WO2018135794A1 - Lyocell heat-treated cord having improved fatigue resistance, comprising additive - Google Patents

Abstract

The prevent invention provides a lyocell heat-treated cord having improved fatigue resistance, which is particularly suitable for a tire cord, the lyocell heat-treated cord: dissolving NMMO hydrate in cellulose by using a solvent, adding an additive having a glycerol structure or an additive having a soybean oil structure, and then suitably controlling spinning of the solution, washing, oiling, and drying conditions, thereby obtaining an industrial lyocell filament; and using the same so as to perform twisting and heat treatment. In addition, according to a preferred embodiment of the present invention, provided is a pneumatic radial tire using, in a monolayer or bilayer structure, the lyocell heat-treated cord on a carcass layer or cap fly layer.

Description

Lyocell Heat Treatment Cord with Improved Fatigue Resistance Containing Additives

According to an embodiment of the present invention, in a lyocell heat treatment cord prepared by immersing and curing a lyocell raw cord consisting of at least two lyocell multifilaments in a dipping liquid, an additive or soybean having a glycerol structure during cellulose dope preparation A method of providing a lyocell heat treatment cord having improved fatigue resistance by adding an additive of a soybean oil structure is provided. The heat treatment cord according to the present invention may preferably be a lyocell heat treatment cord for a tire cord, and the cellulose is dissolved in N-methylmorpholine N-oxide (hereinafter referred to as NMMO) / water and then spun through an appropriately designed spinning nozzle. It can be prepared by the method.

In general, tire cords are widely used as a skeleton that forms the inside of a tire, which is considered to be an important factor in maintaining tire shape or riding comfort. Cord materials that are commonly used today include polyester, nylon, aramid, rayon and steel, but they do not satisfy the various functions required for tire cords. Basic performances required for these tire cord materials include: (1) high strength and initial modulus, (2) heat resistance, not embrittlement in dry and wet heat, (3) fatigue resistance, (4) form stability, and (5) rubber and And excellent adhesiveness. Therefore, the purpose of the code is determined according to the unique physical properties of each code material.

Among them, the biggest advantage of the rayon tire cord is heat resistance and shape stability, the elastic modulus is maintained even at high temperatures. Therefore, such low shrinkage rate and excellent shape stability has been mainly used in high speed radial tires for passenger cars. However, the rayon tire cord has a drawback in that its strength and modulus are low and moisture and its chemical and physical structure are easily deteriorated due to moisture absorption.

On the other hand, lyocell fiber, an artificial fiber made of cellulose, has lower elongation and heat shrinkage, higher strength and modulus than rayon fiber, and excellent morphological stability, and low moisture content, resulting in strong retention and modulus retention of more than 80% even when wet. It has a high characteristic. Therefore, it has an advantage of relatively less form change compared to rayon (60%), but may be considered as an alternative to the above requirements, but low fatigue resistance due to radioactivity and low elongation and high crystallinity for tire cords It is becoming.

Cellulose has very high affinity with other substances, but due to the crystal structure made by strong hydrogen bonds in molecular chains or chains, it is difficult to dissolve it as a general solvent, and NMMO is widely used among solvents that can destroy this structure to prepare a solution. .

The manufacturing method of lyocell fiber by NMMO is widely used in the process of manufacturing cellulose-based products due to the fact that it is a pollution-free process due to the total amount of solvent recovery and reuse and that the manufactured fibers and films have high mechanical strength. do.

In order to solve the problems of low strength and low initial modulus of existing viscose rayon tire cords, the present invention dissolves cellulose directly using NMMO hydrate as a solvent, and appropriately applies spinning, washing, emulsion and drying conditions of the solution. By adjusting the lyocell filament to obtain the industrial lyocell filament and by using the twisting and heat treatment to provide a particularly suitable lyocell heat treatment cord for the tire cord. In particular, the conventional lyocell tire cord has a problem that the fatigue resistance is low, but the elongation is low, but the change in shape compared to the rayon, in the present invention to solve this problem, additives or soybean oil of glycerol structure in the spinning process of lyocell fiber Adding an additive of the structure provides a lyocell fiber with improved fatigue resistance.

In a lyocell heat treatment cord according to an embodiment of the present invention, a lyocell heat treatment cord prepared by immersing a lyocell raw cord made of at least two lyocell multifilaments prepared by spinning a cellulose solution in a dipping solution and curing The lyocell multifilament has a cross-sectional porosity of 0.5 to 30%, and the cellulose solution contains an additive of a glycerol structure in an amount of 5% or less based on the total weight of the cellulose solution, and the fatigue degree of the heat treatment cord is 10% or more. .

The additive of the glycerol structure has a glycerol having at least two or more alkyl groups as a basic skeleton, one alkyl group has 1 to 50 carbon atoms, the alkyl group may have a structure having less than 10 double bonds.

According to another embodiment of the present invention, a radial pneumatic tire includes a pair of parallel bead cores and at least one radial carcass layer wound around the bead core and a belt layer and a belt layer laminated on the outer circumferential side of the carcass layer. A radial pneumatic tire comprising a circumferential belt reinforcement layer formed on an outer circumferential side, wherein the carcass layer includes the lyocell heat treatment cord, and the carcass layer is used as one layer or two layers.

