmm DESCRIPTIVE t CL2: ............. S £ .Q..fe

To apply for PATENT INVENTION IN SPAIN for 20 years on behalf of KURARAY CO., LTD.

Japanese entity established in 1621 Sakazn, Kurasliiki-City, Japan by: PERFECTING INTRODUCED IN TIRES

RADIAL FABRICS (International Class B60c)

20.6.73

The present invention relates to vinyl poly-alcohol fiber having excellent high temperature properties, such as thread toughness, initial thread modulus, and thread displacement; it also refers to radial folding tires that uti.

Lize said fiber on its breaker rope, winding it under previously determined winding conditions.

In general, the poly-alcohol fiber came. 10 Lico (EVA) outperforms the other synthetic fibers in resistance to breakage, and in initial modulus, and, recently, they have extensive use in the fields of ERE, for example. It is well known that the EVA fibers - which stretch to the stretch limit and are reduced to a minimum in heat shrinkage, exhibit breakage resistance and an outstanding initial module. However, EVA fibers, similar to other synthetic fibers, show the tendency that high temperature properties, as indicated above, can be greatly degraded, in proportion to the temperature rise.

The main purpose of the present invention is to eliminate the previous drawbacks of synthetic fibers, thereby providing a new EVA fiber that has excellent properties at a temperature20.6.75.

high ture, and provide radial folding tires that employ said fiber in the stripper rope. More particularly, synthetic fiber, according to the present invention, is superior to conventional PVA fibers, in the tenacity of the yarn, the initial modulus of the yarn and the displacement of the yarn. The radial folding tire using the PVA fiber of the present invention in its separator rope shows, as will be shown in the description given below, excellent results in the perforator test, high speed test , turning power test, tread wear resistance test, and duration test.

The synthetic VAT fiber and the radial fold tire are indicated in separate description.

I.- PVA synthetic fiber, according to the present invention, has high crystallinity and molecular orientation, and is characterized by its high temperature properties, as indicated below, and its boric acid (H ^ BO ^) or borate content (The description below refers to boric acid), these properties being at elevated temperature, the following:

Thread tenacity at 12020 7.5 g / d and more

Initial module of the thread at 1202C 100 g / d and more

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- 5 414751

Thread offset to 135£C 2% and less

Boric acid content 0.2 to 0.9% of the weight of PVA.

Generally speaking, the ability.

The extent of synthetic fibers increases in proportion to the temperature rise, and the resistance of the initial module may decrease. This phenomenon can be considered to occur due to the movement of molecular chains that begins when the fibers are heated, where the molecular orientation is lower, and the movement soon reaches the area where the molecular orientation is intense. Therefore, it is important in improving the high temperature properties of a synthetic fiber to suppress the movement of the molecular chains as much as possible. This can be achieved, either (1) by intensifying the orientation of the molecular chains to a degree where it is impossible for them to move, or (2) adding to the polymers a certain substance that prevents movement of the molecular chains. However, these two remedies are not capable of achieving the objects of the present invention, that is, the improvement of the high temperature properties, such as the tenacity of the thread, the initial modulus of the thread and the displacement of the thread, when They use separately. For example, the improvement can be expected

20.S.7J.

- 4- -

of the initial modulus of the yarn in a method in which a conventional PVA fiber is subjected to a subsequent treatment with boric acid, while the same procedure can result in a decrease in the tenacity of the yarn to a remarkable degree. Various investigations carried out by the present Inventors have led to the conclusion that the essential factor that performs the main object of the present invention is a fibrous structure whose orientation of the molecular chains is quite intense, as a whole, but which contains a substance to prevent the movement of molecular chains when said molecular orientation is relatively free. That is, part or all of the boric acid contained in the fiber can be combined with the

EVA in relatively free orientation, to prevent the movement of molecular chains caused by heating. When the boric acid content does not reach 0.2% of the weight of the PVA, it is insufficient to restrain the movement of the chains, while if it exceeds the amount of 0.9%, it will be impossible for the molecular chains remain highly oriented, thereby causing a decrease in the resistance of the wire.

