JP3891357B2 - Polyester cord for rubber reinforcement and method for producing the same - Google Patents

Description

The present invention is a polyester cord for reinforcing rubber having a high elastic modulus and improved adhesion to rubber, particularly when exposed to a high temperature for a long time in a state where it is embedded in a rubber compound or in a high temperature atmosphere. The present invention relates to a polyester cord for rubber reinforcement in which the heat-resistant adhesive property of the rubber is remarkably improved and the cord hardness is softened to a practically no problem level from the viewpoint of fatigue resistance and molding processability of rubber-reinforced products, and a method for producing the same.
The polyester cord for reinforcing rubber obtained by the present invention is suitable for a cap cord used for a tire cord, particularly a belt outer layer portion of a radial tire.

Polyester fibers represented by polyethylene terephthalate have excellent mechanical properties and dimensional stability, but have better adhesion to rubber than nylon fibers, especially when exposed to high temperatures for a long time when embedded in rubber compounds. There is a disadvantage that the adhesive strength is significantly reduced. The cause of the decrease in adhesive strength in rubber compounds is said to be due to the degradation of polyester fibers due to the action of amines and moisture in the rubber compound, and many proposals have been made to eliminate this drawback. Has been made. For example, Patent Document 1 proposes a method in which a polyester fiber having a carboxyl end group amount of 10 eq / 10 ⁶ g or less is subjected to an epoxy compound treatment, a polyisocyanate compound treatment, and an RFL treatment. It is not practical due to the fact that it is performed in 3 steps and a three-stage dip process.

  Patent Document 2 proposes a method for producing a polyester fiber material that causes a decrease in adhesive strength when exposed to a high temperature in rubber for a long time by performing a treatment with a carrier-containing liquid at least prior to the adhesive treatment. However, although it has the effect on heat-resistant adhesiveness, there is a problem that strength and fatigue resistance deteriorate.

  Further, Patent Document 3 and Patent Document 4 sacrifice strength and fatigue resistance by treating with a carrier-containing treatment liquid, a blocked isocyanate aqueous solution, an epoxy resin dispersion, and a resorcin-formaldehyde-latex mixed liquid. A method for producing a polyester fiber material for reinforcing rubber with significantly improved heat-resistant adhesion when exposed to a high temperature for a long time without being embedded in a rubber compound has been proposed. With regard to cord hardness, although fatigue resistance is improved in a relatively short period of time, cord fatigue is still a problem in actual use, and the molding processability of rubber-reinforced products deteriorates because the cord is hard. Have.

  For tire cord applications, properties such as high strength, high elastic modulus, low shrinkage, adhesion, and fatigue resistance are required. Polyethylene terephthalate fiber is a carcass ply cord for radial tires due to its superior performance and cost. However, in recent years, high-performance tires have become widespread in terms of safety and comfort, and cap ply cords used for belt outer layers where demand is increasing are particularly resistant to heat. Therefore, nylon 66, which has excellent adhesion, is the mainstream.

  Nylon 66 fiber, on the other hand, has a low modulus of elasticity, so it has issues such as tire uniformity and flat spots. Further, for tires that emphasize high-speed durability, measures such as increasing the number of cords to be driven are necessary. In addition, there is a drawback that the weight of the tire becomes heavy. On the other hand, it has been proposed to use polyethylene terephthalate fibers having a high modulus of elasticity, but it is difficult to satisfy all of heat-resistant adhesiveness, fatigue resistance, etc., and it has not reached a practically usable level. The current situation (see, for example, Patent Document 5).

JP-A 51-70394 Japanese Patent Publication No. 60-31950 JP 2000-8280 A JP 2000-212875 A JP 59-124407 A

The present invention has been made against the background of the problems of the prior art, and has a high elastic modulus, and when it is exposed to a high temperature for a long time in a state where it is embedded in a rubber compound, it has a heat resistant adhesiveness in a high temperature atmosphere. An object of the present invention is to provide a polyester cord for reinforcing rubber and a method for producing the same, which is remarkably improved and further softened to a level where the cord hardness is practically satisfactory from the viewpoint of fatigue resistance and molding processability of rubber-reinforced products. Is.
The polyester cord for rubber reinforcement obtained from the present invention. It is suitable for a cap ply cord used for a tire cord, particularly a belt outer layer portion of a radial tire.

  As a result of intensive studies to solve the above problems, the present invention has finally been completed. That is, the present invention has the following configuration.