According to another embodiment of the present invention, a radial pneumatic tire includes a pair of parallel bead cores and at least one radial carcass layer wound around the bead core, and a belt layer and a belt layer laminated on the outer circumferential side of the carcass layer. A radial pneumatic tire comprising a circumferential belt reinforcement layer formed on an outer circumferential side of the belt reinforcement layer, wherein the belt reinforcement layer includes a lyocell heat treatment cord according to any one of claims 1 to 2, and a cap The ply is characterized in that it is used in one or two layers.

The lyocell heat treatment cord according to another embodiment of the present invention is a lyocell heat treatment cord prepared by immersing and curing a lyocell raw cord made of at least two lyocell multifilaments prepared by spinning a cellulose solution in a dipping solution. The lyocell multifilament has a cross-sectional porosity of 0.5 to 30%, and the cellulose solution contains an additive of a soybean oil structure in an amount of 5% or less based on the total weight of the cellulose solution, and the heat treatment cord The fatigue level of is more than 10%.

The additive of the soybean oil may include a structure having at least three epoxy groups and at most 15 epoxy groups in a molecular structure, and having at least three alkyl group chains having at least 10 carbon atoms.

According to another embodiment of the present invention, a radial pneumatic tire includes a pair of parallel bead cores and at least one radial carcass layer wound around the bead core, and a belt layer and a belt layer laminated on the outer circumferential side of the carcass layer. A radial pneumatic tire comprising a circumferential belt reinforcement layer formed on an outer circumferential side of the carcass layer, wherein the carcass layer includes the lyocell heat treatment cord, and the carcass layer is used as one or two layers. .

According to another embodiment of the present invention, a radial pneumatic tire includes a pair of parallel bead cores and at least one radial carcass layer wound around the bead core, and a belt layer and a belt layer laminated on the outer circumferential side of the carcass layer. In the radial pneumatic tire comprising a circumferential belt reinforcement layer formed on the outer circumferential side of the, wherein the belt reinforcement layer cap ply includes the lyocell heat treatment cord, characterized in that the cap ply is used as one or two layers do.

According to a preferred embodiment of the present invention, NMMO hydrate is dissolved in cellulose using a solvent and glycerol structure additive or soybean oil structure additive is added, and then the spinning, washing, tanning and drying conditions of the solution are properly adjusted. Thus, by obtaining the industrial lyocell filament and performing the twisting and heat treatment using the lyocell filament, a lyocell heat treatment cord having improved fatigue resistance, which is particularly suitable for a tire cord, is provided.

Further, according to a preferred embodiment of the present invention, a pair of parallel bead cores and at least one radial carcass layer wound around the bead core and a belt layer laminated on the outer circumferential side of the carcass layer and a circumference formed on the outer circumferential side of the belt layer In a radial pneumatic tire comprising a belt reinforcing layer in a direction, a radial pneumatic tire using the lyocell heat treatment cord in a carcass layer or a cap ply layer in a single layer or a two layer structure is provided.

1 schematically illustrates a manufacturing process of a lyocell heat treatment cord according to embodiments of the present invention.

2 is a partial cross-sectional view of a structure of a tire manufactured using a lyocell cord according to embodiments of the present invention.

Hereinafter, the preferred embodiment according to the present invention will be described in detail. In addition, the present embodiment is not intended to limit the scope of the present invention, but is presented by way of example only, and various modifications may be made without departing from the technical spirit of the present invention.

In order to produce a homogeneous lyocell fiber with minimal cellulose degradation and undissolved cellulose particles, the cellulose powder is uniformly mixed with NMMO injected into the liquid phase at low temperature within a short time. The process of swelling is necessary.

The method for producing a homogeneous cellulose solution for lyocell according to the embodiments of the present invention for achieving the above object can be expected to have high strength and elastic modulus by inducing high orientation structure and high crystallization using cellulose molecules having high polymerization degree. have. In addition, in order to produce high quality cellulose fibers, it is preferable to use those having a high α-cellulose content. The cellulose sheet prepared as described above is pulverized after passing through a dryer and 50 to 100 powdered cellulose and concentrated liquid NMMO containing 1 to 10% by weight or less, more preferably 1 to 5% by weight or less. The cellulose solution for lyocell is prepared by continuously injecting into a coaxial twin screw extruder varying at a temperature of 100 ° C. and a rotation speed of 100 to 250 rpm to swell and dissolve.

If the moisture content is less than 1% by weight, economical efficiency is lowered, and if the water content is more than 10% by weight, mechanical properties are lowered, which is not preferable.

The cellulose solution may include an additive of glycerol structure or an additive of soybean oil structure. Additives of glycerol structure or additives of soybean oil structure serve to increase fatigue resistance.

In addition, the present invention, in the lyocell heat treatment cord produced by immersing the lyocell raw cord consisting of at least two lyocell multifilament in a dipping liquid to cure the lyocell multifilament, (a) the concentrated liquid Preparing an N-methylmorpholine N-oxide (hereinafter NMMO) solution; (b) drying and pulverizing the cellulose sheet to produce a cellulose powder maintained at a constant moisture; (c) preparing a cellulose solution by swelling and dissolving the liquid NMMO solution, the cellulose powder and the additive of the glycerol structure, or the additive of the soybean oil structure, respectively, by pouring into a twin screw extruder; (d) spinning the cellulose solution to provide a lyocell heat treatment cord comprising the step of preparing a cellulose filament.