The PVA fiber of the present invention is produced according to the procedure comprising: Pre20.6.75

- κ · stop an aqueous solution Le PVA containing boric acid or borate (the spinning solution); spinning in a coagulation bath comprising, mainly, water containing sodium hydroxide or potassium hydroxide and sodium sulfate, said elements being in a previously determined amount; stretch between rollers; neutralize the alkali adhered to the fiber by an acid; stretch in moist heat; wash with water to adjust the amount of boric acid that remains in the PVA fiber, within a previously determined interval; dehydrate and dry; and, stretch in dry heat.

Working on the composition of the coagulation bath, the concentration of the coagulation bath that has been used in the conventional wet spinning method, to produce PVA fibers that contain neither boric acid nor borate, is almost saturated with sodium sulfate, when sodium sulfate is used as a bath, which is a dehydrating salt. This is due to the fact that the fibers can be held tight, with one another, due to insufficient coagulation, when the concentration of said bath is less than 3θθ g / l.

For this reason, the coagulation bath used in the present invention is further combined with sodium hydroxide or potassium hydroxide, in a predetermined amount, thereby facilitating spinning of the solution of

20.6.73.

20.S.73.

spinning, which contains boric acid or borate. In addition, the properties of the PVA fiber produced in this way depend very little on the temperature. It is often observed that when the sodium sulfate content in the coagulation bath is high, the product's stretching capacity tends to decrease. The synthetic PVA fiber produced in accordance with the present invention has a capacity. higher stretch and less temperature dependence, compared to conventional PVA fibers that do not contain boric acid.

The inventors have repeated investigations and experiments that vary, on the coagulation capacity of the aqueous PVA solution that contains neither boric acid nor borate, and the properties of the product obtained therefrom, and have found a method and conditions for produce synthetic PVA fiber that has a tenacity of the yarn, an initial modulus of the yarn and a displacement of the yarn that hardly depends on the temperature. SI method comprises spinning an aqueous solution of PVA containing boric acid or borate, in a coagulation bath that is kept strongly alkaline by adding 10 to 100 g / l of sodium hydroxide or potassium hydroxide and 100 to 35θ g / l sulfate sodium, and so. then thread the thread to subsequent treatments such as roller stretching, neutralization of its alkali,

- 7 10

wash with. water to adjust the boric acid residue that remains in the fiber within the range of 0.2 to Oj9; Ú of the weight of VAT, dehydration and drying, and stretched in dry heat.

It is preferable to add boric acid or borate to the spinning solution, in an amount between 1 and 5.5 of the VAT weight. The solution remains weakly acidic, specifically between pH 5 and pE 5, Ξ1 acid to be added to the solution can be an inorganic acid, such as sulfuric acid, nitric acid and hydrochloric acid; an organic acid such as acetic acid, tartaric acid, etc; or a combination of an organic acid and one of its salts, for example, citric acid and sodium citrate, acetic acid and sodium acetate, tartaric acid and potassium tartrate, tartaric acid and sodium citrate, etc.

When the spinning solution has a pH of less than 3, the coagulation rate in the coagulation bath is delayed and corrosion of the apparatus may occur due to acidity, which is too strong. On the other hand, when the pH is higher than 5j, the solution becomes unstable, due to the increase in viscosity, thereby greatly damaging the spinning conditions.

The concentration of PVA in the solution pa

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- 8 414751

The spinning is preferably between 10 and 50 $ by weight; it is preferred that the degree of polymerization thereof is greater than 5 °. · This solution, as indicated, is spun in a strongly alkaline coagulation bath, which mainly contains water and sodium hydroxide or potassium hydroxide at a concentration from 10 to 100 g / 1 and sodium sulfate in the concentration of 100 to 550 g / 1. A sodium hydroxide or potassium hydroxide content of less than 10 g / 1 results in unfavorable effects, such as delayed coagulation speed and reduced stretching capacity, at the time of spinning. That said additives exceed 100 g / 1 is undesirable, since the salifying action due to the alkali becomes so. active, which makes properties such as the tenacity of the thread, the initial modulus of the thread and the displacement of the thread more dependent on temperature. When the concentration of sodium sulfate is less than 100 g / 1, the gelling action due to alkali predominates over dehydration and the coagulant action due to sodium sulfate. This can cause fiber lynching at the time of coagulation, which provides detrimental effects on the quality of the product. On the other hand, a concentration of sodium sulfate exceeding 530 g / 1 causes deformation in the fiber section whose shape

20.6.73.