1. When the polyester fiber material, which has been preliminarily imparted with an epoxy compound in the yarn-making stage or the twisted-yarn cord stage, and imparts adhesiveness to rubber, (A) an aqueous solution of blocked isocyanate, (B) an epoxy resin dispersion And (C) the polyester fiber material is treated in a single stage or two or more stages by a treatment liquid containing three of resorcin-formaldehyde-latex (RFL) mixed liquid, and then 0.2 cN / dtex or more A method for producing a polyester cord for reinforcing rubber, which is subjected to a heat treatment under a normalizing tension adjusted to.
2. 2. The method for producing a polyester cord for reinforcing rubber according to 1 above, wherein the solid content weight ratio of blocked isocyanate / latex in the treatment liquid is 0.20 / 1 to 1/1.
3. 3. The method for producing a polyester cord for reinforcing rubber according to 1 or 2 above, wherein the (A) blocked isocyanate aqueous solution is an aqueous solution containing at least polymethylene polyphenyl isocyanate having a trifunctional or higher functionality.
4). The method for producing a polyester cord for reinforcing rubber according to any one of the above items 1 to 3, wherein (A) the blocked isocyanate has a thermal dissociation temperature of the blocking agent component of 100 ° C to 200 ° C.
5). The latex component of the (C) resorcin-formaldehyde-latex (RFL) mixed solution contains three components of vinyl pyridine, styrene and butadiene, and the composition ratio (weight ratio) is 25% of the sum of the vinyl pyridine ratio and the styrene ratio. The method for producing a polyester cord for rubber reinforcement according to any one of the above 1 to 4, which is blended so as to be -55%, a vinylpyridine ratio is 5% -20%, and a butadiene ratio is 45% -75%.
6). 6. The method for producing a rubber-reinforcing polyester cord according to any one of 1 to 5 above, wherein the normalizing tension is 0.3 cN / dtex or more.
7). The method for producing a polyester cord for reinforcing rubber according to any one of 1 to 5 above, wherein the normalizing tension is 0.4 cN / dtex or more.
8). Polyester fiber material, manufacturing method of the rubber reinforcing polyester cord according to any one of the above 1 to 7 which is polyethylene terephthalate-based textiles treated with epoxy compound having a bifunctional or more epoxy groups in a spinning or post-process.
9. 9. The method for producing a polyester cord for reinforcing rubber according to any one of 1 to 8 above, wherein the polyester fiber material is a woven fabric obtained by weaving a cord obtained by twisting drawn yarn.
10. A tire cap ply cord using a rubber-reinforced polyester cord produced by the method according to any one of 1 to 9 above.
11. When the polyester fiber material, which has been preliminarily imparted with an epoxy compound in the yarn-making stage or the twisted-yarn cord stage, and imparts adhesiveness to rubber, (A) an aqueous solution of blocked isocyanate, (B) an epoxy resin dispersion And (C) a resorcin-formaldehyde-latex (RFL) mixed solution containing three components, processed in one or more stages, and the strength of the treatment cord is 4.5 cN / dtex or more The elongation at the time of 2.0 cN / dtex load is 5.0% or less, the Gurley cord hardness is 30 mN to 90 mN, and the rubber coverage after the initial vulcanization in the peel adhesion test at room temperature is 90 % Polyester cord for reinforcing rubber with a rubber coverage after overvulcanization of 80% or more.
12 When the polyester fiber material, which has been preliminarily imparted with an epoxy compound in the yarn-making stage or the twisted-yarn cord stage, and imparts adhesiveness to rubber, (A) an aqueous solution of blocked isocyanate, (B) an epoxy resin dispersion And (C) a resorcin-formaldehyde-latex (RFL) mixed solution containing three components, processed in one or more stages, and the strength of the treatment cord is 4.5 cN / dtex or more The elongation at the time of 2.0 cN / dtex load is 5.0% or less, the Gurley-type cord hardness is 30 mN to 90 mN, and after the initial vulcanization in the heat peel adhesion test in a 150 ° C. atmosphere. A polyester cord for reinforcing rubber having a rubber coverage of 90% or more and a rubber coverage after overvulcanization of 80% or more.
13. 13. The polyester cord for rubber reinforcement according to 11 or 12 above, wherein the treated cord has an elongation at a load of 2.0 cN / dtex of 4.0% or less.
14 13. The polyester cord for rubber reinforcement according to 11 or 12 above, wherein the treated cord has an elongation at a load of 2.0 cN / dtex of 3.5% or less.
15. The polyester cord for rubber reinforcement according to any one of the above 11 to 14 , wherein the twist coefficient K of the treatment cord represented by K = T√D is 2500 or less.
Here, T is the number of twists of the cord (times / 10 cm), and D is the standard fineness (dtex) of the cord.
16. A tire cap ply cord using the rubber-reinforced polyester cord according to any one of the above 11 to 15 .
17. A pneumatic tire using the cap ply cord described in 16 above.