More specifically, the homogeneous cellulose solution according to the embodiments of the present invention,

(a) concentrating 25% by weight of NMMO hydrate collected from the wash liquor into 86.5% by weight of liquid NMMO (monohydrate) by a thin film drop concentrator;

(b) After passing through the dryer while decomposing the roll-like cellulose sheet, the cellulose sheet is treated by adjusting the drying temperature so that the cellulose sheet has a moisture content of 7%, immediately cooled with dry air, injected into a grinder, and then to 500 μm or less. Preparing powdered cellulose;

(c) The liquid NMMO and cellulose powder prepared in (a) and (b) are dissolved by supplying an additive of glycerol structure or an additive of soybean oil to a twin screw extruder adjusted to a temperature range of 50 to 100 ° C. It is manufactured through a step. In particular, the twin-screw extruder prepared at this time minimizes the decomposition of cellulose by arranging the screws to have a narrow residence time distribution.

Hereinafter, a method for producing a homogeneous cellulose solution for lyocell and a fiber according to embodiments of the present invention will be described in more detail.

When the cellulose pulp sheet is pulled by the nip roller and supplied to the grinder, the pulp sheet is passed through a drying chamber adjusted to a constant temperature and then cooled with dry air to be maintained at 25 ° C. Prior to passing through the nip rollers, a contact moisture measuring device is used to control the drying temperature of the drying chamber so that the moisture content does not exceed 7%. Generally, the pulp supplied has a moisture content of about 8 to 10%, but shows a variation in the moisture content of the powdered cellulose stored in the storage tank after pulverization according to seasonal humidity and temperature change. High moisture content tends to cause pulp to clump together, making it difficult to obtain a homogeneous solution. In addition, since the composition of the NMMO / cellulose / water shows a deviation of the thickness of the fiber spun through the nozzle also can not cause a uniform quality. The length of the powdered cellulose can be adjusted according to the size of the screen sieve mounted inside the grinder with a knife, and it is preferable to use a powder of 500 μm or less, preferably 300 μm or less. In the case of 500 μm or more, pulp aggregates easily occur when mixed with NMMO, which acts as an inhibitor to prepare a homogeneous solution. The powdered cellulose passing through the screen sieve of the grinder is supplied to the bag filter through the blower, the air is discharged to the outside, and the powdered cellulose is supplied to the powdered cellulose storage tank through the rotary valve. This powdered cellulose is fed into the extruder through a precision weighing device.

A 25 wt% NMMO aqueous solution is prepared from a coagulation bath recovered from a coagulation bath and a washing bath, the coagulation bath and coagulation bath are continuously exchanged, and the concentration is maintained by pure water and 50 wt% NMMO. The prepared 25 wt% NMMO aqueous solution is supplied to a purification tower using an ion exchange resin to remove ionic substances and carbonized impurities and stored in the feed tank of the concentration tower. Again, it is quantitatively supplied to three thin film descending concentration towers from the concentration tower feeder to prepare a final 86.5 wt% NMMO aqueous solution. Concentrated to 86.5% by weight, NMMO is fed into a jacketed reservoir maintained at 90 ° C. and metered into the extruder through a gear pump.

The additive of the glycerol structure has a glycerol having at least two alkyl groups as a basic skeleton, one alkyl group having 1 to 50 carbon atoms and less than 10 double bonds, and the amount of the additive is 5% of the total cellulose solution It is added in the following amounts. Including less than two alkyl groups, or having more than 50 carbon atoms or having more than 10 double bonds in one alkyl group, the strength of the cellulose fibers is lowered, which is undesirable, and an additive of more than 5% may also It is not preferable because it lowers the strength.

The soybean oil structure has at least 3 epoxy groups and at most 15 epoxy groups in the molecular structure, and has at least 3 alkyl group chains having at least 10 carbon atoms. It is added in an amount of 5% or less relative to the cellulose solution. Additives containing less than 3, more than 15, alkyl groups having less than 10 carbon atoms, or containing less than 3 alkyl groups are undesirable because they lower the strength of the cellulose fibers and exceed 5%. Additives are also undesirable because they lower the strength of cellulose fibers.

The internal temperature of the twin screw extruder is adjusted from 50 ° C. to 100 ° C. to dissolve after a complete swelling step by temperature rise and shear force. The dissolved cellulose solution passes through the filter and the solution discharged through the nozzle is washed with water and dried to form cellulose fibers.

Cellulose fibers prepared according to the present invention is characterized in that the cross-sectional porosity of the yarn is 0.5 to 50%, more preferably 0.5 to 30%. Increasing the porosity results in higher body and higher fatigue resistance. If the porosity is less than 0.5%, fatigue fatigue is not appropriate, and if it is more than 30%, the strength of the fiber is reduced and not appropriate.

The lyocell filament manufacturing process is as follows. The solution extruded from the spinneret passes through the air gap in the vertical direction and solidifies in the coagulation bath. The air gap is appropriately 10 to 300 mm long in order to obtain dense and uniform fibers and to impart a smooth cooling effect.

After passing through the coagulation bath, the filament passes through the washing tank. It is preferable that the temperature of the coagulation bath and the water washing tank is about 10 to 25 ° C. in order to prevent the deterioration of physical properties due to the rapid desolvent.

After passing through the water bath, the fibers pass through the squeegee roller to remove moisture, and then pass through the primary tanning apparatus.