- 9 414751 resembles a cocoon, since dehydration and coagulant action overlap other actions. The deformed section of the fiber is a cause of decreased stretch capacity.

In the present invention, the PVA fiber spun in this manner is subjected to subsequent treatments such as roller stretching, alkali neutralization by using acid, stretching, moist heat and washing with water to adjust the amount of boric acid that it remains in the fiber so that it is between 0.2 and 0.9% of the weight of the PVA. The boric acid residue after washing with water should be greater than 0.2% of the weight of the PVA, since swelling of the fiber can take place, at the time of washing, when it is less than the given amount. The swelling of the fiber can cause looseness in the fiber, which can then be grasped on the roller, resulting in an unstable operation, thereby decreasing properties such as the tenacity of the thread, the initial modulus of the thread and thread displacement

These drawbacks are not observed in the present invention, because the boric acid residue present in the fiber can either react with the PVA which has the effect of forming inter25 or intramolecular reticles, which are supported by the PVA chains,

20.6.73.

- 10 414751

or remain unreacted. This is one of the characteristics that give importance to the present invention. When the amount of said boric acid exceeds 0.9% by weight, the stretching capacity decreases. Therefore, this results in a decrease in the absolute values of the tenacity of the thread and the initial module of the thread.

It can then be said that by selecting the optimal conditions for coagulation, the process will be stabilized for the production of an anticipated fiber, which has a high stretching capacity. In addition, by determining the conditions for washing with water, so that the boric acid residue is maintained between 0.2 and 0.9% by weight, a product is obtained that has properties that hardly depend on temperature, without decrease the ability to stretch to dry heat.

In the present invention, it is necessary to carry out the dry heat stretching of the PVA fiber, after washing with water, dehydration and drying, in order to achieve the total stretching ratio of more than 1500%. If the total stretch ratio is less than 1500%, it is difficult to obtain the PVA fiber having the aforementioned properties. According to this invention, PVA fiber can be stretched, being

20.6.75.

the total stretch ratio of 1800%.

The properties of the PVA fiber thus obtained are: The tenacity of the yarn at 1202C, of more than 7.5 g / d; the initial module of the thread at 1202C, of more than

100 g / d; and the thread slip to 135QOj of less than 2% (degree of elongation under the load of 1 g / d for 60 minutes). It contains 0.2 to 0.9% boric acid. The fiber is superior to conventional PVA fibers that contain neither boric acid nor borates, in their high temperature properties.

The measurement of boric acid that remains in the synthetic fiber is carried out according to the following method:

A fiber that weighs, in terms of PVA,

two g, approximately, is placed in a crucible, and 0.1 molar aqueous sodium hydroxide solution is added to cover the fiber. After placing in a drying oven, at IO52C overnight, it is heated in a non-electric oven at 4002-50020 for 60 minutes. The fiber 20 of the crucible is then placed in a glass to which water that has been passed through an ion exchanger is added and allowed to stand for 60 minutes. After this 0.1 molar hydrochloric acid is added until the color changes from red to yellow using phenolphthalein as indicator. After boiling for 30-60 minutes, it is cooled and

20.6.73.

- 12 20.6.75.

neutralize to pH 7, with sodium hydroxide or water odor, mannite is added and neutralized again to pH 7, titrating with 0.1 molar sodium hydroxide. The volume (cc) used 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 test product, measured according to the method indicated above, and fyv (cc) are respectively , the concentration and volume used of 0.1 molar aqueous solution of sodium hydroxide:

0.62 xfxv

W

II.- The synthetic PVA fiber produced according to the present invention, which has excellent high temperature properties, exhibits its characteristics in its entirety when used in a radial fold tire.

To accommodate high-speed, always on the rise, cars in recent years, a tire of improved qualities, such as high-speed performance and handling characteristics, is widely used. This tire is commonly known as a radial fold tire.