  According to the present invention, when it is exposed to high temperature for a long time when it is embedded in a rubber compound and has a high elastic modulus, the heat-resistant adhesiveness under a high temperature atmosphere is remarkably improved, and fatigue resistance and It is possible to provide a polyester cord for reinforcing rubber and a method for producing the same, in which the cord hardness is softened to a level where there is no practical problem in terms of molding processability of rubber-reinforced products.

Hereinafter, the present invention will be described in detail.
The polyester fiber material used in the present invention is a cord (raw cord) obtained by twisting drawn yarn (raw yarn) obtained by melt spinning polyethylene terephthalate or polyethylene terephthalate copolymerized with a small amount of a third component, or weaving it. Woven fabric.

  The polyethylene terephthalate raw yarn is preferably made of polyester fiber surface-activated with an epoxy compound or an isocyanate compound at the stage of undrawn yarn or drawn yarn, as shown in Japanese Patent Publication No. 47-49768, In particular, the polyethylene terephthalate raw yarn is preferably treated with an epoxy compound having a bifunctional or higher functional epoxy group in the spinning, drawing or post-treatment step. Preferable examples of the epoxy compound include polyglycidyl ether compounds of aliphatic polyhydric alcohols such as glycerol / polyglycidyl ether, diglycerol / polyglycidyl ether, polyglycerol / polyglycidyl ether, and sorbitol / polyglycidyl ether.

  Furthermore, it is preferable to age the fiber material treated with the epoxy compound and the curing agent. The aging is preferably performed at 30 ° C. or more and 80 ° C. or less for 12 hours or more. If the temperature exceeds 80 ° C., the adhesion between the polyester fiber and the rubber becomes strong, but it is not preferable in terms of strength reduction, cord hardening, fatigue reduction, and the like. Moreover, if it is 30 degrees C or less, in order to acquire sufficient adhesiveness, the very long aging time will be required and it is unpreferable. The aging time depends on the aging temperature, but is preferably 12 hours or more in order to obtain sufficient adhesive properties.

  In JP-A-2000-8280 and JP-A-2000-212875, a treatment liquid containing a carrier and a treatment liquid containing a blocked isocyanate aqueous solution are used as the first treatment liquid. When these treatment liquids are used, heat resistance However, it is not preferable in that the processing cord becomes hard and the workability of the rubber-reinforced product is deteriorated.

  The use of a carrier is not preferable because it promotes the penetration of the amine in the rubber compound into the fiber, promotes the deterioration of the fiber, and lowers the cord strength and fatigue resistance. In addition, this carrier is considered to have a high environmental load, and it is not preferable to use it in consideration of the environment.

  Therefore, as a result of the inventor's all-out efforts, when the epoxy compound is preliminarily imparted in the yarn production stage or the twisting cord stage and the polyester fiber material subjected to the adhesion activation treatment is imparted with adhesiveness to rubber, (A) blocked The polyester fiber material is processed in one or more stages by a treatment liquid containing an isocyanate aqueous solution, (B) an epoxy resin dispersion, and (C) a resorcin-formaldehyde-latex (RFL) mixture. It was found that a polyester cord having a good adhesive force even after being exposed to a high temperature was obtained by performing a heat treatment under a normalizing tension adjusted to 0.2 cN / dtex or more after the treatment.

  That is, by not containing a carrier in the treatment liquid, there is no problem with respect to fatigue resistance, and a polyester cord can be obtained in which the cord hardness is softened to a practically no problem level from the viewpoint of tire moldability. It is. In addition, as a process, it is preferable from the point of manufacturing cost that the fiber material can be made more flexible, and a one-step process is possible.