Thereafter, the filament yarn passed through the primary emulsion treatment apparatus is dried while passing through the drying apparatus. At this time, the drying temperature, drying method, and drying tension have a great influence on the post-processing and physical properties of the filament. In the present invention, the drying temperature was adjusted so that the process moisture content may be 7 to 13%.

The filament passed through the drying apparatus is finally wound up in the winder via a secondary tanning apparatus.

Although it does not restrict | limit especially about the fineness of the lyocell filament wound by the winder, It is preferable that single yarn fineness is 0.01-10 denier. In order to maintain the high strength characteristics of the lyocell filament, the single yarn fineness is preferably 0.5 to 10 denier, more preferably 0.7 to 3 denier, and most preferably 0.7 to 2 denier. In addition, the total fineness is not particularly limited, but is usually 5 to 30000 denier and preferably 100 to 5000 denier for industrial materials.

The lyocell heat treatment cord of the present invention undergoes a step (twisting process) of manufacturing a live cord by twisting the cord as a pre-production stage of cord manufacture.

The twisted yarn is manufactured by adding a twisted twist to a lyocell yarn and then adding a twisted twist, and in general, the twisted twist and the lower twist are subjected to the same softening (level of twist) or other softening as necessary.

In the present invention, the soft water of the lyocell deep cord is 200/200 TPM (Twist Per Meter) to 600 to 600 TPM with the same upper and lower edges. When the upper and lower edges have the same value, the manufactured dip cords can easily maintain a straight line without exhibiting rotation or twisting, thereby maximizing physical properties. At this time, when the number of upper and lower stations is less than 200/200 TPM, the extension of the raw cord is reduced and fatigue fatigue easily decreases, and when it exceeds 600 to 600 TPM, the strong deterioration is large, which is not suitable for the tire cord.

The raw code consists of at least two lyocell multifilaments. In the case of 2 copies, the performance is added while joining the lower stage, and in the case of 3, the additional twister may be placed on the lower edge and added, followed by the performance. If more than three, the strength drop is large and is not suitable for tire cords.

The produced 'Raw Cord' is woven into a fabric using a weaving machine and the obtained fabric is immersed in a dipping liquid. Then, the fabric is cured to produce a 'Dip Cord' for a tire cord having a resin layer attached to the raw cord surface.

The raw cord woven into the fabric and heat treated is immersed in the dipping liquid, and then the fabric is cured to produce a 'Dip Cord' for a tire cord having a resin layer attached to the surface of the raw cord.

In the above process, dipping refers to impregnating a surface of a fiber with a resin layer called Resorcinol Formaline Latex (RFL). This is done to ameliorate the disadvantages of the fibers for tire cords which are inherently poor in adhesion with rubber.

In the present invention, the adhesive solution for the adhesion of the cord and rubber can be prepared using the following method.

Manufacturing method of adhesive liquid

45.6 parts by weight of 29.4 wt% resorcinol;

255.5 parts by weight of distilled water;

20 parts by weight of 37% formalin; And

10 wt% sodium hydroxide 3.8 parts by weight

Prepare a solution containing the reaction after stirring for 5 hours at 25 ℃ add the following components.

40wt% VP-latex 300 parts by weight

129 parts by weight of distilled water

23.8 parts by weight of 28% aqueous ammonia.

After the addition of the ingredients it is aged for 20 hours at 25 ℃ to maintain a solid concentration of 19.05%.

The adhesive is applied after the cord is dried. In order to control the adhesion amount of the adhesive liquid, a stretch of 0 to 4% is required, and preferably 1 to 2% of stretching can be made. If the elongation ratio is too high, the adhesion amount of the adhesive liquid can be controlled but the elongation is reduced and consequently the fatigue resistance is reduced.

The adhesive amount is preferably 1.5 to 3.5% by weight of the fiber based on the solid content. After passing through the adhesive liquid, the dip cord is dried at 120 to 170 ℃. The drying time can be from 180 seconds to 220 seconds, and the dip cord can be stretched by 1 to 2% in the drying process. When the elongation ratio is low, the core and the elongation of the cord may increase, indicating physical properties that are difficult to apply to the tire cord. On the other hand, if the elongation rate is over 3%, the neutrophil level is appropriate but the body length is too small, which may reduce fatigue resistance.

After drying, heat treatment is carried out in a temperature range of 130 to 240 ℃. Elongation rate during the heat treatment is maintained between -2 to 2.0%, heat treatment time is appropriate 50 seconds to 90 seconds. If the heat treatment is performed for less than 50 seconds, the reaction time of the adhesive liquid is insufficient, resulting in low adhesive strength, and if the heat treatment exceeds 90 seconds, the hardness of the adhesive liquid may be increased, thereby reducing the fatigue resistance of the cord. have.

The lyocell dip cord manufactured according to the above method can be advantageously used as a tire cord for a passenger car. The dip cord can be used for the manufacture of the capply layer. And high performance radial tires made in accordance with the present invention comprise such capply layers.

Figure 2 shows a partial cross-sectional view of the structure of a tire for a passenger car manufactured using a lyocell dip cord according to embodiments of the present invention as a cap ply.