The radial folding tire comprises the frame or carcass made of rope that is arranged in

parallel to the axis of the section, did I read the tire, and the separator provided with a belt-like layer where the tire rope is arranged, substantially parallel to the circumference of the tire and on the outer side of the frame, to reinforce the tread. IF radial folding tire is very different in structure from conventional biased folding tires, in which the rope entwined in the rope fabric is cut biased and arranged at an angle of 40 to 60 degrees facing the direction frame circumferential. The most peculiar characteristics in radial folding tires is the provision of the belt-like layer. The structure that has the aforementioned characteristics, in the radial folding tire, will allow many of the advantages in the results, when accompanied by the use of tire rope for the separator, which has properties corresponding to the structure.

The inventors have carried out studies on the raclial fold tire, especially in its tire rope for the separator, before being successful in providing a new radial folding tire, which uses the synthetic VAT fiber of the present Invention.

Sn the radial fold tire of the

20.6.75.

Invention Invention, the rope is made of synthetic fiber. Ethics of PVA containing boric acid or borate in the range of 0.2 to 0.9% of the weight of PVA and having the tenacity of the yarn of more than 7.2 g / d, at 12020, the initial modulus of the yarn of more than 100 g / day 12020 and the displacement of the thread of less than 2% (under the load of 1 g / d for 60 minutes). The torsion constant of the fold of said PVA thread in the rope is 800 to 1500. The twisting of the cable (vu.eltas / 10 cm) is carried out in the proportion of 80 to 100% of the twist of the fold (turns / 10 cm).

Simply put, the separator ”is what the fence is to a vat. The main qualifications of the material for the rope of the tire, to be used in the separator are, therefore, that it has a high tenacity and a high modulus, and the synthetic fibers. PVA cas are generally known to have high tenacity and high modulus. However, conventional PVA fiber has the defect that it shows a marked decrease in toughness and modulus, when the temperature rises, similar to other thermoplastic synthetic fibers such as polyesters and polyamides. In addition, the interior of a tire, when in use, is usually in a state of high temperature, approximately 10020, due to the heat caused by the

20.6.75.

operation of the tire, which also occurs, necessarily, in radially folded tires, and since the rope of the tire for the separator is afee, also taken for said temperature increase. Radial folding tires using conventional PVA fiber, whose high temperature properties are highly dependent on temperature, will not be able to exhibit the main function of the separator, strong and non-extensible, that restrains the deformation of the tire.

Of course, it is not completely impossible to replace this lack of resistance and modulus, in the PVA fiber with venational, increasing the amount of fiber used in a tire. However, this brings with it the great problem that the duration of the tire decreases greatly15, because the heat produced is increased, corresponding to the increase in the amount of fiber used, thus decreasing adhesion and fatigue resistance

In view of the foregoing, the inventors suggest a radial fold tire that utilizes the PVA fiber of the present invention and that has excellent properties at elevated temperature. The inventors have discovered that a radial folding tire will not be able to show its advantages, unless the PVA fiber containing boric acid or borate is used in the

20.6.73.

- 16 aiu βτι '414751 range from 0.2 to 0.9 / by weight, and has a wire tenacity of more than 7.5 g / d at 1202C, an initial thread module of more than 100 g / d at 12020 and a thread offset of less than $ 2 to 1352θ · This fact remains valid, regardless of the conditions of the construction of the rope, the heat treatment of the c / r.er da or the structure of the tire.

One of the factors that must be taken into account is the construction of the rope, 3r In ese peeial the number of laps has a great influence on the results of the final product. There is no limited number of turns suitable for any material. This is inseparably related to the properties of the material. Therefore, it is impossible to apply the appropriate number of turns for the fiber with PVA or other fibers, to the PVA fiber of the present invention. The inventors have repeated tests by actually operating the tire with the PVA fiber of the present invention in varying numbers of turns, to determine the winding optimum for the separator rope.

Another complication is that the properties of a tire are in both direct and inverse ratio to the number of turns. For example, fatigue resistance improved directly because of the increase in fatigue.

20.6.73.

the number of turns, while the properties related to the module, such as rolling resistance, turning characteristics and wear resistance of the tread, are inversely proportional.

It is necessary for any type of ncrmático, not only for radial folding tires, to satisfy the various required qualifications of the same. The results of the aforementioned tests have indicated that the synthetic PVA fiber of the present invention is very limited in its number of turns adapted to make the separator rope in the radial fold tire, that is, the constant of Twist of the fold is 800 to 1500 and the twist of the cable (turns / 10 cm) is 80 to 100% of the twist of the fold (turns / 10 cm). The constant torsion expression used in the present invention is designated K in the following equation where D is denier and T is the number of turns (number / 10 cm):

20.6.75.