  Here, the solid content weight ratio of the blocked isocyanate in the treatment liquid (A) and the latex component in the treatment liquid (C) RFL was excellent when blocked isocyanate / latex = 0.20 / 1 to 1/1. Heat resistant adhesiveness can be obtained. Furthermore, blocked isocyanate / latex = 0.40 / 1 to 0.80 / 1 is preferable. This heat-resistant adhesive effect is due to the crosslinking modification of the latex with isocyanate, and if the blocked isocyanate component is small, the crosslinking modification effect is small and sufficient heat-resistant adhesiveness cannot be ensured. Further, when the latex component is small, sufficient initial adhesiveness cannot be obtained, and the treated fiber material becomes hard due to the cross-linking curing reaction, which is not preferable.

  Furthermore, it is preferable that 0.1-10 weight part of (B) epoxy compound solid content is mix | blended with respect to 100 weight part of total solids of a process liquid. If it exceeds this range, good adhesiveness cannot be obtained.

  It is preferable that the resin adhesion amount with respect to the polyester fiber material of a process liquid is 5 to 10 weight%. If the amount is less than 5% by weight, sufficient initial adhesion and heat-resistant adhesion cannot be obtained. If the amount is more than 10% by weight, the treated fiber material becomes hard and the fatigue resistance is lowered. Is not preferable.

  (A) Blocked isocyanate and (B) Epoxy resin dispersion are used as the treatment liquid for imparting adhesiveness to the fiber. As a result of intensive studies by the present inventors, the treatment liquid (A) blocked isocyanate of the present invention is used. Is water-soluble and has an excellent heat resistance when it contains at least polymethylene polyphenyl isocyanate having an average number of functional groups of 3 or more, more preferably 4 or more (a difunctional diphenylmethane diisocyanate may be mixed). Obtainable. Polyfunctionalization of isocyanate groups makes the treated fiber material harder compared to the resin adhesion amount, suggesting that the resin crosslink density is improved, and as a result, excellent heat resistance even when the resin adhesion amount is lowered There is an advantage that adhesiveness can be obtained. When the functional number is less than trifunctional, although the hardness of the treated fiber material can be suppressed, the crosslink density of the resin is low, so that sufficient heat-resistant adhesiveness cannot be obtained.

  The thermal dissociation temperature of the blocking agent component is 100 ° C. to 200 ° C., and preferred examples include phenols, lactams, oximes and the like. When the thermal dissociation temperature is lower than 100 ° C., the crosslinking reaction of isocyanate starts in the drying stage, and the infiltration into the fiber becomes uneven. On the other hand, when the temperature is higher than 200 ° C., a sufficient crosslinking reaction cannot be obtained, and in all cases, the heat resistant adhesiveness is lowered.

  The use of water-soluble blocked isocyanate makes the penetration and diffusion of isocyanate into the fiber more uniform, improving the reactivity with the fibers activated by epoxy treatment, and improving the heat-resistant adhesion. The resin is formed by forming an adhesive layer having an adhesive property, and more effectively acting as an amine scavenger in the rubber compound causing isocyanate to decrease the heat-resistant adhesive force, and by drying at a temperature higher than the dissociation temperature. This is considered to be a result of suppressing the deterioration of the polyester by increasing the crosslinking density and improving the barrier property against the penetration of the amine into the fiber. This is also suggested by the excellent strength retention after overvulcanization.

  The treatment liquid (B) epoxy resin of the present invention is not particularly limited, but preferably a bifunctional or higher polyfunctional epoxy increases the crosslink density of the resin and provides excellent heat resistant adhesiveness. Preferred examples of the epoxy compound include glycerol / polyglycidyl ether, diglycerol / polyglycidyl ether, polyglycerol / polyglycidyl ether, sorbitol / polyglycidyl ether, and the like. Show.

  The treatment liquid (C) RFL of the present invention uses a mixed aqueous solution of an initial condensate obtained by reacting resorcin and formaldehyde in the presence of an acid or alkali catalyst and a rubber latex containing three components of vinylpyridine, styrene and butadiene.

Here, the composition ratio (weight ratio) of vinylpyridine, styrene, and butadiene is 25% to 55% of the sum of the vinylpyridine ratio and styrene ratio, the vinylpyridine ratio is 5% to 20%, and the butadiene ratio is 45% to 75%. It is necessary to blend so as to be.
In the present invention, if the sum of the vinyl pyridine ratio and the styrene ratio is less than 25%, or the vinyl pyridine ratio is less than 5%, excellent heat-resistant adhesiveness cannot be obtained, and the sum of the vinyl pyridine ratio and the styrene ratio is If it exceeds 55%, the treated fiber material becomes too hard, and if the butadiene ratio is less than 45%, the co-vulcanizability with rubber decreases as the ratio decreases, and the adhesive strength with rubber decreases.