Referring to FIG. 2, the bead regions 35 of the tire 31 become annular bead cores 36 that are each non-extensible. The bead core 36 is preferably made from a single filament steel wire wound continuously. In a preferred embodiment, the high strength steel wire having a diameter of 0.95 mm to 1.00 mm becomes a 4x4 structure or a 4x5 structure. In the embodiment of the tire cord according to the present invention, the bead region 35 may have a bead filler 37, the bead filler 37 should have a hardness of a predetermined level or more, preferably Shore A hardness ( Shore A hardness) It may have a hardness of 40 or more.

According to the present invention, the tire 31 may be reinforced with the crown portion by the belt structure 38 and the cap fly 39. The belt structure 38 comprises a cutting belt ply 40 consisting of two belt cords 41 and 42 and the belt cord 41 of the belt ply 40 is about 20 with respect to the circumferential center surface of the tire. Can be oriented at an angle of degrees. One belt cord 41 of the belt ply 40 may be arranged in a direction opposite to the circumferential center surface, opposite to the direction of the belt cord 42 of the other belt ply 40. However, the belt structure 38 may comprise any number of plies, and may preferably be arranged in the range of 16 to 24 degrees. The belt structure 38 serves to provide lateral stiffness to minimize the rise of the tread 33 from the road surface during operation of the tire 31. The belt cords 41 and 42 of the belt structure 38 may be made of steel cords, and have a 2 + 2 structure, but may be made of any structure. The cap ply 39 and the edge ply 44 are reinforced on the upper portion of the belt structure 38. The cap ply cord 45 of the cap ply 39 is reinforced in parallel to the circumferential direction of the tire to prevent the tire from rotating at high speed. The cap fly cord 45 of the cap ply 39 which acts to suppress the size change in the circumferential direction and has a large heat shrinkage stress at high temperature is used. The capply cord 45 of the capply 39 may be manufactured using a deep cord made of a high strength yarn manufactured according to the method of the present invention. One layer of cap ply 39 and one layer of edge ply 44 may be used, preferably one or two layers of cap plies and one or two layers of edge plies.

Reference numerals 32 and 34, which are not described in FIG. 2, represent the carcass layer 32 and the fly turn up 34. Reference numeral 33 denotes a carcass layer reinforcing cord 33.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited by the following Examples.

In the following Examples and Comparative Examples, physical property evaluation was measured or evaluated as follows.

(a) Tire cord strength (kgf) and middle elongation (%)

After drying for 2 hours at 107, using a low-strength tensile tester of Instron, the sample length was measured at 250 mm and a tensile speed of 300 m / min. Elongation at specific load was measured at a load of 4.5 kg.

(b) Dry heat shrinkage (%, Shrinkage)

After leaving for 24 hours at 25, 65% RH, using the ratio of the length (L0) measured at a static load of 0.05g / d and the length (L1) after treatment at a static load of 0.05g / d for 30 minutes at 150 Dry heat shrinkage was shown.

S (%) = (L0-L1) / L0 X 100

(c) Tire code E-S value

Elongation under a constant load is referred to as the median elongation (E) in the present invention, 'S' means the dry heat shrinkage of the above (b), the sum of the median elongation (E) and dry heat shrinkage (S) to 'ES' Indicated.

E-S = median elongation (%) + dry heat shrinkage (%)

(d) even with fatigue

The fatigue strength was measured by using the Belt Fatigue Tester which is commonly used for the fatigue test of tire cords. Fatigue test conditions were made by topping two layers of rubber to 28 ~ 30 EPI (Ends Per Inch) spacing and vortexing for 160 to 20 minutes to make a specimen and applying a 70kg load in a bent fatigue tester. The condition was repeated 60,000 times at room temperature, and the residual strength was measured by separating the rubber and the cord after the fatigue test. The residual strength was measured after 107 2 hours of drying using a conventional tensile strength tester according to the method (a) above.

(e) Tire cord polymerization degree (%) reduction rate (%)

Intrinsic viscosity [IV] of the dissolved cellulose was measured in a concentration range of 25 to 0.1 to 0.6 g / dl using a 0.5 M cupriethylenediamine hydroxide solution prepared according to ASTM D539-51T using a Uberod viscometer. Intrinsic viscosity is obtained by extrapolating specific viscosity according to concentration, and substituting this into Mark-Houwink's formula to obtain polymerization degree.

[IV] = 0.98 ^-2 DPw ^0.9

First, measure DP (Do) of the raw cord before heat treatment, measure DP (D ₁ ) of the heat treatment cord after heat treatment, and calculate the reduction rate according to the following equation.

% Of DP degradation = (Do-D ₁ ) / Do X 100

Containing additives of glycerol structure Lyocell  Preparation of heat treated cords and radial pneumatic tires made therefrom

<Examples 1 and 2>

A cellulose solution prepared using Buckeye's V-81 pulp, NMMO ₂ O, and propyl gallate, having a degree of polymerization (DPW) of 1200 (a-cellulose content; 97%), was used at 0.045 wt% relative to the solution. At this time, the concentration of cellulose was 11.5% and Glyceryl trioleate was added as an additive. The ratio of the additive was 0.6 to 3.0 wt% relative to the total solution, the number of orifices was 1,000, and the orifice diameter was used as 200 μm. The solution discharged from the nozzle was cooled with an air gap length of 100 mm, the spinning speed was 150 m / min, and the final filament fineness was 1,500 denier. The coagulating solution temperature was adjusted to 23, the concentration was adjusted to 80% water and 20% NMMO, and the coagulating solution temperature and concentration were continuously monitored using a refractometer. The filament which escaped the coagulation bath removes the remaining NMMO by washing with water. It was dried after the first tanning and then wound up by a second tanning. The two lyocells were given twists of 400 TPM, respectively, and the twists of 400 TPM were given to prepare raw cords. The obtained raw cord was dried for 100 to 130 seconds, and then passed through an adhesive liquid prepared by the following method to give an adhesive liquid.