The number of turns increases in correspondence with the increase of the K value.

When the torsion constant of the fold is less than 800, not only (1) the configuration of the rope becomes very uneven and the result of the tire is 18 414751 il. 'tu tico low, but also (2) the fatigue resistance of the rope becomes insufficient, so much so that it can reduce the breakage of the rope before the tread is worn, whereby the life of the tire is shortened. The cable torsion figure (turns / 10 cm) has a much greater influence on fatigue resistance than the torsion of the fold (turns / 10 cm). The duration of the tire also decreases when the twist of the cable (turns / 10 cm) is less than 80% of the twist of the fold (turns / 10 cm).

On the other hand, when the torsion constant of the fold exceeds 1300, the properties of the PVA fiber, such as high toughness and high modulus, are lost, thereby losing the advantage;

of the radius fold tires) - when they resist rolling resistance, wear resistance of the tread, and turning characteristic. It is also undesirable that the cable twist (turns / 10 cm) exceeds the limit specified above, that is, the

100% of the twist of the fold (turns / 10 cm), since this not only reduces the tenacity and modulus of the rope in a remarkable proportion, but also causes twists of the rope, due to relaxation, and handling difficulties.

The tire rope is submitted habi20.6.73.

- 19 414751

also to an immersion treatment, in order to give it adhesion to rubber. IF adhesive used in the present invention is not limited to specific types, but any of the known adhesives, used in the rubber industry, may be employed, with PPL being the most preferred (mixture of an initial alkaline condensate of resorcinol and formalin with latex), or that used concurrently with a latex containing polyvinyl pyridine. The condition for the immersion treatment may be as the treatment employed in the method for the biased tire rope. The drying, heating, elongation and heat treatment are carried out at a temperature higher than 200 & C.

To carry out the present invention, any of the materials used in ordinary biased folding tires may be used in the frame.

The present invention may be applicable to the manufacture of biased tire tires, provided with a belt-like layer, of tire rope, arranged substantially in parallel with the circumference of the tire and located outside the frame or shell to reinforce the belt. of rolling, similar to that of radial folding tires, but cu

2O.S.73.

- 20 414751

The frame is already the same structure as the biased folding ordinary tires.

Before proceeding to the description of the examples, according to the present invention, the description is now made, in the various tests, on the properties of a radial fold tire and the materials evaluated.

A. - Perforator test.- The result is evaluated in the energy (kg. 10 cm) consumed, before the tire is broken, by slowly penetrating the perforator. Here, the internal tire pressure is 1.7 kg / cm. The higher the value, the stronger the tire.

B. - High speed test

According to MVSS II2 109 (ASTM) tires whose air is adjusted to 1.7 kg / cm, are operated at 80 km / hr on a test cylinder. The speed is gradually increased, in the event that there are no defects in the tires, after running a previously determined time. The result is evaluated by the maximum speed (km / hr) at the break of the tire and the operating time (minutes) at the same speed. The larger the numerical value, the greater its resistance at high speed.

0. Turning power

20.6.75.

The force due to the turn (kg) of a tire or mático whose air pressure is adjusted to 1.7 kg / cm, is measured at a speed of 30 km / hr, a load of 125 hg and a sliding angle of 102 The value obtained by dividing said force due to the turn by the sliding angle, indicates the turning power (kg / degree), ... The higher the value, the better the turning characteristics.

D. Wear resistance of the tread

A car with tires whose air pressure is adjusted to 1.7 kg / cm is operated on a test circuit.

After traveling 20,000 km at a speed of 80 to 100 km / hr approximately, the amount of abrasion of the tread is measured as it touches the ground. The wear resistance of the tread is expressed as the distance the tire travels before the tread wears 1 mm. The higher the value, the greater the wear resistance of the tread.

E. - Duration-r

A car with tires whose pressure or air is adjusted to 1.7 kg / cm, is operated in a test circuit, for 20,000 km, at a speed of about 80 to 100 km / hr. Sample of the rope of 20.6.73 is taken.