  The rubber latex containing the above three components is one or two kinds of styrene butadiene latex, carboxy modified styrene butadiene latex, styrene butadiene vinyl pyridine latex, carboxy modified styrene butadiene vinyl pyridine latex, acrylonitrile butadiene latex, natural rubber, polybutadiene latex and the like. It is a blend of the above.

The mixing ratio of the RFL resorcin-formaldehyde initial condensate (RF) and the rubber latex (L) is 1/2 to 1/15, particularly 1/4 to 1/12 in terms of the solid content weight ratio. Is preferred.
In the present invention, if the weight ratio of the solid content of RF and L is less than 1/2, the treated fiber material becomes too hard and the latex component is reduced, so that the adhesion to rubber is deteriorated. On the other hand, when it is larger than 1/15, not only the adhesiveness is deteriorated but also the tackiness of the treated fiber material is increased, which is not preferable.

  The strength of the treatment cord subjected to a treatment for imparting adhesiveness to rubber (hereinafter referred to as dip treatment) is preferably 4.5 cN / dtex or more, more preferably 5.0 cN / dtex or more. This is indispensable as the basic performance of the tire cord, and if it is less than this, it is not suitable for use as a tire cord. Here, the cord strength is a value obtained by dividing the cord strength by a reference fineness in cord constitution (for example, 2200 dtex if two original yarns of 1100 dtex are twisted together).

  The cord strength can be obtained by twisting a polyester raw yarn of 4.5 cN / dtex or more obtained by a known method and dipping. At this time, the twist number K of the treated cord represented by K = T√D is preferably 2500 or less. In this equation, T is the number of twists of the cord (times / 10 cm), and D is the standard fineness (dtex) of the cord. When the twist coefficient K exceeds 2500, the strength is reduced and the tire cap ply cord is not suitable.

  In addition, the dip treatment is preferably performed by applying the treatment liquid described above to the cord, drying at a temperature of 60 ° C. to 200 ° C. for 30 to 240 seconds, and then performing a heat treatment at 180 ° C. to 245 ° C. for 30 to 200 seconds.

  As an evaluation measure of the elastic modulus, the elongation at a load of 2.0 cN / dtex (hereinafter referred to as intermediate elongation) is used. The intermediate elongation is preferably 5.0% or less, more preferably 4.0% or less. More preferably, it is 3.5% or less. It is a well-known fact that, in the tire cap ply cord, by using a cord having a high elastic modulus, reduction of tire road noise and improvement of high-speed performance can be obtained. If the intermediate elongation is higher than 5.0%, it is not suitable as a tire cap ply cord.

  The intermediate elongation of the treatment cord largely depends on the tension of the final heat treatment zone (normalizing zone) in the dip treatment, preferably 0.2 cN / dtex or more, more preferably 0.3 cN / dtex or more, and still more preferably Is 0.4 cN / dtex or more. If the normalizing tension is less than 0.2 cN / dtex, the intended high elastic modulus cord cannot be obtained.

  Further, the factor contributing to the intermediate elongation includes the number of twists of the cord, and the twist coefficient K of the treated cord represented by K = T√D is preferably 2500 or less. When the twist coefficient K exceeds 2500, it becomes difficult to obtain a high elastic modulus necessary for a tire cap cord.

  When the Gurley-type cord hardness of the treated cord is 30 mN to 90 mN, the heat-resistant adhesiveness is significantly improved when exposed to a high temperature for a long time when embedded in a rubber compound or in a high-temperature atmosphere. It has been found that a polyester cord is obtained that has good fatigue properties and is softened to a level at which the cord hardness is practically acceptable from the viewpoint of molding processability of rubber-reinforced products. When the cord hardness is less than 30 mN, sufficient heat-resistant adhesiveness cannot be secured, and when the cord hardness is more than 90 mN, the treated fiber material becomes hard, fatigue resistance is lowered, and molding processability is deteriorated. As a known method for softening a treated fiber material, there is a method for imparting flexibility by bringing the treated fiber material into contact with an edge, and according to this method, a certain degree of flexibility is imparted to the treated fiber material. Although it can be applied, a part of the fiber resin layer is scraped off in the softening treatment step, resulting in a disadvantage that uniformity of resin adhesion is lowered and adhesiveness is reduced. In the present invention, it is possible to obtain a polyester cord that can maintain a level of hardness that causes no problem in molding without using a softening device, has excellent heat-resistant adhesiveness and fatigue resistance, and also has flexibility. .