45.6 parts by weight of 29.4 wt% resorcinol; 255.5 parts by weight of distilled water; 20 parts by weight of 37% formalin; And after preparing a solution containing 3.8 parts by weight of 10wt% sodium hydroxide, the reaction was stirred at 25 to 5 hours and the following components were added:

40 wt% VP-latex 300 parts by weight, distilled water 129 parts by weight, 28% ammonia water, 23.8 parts by weight after the addition of the ingredients were aged for 25 to 20 hours to maintain a solid concentration of 19.05%.

After the adhesive liquid was applied and dried at 150 for 2 minutes, heat treatment was performed at 170 to 60 seconds to terminate the adhesive treatment. The physical properties of the prepared dip cords are shown in Table 1 below.

Comparative Example 1

A raw cord and a dip cord were prepared in the same manner as in Example 1 except that 0 wt% of an additive was added to the cellulose solution. Table 1 shows the physical properties of the dip cord thus prepared.

division	Treatment Code Properties
	Strong (kg)	Fatigue resistance (%)	Additive Ratio (wt%)
Example 1	16.4	39.1	0.6
Example 2	14.2	14.2	3.0
Comparative Example 1	17.0	9.5	-

<Example 3>

The radial tire manufactured by using the deep cord manufactured according to Example 1 of the present invention as a cap ply has a carcass layer having a radially outer fly turn up, and the carcass layer was installed to include one layer. At this time, the specifications of the carcass cord were as shown in Table 2 below, and were oriented at a 90 degree angle with respect to the circumferential intermediate surface of the tire. The fly turn-up 34 was to have a height of 40 to 80% with respect to the tire maximum cross-sectional height. The bead part 35 was formed to have a bead core 36 having a high strength steel wire having a diameter of 0.95 to 1.00 mm and a bead filler 37 having a hardness of 40 or more shore A hardness. The belt 38 is reinforced by a belt reinforcement layer having a capply 39 on one layer and an edge ply 44 on a first layer so that the capply cord in the capply 39 is parallel to the circumferential direction of the tire. Placed.

<Example 4>

A tire was manufactured in the same manner as in Example 3, except that a cord material for manufacturing a tire was used as the dip cord prepared in Example 2.

Comparative Example 2

A tire was manufactured in the same manner as in Example 3, except that a cord material for manufacturing a tire was used as a dip cord prepared in Comparative Example 1.

		Example 3	Example 4	Comparative Example 2
Carcass	Material	PET	PET	PET
	Specification (d / ply twisted yarn)	1500d / 2	1500d / 2	1500d / 2
	Strong (kg)	24	24	24
	Modulus of elasticity (g / d)	60	60	60
Cap fly	Material	Deep Code of Example 1	Deep Code of Example 2	Deep Code of Comparative Example 1
tire	Flat ratio	0.60	0.60	0.60
	Carcass floors	One	One	One
	Cap fly floor	One	One	One

Example 5

The radial tire manufactured using the dip cord manufactured according to Example 1 of the present invention had a carcass layer having a radially outer fly turn up, and the carcass layer was installed to include two layers. At this time, the specifications of the cap ply and carcass cord were as shown in Table 3 below, and tires were manufactured in the same manner as in Example 3.

<Example 6>

A tire was manufactured in the same manner as in Example 3, except that a cord material for manufacturing a tire was used as the dip cord prepared in Example 2.

Comparative Example 3

A tire was manufactured in the same manner as in Example 3, except that a cord material for manufacturing a tire was used as a dip cord prepared in Comparative Example 1.

		Example 5	Example 6	Comparative Example 3
Carcass	Material	Deep Code of Example 1	Deep Code of Example 2	Deep Code of Comparative Example 1
Cap fly	Material	Nylon 6,6	Nylon 6,6	Nylon 6,6
	Specification (d / ply twisted yarn)	1260D / 2P	1260D / 2P	1260D / 2P
	Strong (kg)	22.4	22.4	22.4
tire	Flat ratio	0.60	0.60	0.60
	Carcass floors	2	2	2
	Cap fly floor	One	One	One

The 205/65 R15 V tires manufactured according to Examples 3, 4, 5, 6 and Comparative Examples 2 and 3 were mounted on a 2000cc class passenger car, and the noise generated in the vehicle was measured while driving at a speed of 60 km / h. The values in the audible frequency range were expressed in noise (dB), and the steering stability and ride comfort were evaluated by experienced drivers on a test course in units of 5 points out of 100 points, and the results are shown in Table 4 below. Durability is based on the P-metric tire endurance test method of FMVSS 109 with a temperature of 38 degrees Celsius and 85, 90, and 100% of the tire's nominal load. A total of 34 hours of travel was judged as OK when no trace of bead separation, cord cutting, belt separation, or the like was found in any part of the tread, sidewall, carcass cord, inner liner, or bead.