- 22 414751

- Η

separator tire, before and after the test. The resistance of the rope is measured. This is expressed in residual resistance (%) of the tire cord tested, compared to the original rope. The higher the value the greater the duration.

It can be added to the description, that PVA synthetic fiber whose high temperature properties are improved, can be applied to the benzion member for a V-belt and for the reinforcement of flush sleeves. The high module and the small displacement at elevated temperature, allows the provision of V-belts whose dimensional stability remains stable when in use. The hoses for high pressure to be used in machines and utensils for work under pressure of oils, become advantageous through the use of PVA fiber, because the expansion of the hose against the internal pressure is maintained very Small, due to the functions of high modulus at high temperature.

Example 1

10 kg of aqueous solution of

PVA containing 1.7 kg a PVA, with polymerization degree of 1 · 75θ and saponification degree of 99.5 mol%, and 54- g of boric acid, and a small amount of nitric acid to adjust the pH to 4.3. The spinning solution

20.6.75.

'3, through the rows comprising 600 0.08 mm diameter spinning holes, is passed to the coagulation bath containing JO g / l of sodium hydroxide and 250 g / l of sodium sulfate. The fiber thus spun, is removed after bathing at a speed of 10 m / min, and then subjected to subsequent treatments such as, 100% roll stretching, neutralization in a bath comprising 70 g / l sulfuric acid and 300 g / l of sul. sodium fato; stretched in moist heat, 150%, washed with water to adjust the amount of boric acid to be 0.4-5%, dehydration and drying and stretched 220% in dry heat. The final product obtained is stretched to a total stretch ratio of 1,500%.

The product thus obtained, has a thread stiffness of 9.5 g / d at 1202C, an initial module of 155 g / d at 1202C and a displacement of the thread from 1.4% to 135SC.

When manufacturing radial fold tires for passenger vehicles, size 165-13, with the use of PVA synthetic fiber of the present invention, the 1,200 d / 600f PVA fiber (f is the number of filaments) is used in the separator, while in the frame high-tenacity rayon is used, super 2 I.65O d / l.lOOf. Both threads are twisted and intertwined in a rope fabric, the specifications of which are indicated in Table 1.

20.6.73.

- 24 Material A Material

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- 25 414751

Both rope fabrics A and B undergo normal immersion with the use of HFL solution. The rope fabric A is then treated in dry heat, at 2002C for 3 minutes, while the rope is stretched 2.5%. On the other hand, the B string fabric dries at 150-0 while maintaining its primitive length.

The tire of the present invention is obtained with the use of the above-mentioned rope fabrics in the separator and the frame, according to procedures such as rubber covers, tire formation, vulcanization and swelling after curing.

However, the tire was built, with 4 folds in the spacer and 2 folds in the frame.

The results of various tests on the characteristics of the tire are shown in Table 2. The comparative examples in the table are radial-fold tires, identical to the tire of the present invention in structure and size, but using, in the separator, PVA fiber that does not meet any of the manufacturing conditions and properties of the present invention . The results of the tests are also indicated in the table.

20.6.73.

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Example Compare 1 tion. one"

<td></td><td>Material: Degree of polymerization of the Degree of saponification of '</td><td>PVA PVA (mol%)</td><td> 1.750 99,5</td><td> 1.730 99,5</td>

<td></td><td>Spinning Solution:</td><td></td><td></td><td></td>

<td></td><td>PVA concentration (%)</td><td></td><td> 17</td><td> 17</td>

<td></td><td>The added amount of acid</td><td>boric (%)</td><td> 2,0</td><td> 2,2</td>

<td>Terms</td><td>pH</td><td></td><td> 4,3</td><td> 4,1</td>

<td>from</td><td>Solidification bath:</td><td></td><td></td><td></td>

<td>manufacturing</td><td>Ha OH (g / l)</td><td></td><td> 30</td><td> 8</td>

<td></td><td>Neutralization bath:</td><td></td><td></td><td></td>

<td></td><td>Stretched:</td><td></td><td></td><td></td>

<td></td><td>Total stretch ratio</td><td> (%)</td><td> 1.500</td><td> 1.100</td>

<td></td><td>Stretched with roller</td><td> (%)</td><td> 100</td><td>bad case</td>

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

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

<td></td><td>Stretched to moist heat</td><td> (%)</td><td> 150</td><td></td>

<td></td><td>Stretched to dry heat</td><td> (%)</td><td> 220</td><td></td>

20.6.73.