  As a measure for evaluation of heat-resistant adhesion, rubber coverage in a rubber-cord peel adhesion test during overvulcanization and / or heat is used. In general, when polyester fibers are exposed to a high temperature in rubber for a long time, the adhesive strength decreases. This phenomenon is thought to be due to deterioration of rubber and adhesive (dip resin) and fibers and their interfaces. In the conventional polyester fiber, since the rubber hardly adheres to the cord after the adhesion failure, the fiber and / or the adhesive and the interface thereof are broken faster than the cohesive failure of the rubber. On the other hand, in the nylon 66 excellent in heat-resistant adhesiveness, the cord after adhesion failure is almost covered with rubber, and the fracture site is shifted to the rubber side, not the layer from the fiber to the adhesive. From these viewpoints, it is possible to determine the superiority or inferiority of the heat-resistant adhesiveness by evaluating the rubber coverage.

  For tires and / or industrial materials that use polyester cords for rubber reinforcement, the rubber coverage after initial vulcanization is 90% or more in any room temperature atmosphere or 100 ° C to 150 ° C high temperature atmosphere. It is necessary that the subsequent rubber coverage is 80% or more. If it is less than this, it is unsuitable for the use which requires heat-resistant adhesiveness.

  The polyester cord of the present invention thus obtained has a high elastic modulus suitable for tire cap ply use, and when exposed to a high temperature for a long time while embedded in a rubber compound, or in a high temperature atmosphere. Remarkable improvement in heat-resistant adhesion, with coverage as a representative evaluation measure, and further improved the hardness of the treated cord to a level that is practically acceptable in terms of fatigue resistance and molding processability of rubber-reinforced products Is something.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto. Each physical property value is measured by the following method.

  Strength and elongation: Based on JIS-L1017 8.5 (2002), after standing for 24 hours or more in a temperature-controlled room at 20 ° C. and 65% RH, the strength and elongation were measured with a tensile tester.

  Fineness: Based on JIS-L1017 8.3 (2002), the fineness was measured after standing in a temperature-controlled room at 20 ° C. and 65% RH for 24 hours or more.

Cord hardness: It evaluated by the Gurley method of JIS-L1096 8.20.1 A method (1999). A load of 25 g is attached to a position 5.08 cm below the pendulum fulcrum of the Gurley Stephine Tester. A sample with a cord length of 3.81 cm is attached to the chuck of the movable arm (the test length between the chuck and the free end of the pendulum is 2.54 cm), the movable arm is operated, and the scale at the moment when the sample leaves the free end of the pendulum RG was used, and the cord hardness was obtained from the following equation.
Cord hardness (mN) = RG x 0.969 / cord gauge (cm)

  Peel adhesion: JIS-K6256 (1999) “Cloth and vulcanized rubber peel test” was measured by an improved method. A test piece was prepared by laminating the treated cord and the rubber for tire shown in FIG. 1 (rubber thickness 0.7 mm, width 25 mm, number of cords to be corded 33 between the cord and cord), and 40 at 140 ° C. After vulcanization for 60 minutes (over vulcanization) at 170 ° C. (initial) or at room temperature, the upper and lower parts (parts a and b in FIG. 1) of the test piece are pinched at room temperature and peeled off at 50 mm / minute with a tensile tester. This is the force required to make it expressed in N / 25 mm. Furthermore, the test piece was heat-treated in an oven at 150 ° C. for 10 minutes, and the peel strength was measured in the same manner (when hot). After the test, the rubber coverage of the cord on the peeled surface was visually evaluated. When the cord was completely covered with rubber, the coverage was 100%, and when no rubber was attached at all, the cord was 0%.

  Pull-out adhesion: The T test (Method A) in JIS-L1017 Annex 1 3.1 (2002) was evaluated by a modified H test. The treated cord is embedded in a rubber for tires with a length of 1 cm, vulcanized at 140 ° C. for 40 minutes (initial) or 170 ° C. for 60 minutes (overvulcanization), and then the cord is pulled out from the rubber at a normal temperature at 300 mm / min. Is the force required for N / cm.