division	Tire weight (kg)	Ride	Steering stability	durability	Uniformity	Noise (dB)
Example 3	9.54	100	100	OK	100	61.2
Example 4	9.70	100	100	OK	100	61.4
Comparative Example 2	9.60	96	95	OK	96	63.5
Example 5	9.64	100	100	OK	100	60.4
Example 6	9.70	100	100	OK	100	61.0
Comparative Example 3	9.60	93	94	OK	92	64.3

Soibin  Containing additives of oil structure Lyocell  Preparation of heat treated cords and radial pneumatic tires made therefrom

<Examples 7-8>

A cellulose solution prepared using Buckeye's V-81 pulp, NMMO ₂ O, and propyl gallate, having a degree of polymerization (DPW) of 1200 (a-cellulose content; 97%), was used at 0.045 wt% relative to the solution. At this time, the concentration of cellulose was 11.5%, and as an additive, Soybean Oil containing 10 epoxy groups in the molecular structure and 3 alkyl group chains having 15 carbon atoms was added. The ratio of the additive was 0.6 to 3.0 wt% relative to the total solution, the number of orifices was 1,000, and the orifice diameter was used as 200 μm. The solution discharged from the nozzle was cooled with an air gap length of 100 mm, the spinning speed was 150 m / min, and the final filament fineness was 1,500 denier. The coagulating solution temperature was adjusted to 23, the concentration was adjusted to 80% water and 20% NMMO, and the coagulating solution temperature and concentration were continuously monitored using a refractometer. The filament which escaped the coagulation bath removes the remaining NMMO by washing with water. It was dried after the first tanning and then wound up by a second tanning. The two lyocells were given twists of 400 TPM, respectively, and the twists of 400 TPM were given to prepare raw cords. The obtained raw cord was dried for 100 to 130 seconds, and then passed through an adhesive liquid prepared by the following method to give an adhesive liquid.

45.6 parts by weight of 29.4 wt% resorcinol; 255.5 parts by weight of distilled water; 20 parts by weight of 37% formalin; And after preparing a solution containing 3.8 parts by weight of 10wt% sodium hydroxide, the reaction was stirred at 25 to 5 hours and the following components were added:

40 wt% VP-latex 300 parts by weight, distilled water 129 parts by weight, 28% ammonia water, 23.8 parts by weight after the addition of the ingredients were aged for 25 to 20 hours to maintain a solid concentration of 19.05%.

After the adhesive liquid was applied and dried at 150 for 2 minutes, heat treatment was performed at 170 to 60 seconds to terminate the adhesive treatment. The physical properties of the thus prepared dip cord are evaluated and shown in Table 5.

<Comparative Example 4>

A raw cord and a dip cord were prepared in the same manner as in Example 7, except that 0 wt% of an additive was added to the cellulose solution. The physical properties of the prepared dip cords are shown in Table 5.

division	Treatment Code Properties
	Strong (kg)	Fatigue resistance (%)	Additive Ratio (wt%)
Example 7	16.4	43.3	0.6
Example 8	14.2	18.0	3.0
Comparative Example 4	17.0	9.5	-

Example 9

The radial tire manufactured by using the deep cord manufactured by Example 7 of the present invention as a cap ply has a carcass layer having a radially outer fly turn up, and the carcass layer was installed to include one layer. At this time, the specifications of the carcass cord were as shown in Table 6 below, and were oriented at a 90 degree angle with respect to the circumferential intermediate surface of the tire. The fly turn-up 34 was to have a height of 40 to 80% with respect to the tire maximum cross-sectional height. The bead part 35 was formed to have a bead core 36 having a high strength steel wire having a diameter of 0.95 to 1.00 mm and a bead filler 37 having a hardness of 40 or more shore A hardness. The belt 38 is reinforced by a belt reinforcement layer having a capply 39 on one layer and an edge ply 44 on a first layer so that the capply cord in the capply 39 is parallel to the circumferential direction of the tire. Placed.

<Example 10>

A tire was manufactured in the same manner as in Example 9, except that a cord material for manufacturing a tire was used as the dip cord prepared in Example 8.

Comparative Example 5

A tire was manufactured in the same manner as in Example 9, except that a cord material for manufacturing a tire was used as a dip cord prepared in Comparative Example 4.

		Example 9	Example 10	Comparative Example 5
Carcass	Material	PET	PET	PET
	Specification (d / ply twisted yarn)	1500d / 2	1500d / 2	1500d / 2
	Strong (kg)	24	24	24
	Modulus of elasticity (g / d)	60	60	60
Cap fly	Material	Deep Code of Example 7	Deep Code of Example 8	Deep Code of Comparative Example 4
tire	Flat ratio	0.60	0.60	0.60
	Carcass floors	One	One	One
	Cap fly floor	One	One	One

<Example 11>

The radial tire manufactured using the dip cord manufactured according to Example 7 of the present invention had a carcass layer having a radially outer fly turn up, and the carcass layer was installed to include two layers. At this time, the specifications of the cap ply and carcass cord were as shown in Table 7 below, and tires were manufactured in the same manner as in Example 9.

<Example 12>

A tire was manufactured in the same manner as in Example 9, except that a cord material for manufacturing a tire was used as the dip cord prepared in Example 8.

Comparative Example 6

A tire was manufactured in the same manner as in Example 9, except that a cord material for manufacturing a tire was used as a dip cord prepared in Comparative Example 4.