<td>Comparison l "</td><td>2 ”comparison</td><td>3 ”comparison</td><td>4 "comparison</td><td>Compare, 5 ~ tion</td><td>Comparison 6</td><td>Comparison 7</td>

<td> 70</td><td> 70</td><td>Be unable spin</td><td>from ?0</td><td> 80</td><td> 80</td><td> 70</td>

<td>the cavity estr- ado</td><td colspan="2">poor spinning capacity</td><td>poor stretching ability</td><td> 100</td><td> 100</td><td> 100</td>

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20.6.73 '414751

Table 2 (Continued)

<td rowspan="2"></td><td></td><td rowspan="2">Example one</td><td rowspan="2">Comparison 1</td><td rowspan="2">Cl c:</td>

<td></td><td>Amount of boric acid residue (%)</td><td> 0,45</td><td> 0,51</td><td> <</td>

<td>Owner-</td><td>Tenacity (1202C) (g / d)</td><td> 9,3</td><td> 6,2</td><td>J</td>

<td>of the</td><td>Initial module (1202C) (g / d)</td><td> 135</td><td> 72</td><td></td>

<td colspan="5">thread</td>

<td></td><td>Displacement (135-0) (%)</td><td> 1,4</td><td> 2,5</td><td></td>

<td></td><td>Perforator test (kg. Cm)</td><td> 5863</td><td> 3524</td><td> 4'</td>

<td colspan="5">Character-</td>

<td></td><td>High speed test / (km / hr); min.7</td><td> 217;20</td><td> 184;10</td><td> 1'</td>

<td colspan="5">ristic</td>

<td>of the</td><td>Turn Power (kg / degree) Wear resistance of the tread</td><td> 40,5</td><td> 31,9</td><td></td>

<td></td><td>Duration (%)</td><td> 95</td><td> 73</td><td>F</td>

Note: φ1 Its pH is adjusted by tartaric acid.

®2 Its pH is adjusted by acetic acid and sodium acetate.

In example 1, and up to comparative example 4, acid r is used

20.6.73.

- 28 '414751

<td>ompara</td><td>Compare</td><td>Compare</td><td>Compare</td><td>Compare</td><td>Compare</td><td>Compare-</td>

read nitric acid to adjust the pH,

30«

Example 2

PVA fiber is obtained which contains sodium bora to and stretches to a total stretch ratio of 1,500%, in the same manner as in the Example

1, except the use of sodium borate in an amount of

1.5% of PVA instead of boric acid, and tartaric acid instead of nitric acid, for pH adjustment,

The product obtained has a wire tenacity of 9.1 g / d at 12020, an initial module of the thread of 127 g / y at

1202C and a thread displacement of 1.5% to 13520 When manufacturing radial fold tires, using the thread, the characteristics of the tire are compared, diversifying the winding of the rope for the separator, as indicated in Table 3.

20.6.73

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20.6.73.

Example 3

To an aqueous solution of PVA, at a concentration of 15% by weight, containing 150 g of PVA, with a polymerization degree of 2.35θ and a saponification ratio of 99.5 mol%, 30 g of boric acid are added (2% of the weight of PVA) and a small amount of acetic acid to prepare a spinning solution, for spinning, at a pH of 4.5. The spinning solution is spun in a strongly alkaline coagulation bath, mainly of water, containing 40 g / l of sodium hydroxide and 25O g / l of sodium sulfate. After removing the thread from the bath at a speed of 10 m / min, it is subjected to a roll stretching of 100%, neutralization, stretching to moist heat of 15 °% »washed with water to adjust the residual amount of Boric acid 0.4% of the weight of PVA, dehydration and drying, and stretched in dry heat, of 200%. The product (1,200d / 600f) is thus stretched to a total stretch ratio of 1,400%. The product thus obtained has a wire tenacity of 9.2 g / d at 1202C, an initial module of the wire of 131 g / d at 1202C, and a thread displacement of 1.9% at 13520; The product is superior in its properties at high temperature.