		Example 11	Example 12	Comparative Example 6
Carcass	Material	Deep Code of Example 7	Deep Code of Example 8	Deep Code of Comparative Example 4
Cap fly	Material	Nylon 6,6	Nylon 6,6	Nylon 6,6
	Specification (d / ply twisted yarn)	1260D / 2P	1260D / 2P	1260D / 2P
	Strong (kg)	22.4	22.4	22.4
tire	Flat ratio	0.60	0.60	0.60
	Carcass floors	2	2	2
	Cap fly floor	One	One	One

The 205/65 R15 V tires manufactured according to Examples 9, 10, 11, 12 and Comparative Examples 5 and 6 were mounted in a 2000cc class passenger car, and the noise generated in the vehicle was measured while driving at a speed of 60 km / h. The values in the audible frequency range were expressed in noise (dB), and the steering stability and ride comfort were evaluated by experienced drivers on a test course in units of 5 points out of 100 points, and the results are shown in Table 8 below. Durability is based on the P-metric tire endurance test method of FMVSS 109 with a temperature of 38 degrees Celsius and 85, 90, and 100% of the tire's nominal load. A total of 34 hours of travel was judged as OK when no trace of bead separation, cord cutting, belt separation, or the like was found in any part of the tread, sidewall, carcass cord, inner liner, or bead.

division	Tire weight (kg)	Ride	Steering stability	durability	Uniformity	Noise (dB)
Example 9	9.54	100	100	OK	100	61.2
Example 10	9.70	100	100	OK	100	61.4
Comparative Example 5	9.60	96	95	OK	96	63.5
Example 11	9.64	100	100	OK	100	60.4
Example 12	9.70	100	100	OK	100	61.0
Comparative Example 6	9.60	93	94	OK	92	64.3

In the above, although the present invention has been described by means of limited embodiments and drawings, the present invention is not limited by this and the technical spirit of the present invention and the following by those skilled in the art to which the present invention pertains. Various modifications and variations are possible, of course, within the scope of equivalents of the claims to be described.

Claims (8)

1. In a lyocell heat treatment cord manufactured by immersing a lyocell raw cord made up of at least two lyocell multifilaments prepared by spinning a cellulose solution in a dipping solution to cure

   The lyocell multifilament has a cross-sectional porosity of 0.5 to 30%,

   The cellulose solution contains a glycerol structure additive of less than 5% of the total weight of the cellulose solution,

   Lyocell heat treatment cord, characterized in that the fatigue degree of the heat treatment cord is 10% or more.
2. The method of claim 1,

   The glycerol structure additive has a glycerol having at least two alkyl groups as a basic skeleton, one alkyl group having 1 to 50 carbon atoms, the lyocell heat treatment code, characterized in that the structure having less than 10 double bonds.
3. Radial air comprising a pair of parallel bead cores and at least one radial carcass layer wound around the bead core, a belt layer laminated on the outer peripheral side of the carcass layer and a circumferential belt reinforcement layer formed on the outer peripheral side of the belt layer. In the mouth tires,

   The carcass layer comprises a lyocell heat treatment cord according to any one of claims 1 to 2, wherein the carcass layer is used as a radial or pneumatic tire.
4. Radial air comprising a pair of parallel bead cores and at least one radial carcass layer wound around the bead core, a belt layer laminated on the outer peripheral side of the carcass layer and a circumferential belt reinforcement layer formed on the outer peripheral side of the belt layer. In the mouth tires,

   The belt ply, which is the belt reinforcement layer, includes a lyocell heat treatment cord according to any one of claims 1 to 2, and the radial pneumatic tire is characterized in that the cap ply is used in one or two layers.
5. In a lyocell heat treatment cord manufactured by immersing a lyocell raw cord made up of at least two lyocell multifilaments prepared by spinning a cellulose solution in a dipping solution to cure

   The lyocell multifilament has a cross-sectional porosity of 0.5 to 30%,

   The cellulose solution contains an additive of a soybean oil structure of less than 5% of the total weight of the cellulose solution,

   Lyocell heat treatment cord, characterized in that the fatigue degree of the heat treatment cord is 10% or more.
6. The method of claim 5,

   The soybean oil structure additive is a lyocell heat treatment code comprising at least three epoxy groups, at most 15 or less epoxy groups in a molecular structure, and at least three alkyl group chains having at least 10 carbon atoms. .
7. Radial air comprising a pair of parallel bead cores and at least one radial carcass layer wound around the bead core, a belt layer laminated on the outer peripheral side of the carcass layer and a circumferential belt reinforcement layer formed on the outer peripheral side of the belt layer. In the mouth tires,

   The carcass layer comprises a lyocell heat treatment cord according to any one of claims 5 to 6, wherein the carcass layer is a radial pneumatic tire, characterized in that used as one or two layers.
8. Radial air comprising a pair of parallel bead cores and at least one radial carcass layer wound around the bead core, a belt layer laminated on the outer peripheral side of the carcass layer and a circumferential belt reinforcement layer formed on the outer peripheral side of the belt layer. In the mouth tires,

   The belt ply, which is the belt reinforcement layer, includes a lyocell heat treatment cord according to any one of claims 5 to 6, and the radial pneumatic tire is characterized in that the cap ply is used in one or two layers.

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