This thread, obtained in this way, is used to construct the plie tire spacer.

20.6.75.

- 51 41 gue radial, winding it on a rope (l.200d / 1/3) under the following conditions:

Twist twist 50 turns / 10 cm

Cable Twist 30

Torsion direction

Fold

Cables

Torsion constant of the fold 1.039

Cable twist / crease twist x 100 (%) 100

20.5.73.

Ho damage was noticed after rolling 3500 km. The duration is 98% and the cornering power of 40.8 kg / degree.

Example 4

It is added to an aqueous solution of PVA at 17% by weight, containing 100 kg of PVA with a polymerization degree of 1.75θ and tm degree of saponification of 99.9 mol%, 2 kg of boric acid (2% of the weight of PVA) and 0.3 kg of acetic acid (0.005 grams equivalent for 100 g of PVA), to prepare the spinning solution.

The pH is maintained at 4.5.

The spinning solution is passed through rows with 1,000 holes of 0.15 mm dia. meter, to the coagulation bath, which contains 5θ g / l L® sodium hydroxide and 200 g / l sodium sulfate. Then, the fibers are taken out of the bath at a speed of 10 m / min.

- 32 10

20.6.75

Α14751

The spinning condition is very stable, in this case; no damage was noticed during a two-week spin, such as clogging of the nozzles. It gives fiber so spun, is then subjected to the same treatment as in Example 3; that is, roll-drawn, neutralization, stretched in moist heat, washed with water to adjust the amount of boric acid remaining to be 0.5% of the weight of PVA, dehydration, drying and drying in dry heat. The product (l.800d / 1.000f) thus obtained is stretched to a total stretch ratio of 1,400%. The product has a wire tenacity of 9.3 g / d at 1202C, an initial thread module of 134 g / d, and a thread displacement of 1.8% at 135-0.

The thread thus obtained is used for cons. Screw the separator of a radial fold tire, winding it on a rope (1.800d / 1/2) under the following conditions:

Twist Twist Twist Cable Twist Direction Twist Cable

Twist constant of the fold

Cable twist / crease twist x 100 (%) turns / 10 cm 30

Z

S

1.272

100

Ho damage was noticed after rolling 35 ° Οθ

- two? “K_

Ion. The duration is 96% and the turning power is 41.2 kg / degree.

The present application corresponding to those filed in Japan, on November 25, 1969, under the number 44-94790 and April 30, 1970, under the number 45-57354, benefits from Article 51 of the current Statute on Industrial property.

Contents56

22 members in 16 offices

This recordMember, by publication datePriority claim6 more offices are in the list below

Priority claims8

Priority claims
Document	Office	Kind	Date
9479069	Japan	A	1969-11-25
9479069	Japan	A	1969-11-25
3735470	Japan	A	1970-04-30
3735470	Japan	A	1970-04-30
4494790	–	–	–
4537354	–	–	–
JP19690094790	–	–	–
JP19700037354	–	–	–

Members22

Family members, oldest first
Document	Office	Kind
BE759394A	Belgium	A	1971-04-30
NL7017196A	Netherlands (Kingdom of the)	A	1971-05-27
ZA707953B	South Africa	B	1971-08-25
FR2072392A5	France	A5	1971-09-24
DE2064969A1	Germany	A1	1972-01-13
DE2055320A1	Germany	A1	1972-05-31
GB1319099A	United Kingdom	A	1973-05-31
ES385833A1	Spain	A1	1973-12-16
JPS4910994B1	Japan	B1	1974-03-14
SE368590B	Sweden	B	1974-07-08
AT316722B	Austria	B	1974-07-25
US3826298A	United States of America	A	1974-07-30
US3850901A	United States of America	A	1974-11-26
US3852402A	United States of America	A	1974-12-03
DK132186B	Denmark	B	1975-11-03
ES414751A1This record	Spain	A1	1976-01-16
PH9761A	Philippines	A	1976-03-12
DK132186C	Denmark	C	1976-03-29
NO134562B	Norway	B	1976-07-26
PL88890B1	Poland	B1	1976-10-30
NO134562C	Norway	C	1976-11-03
CA1007028A	Canada	A	1977-03-22

Abstract

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Priority claims8

Members22

Numbers

Titles2

Classification