  Deterioration of strength in rubber: After the treated cord is embedded in tire rubber and vulcanized at 170 ° C for 180 minutes, the cord is taken out from the rubber and the rupture strength after vulcanization is measured. It is a representation.

  Disc fatigue resistance: evaluated by the disc fatigue strength (Goodrich method) of JIS-L1017 Annex 1 2.2.2 (2002). Two treatment cords are embedded in tire rubber and vulcanized at 140 ° C. for 40 minutes to produce a rubber composite. The test piece was subjected to a deformation of 12.5% compression and 6.3% elongation for 1 cycle at 2600 cycles / min for 72 hours, and then the cord was taken out from the rubber and the fracture strength after fatigue was measured. It is represented by the retention before and after the test.

  Tube fatigue resistance: Evaluated by tube fatigue strength (Goodyear method) of JIS-L1017 Annex 1 2.2.1 (2002). Using an extension / compression fatigue tester, a rubber tubular test piece in which the test piece is buried parallel to the axis is bent and attached at 80 degrees, an internal pressure of 0.34 MPa is applied with compressed air, and the sample is rotated at a rotational speed of 850 rpm. It shows the time until the tube breaks due to elongation / compression fatigue.

Example 1
A polyethylene terephthalate chip having an intrinsic viscosity of 0.95 dl / g was melted and discharged from a spinneret having a pore number of 190 at a spinning temperature of 300 ° C., passed through a heating region of 320 ° C., and then cooled and solidified with cooling air of 20 ° C., The film was taken up at a spinning speed of 550 m / min, and subsequently drawn at a draw ratio of 5.8 times, provided with sorbitol polyglycidyl ether as an epoxy compound, relaxed by 3.0%, and wound up. The thus obtained 1100 dtex, 190 filament polyethylene terephthalate yarn (intrinsic viscosity 0.88 dl / g, strength 8.3 cN / dtex) was aged at 70 ° C. for 48 hours, then twisted together and twisted 47 × 47 A raw cord of (t / 10 cm) was obtained. This cord is immersed in the treatment liquid, and the excess liquid is removed by a squeeze roll in which the pressure of the cord with the treatment liquid is adjusted. The cord to which the treatment liquid was applied was then dried in an oven at 120 ° C. for 56 seconds, and then heat treated in an oven at 235 ° C. for 45 seconds while giving a stretch ratio of 4.0% to the cord to which the treatment liquid was applied. I let you. The hot stretch tension at this time was 11.0 N / cord (0.50 cN / dtex).
Subsequently, it was dried in a 120 ° C. oven for 56 seconds and then heat treated in a 235 ° C. oven for 45 seconds while giving a relaxation rate of −2.0%. The normalizing tension at this time was 5.6 N / cord (0.25 cN / dtex). The treatment liquid composition used in Example 1 is shown in Table 1. Latex includes chemical C (solid content 41%) with a vinylpyridine / styrene / butadiene weight ratio of 12/18/70 and chemical D (solid content 49%) with a styrene / butadiene weight ratio of 50/50. Used as a mixture.

(Example 2)
In the treatment liquid of Example 1, chemical A was changed to water-soluble blocked isocyanate having about 3 functional groups of chemical A ′. Otherwise, the same dipping treatment as in Example 1 was performed.

(Example 3)
In Example 1, the treatment liquid shown in Table 1 was changed so that the solid content weight ratio of blocked isocyanate / latex was 0.24 / 1. Otherwise, the same dipping treatment as in Example 1 was performed.

Example 4
In Example 1, the treatment liquid shown in Table 1 was changed so that the solid content weight ratio of blocked isocyanate / latex was 1/1. Otherwise, the same dipping treatment as in Example 1 was performed.

(Example 5)
In Example 1, instead of the latex (mixture of chemicals C and D) shown in Table 1, a chemical E (solid content 40%) having a vinylpyridine / styrene / butadiene weight ratio of 15/15/70 was used. A treatment liquid having a liquid concentration adjusted to that of Table 1 by adjusting water was used. Otherwise, the same dipping treatment as in Example 1 was performed.

(Example 6)
In Example 1, instead of the latex (mixture of chemicals C and D) shown in Table 1, it was used for chemical E ′ (solid content 38%) having a vinylpyridine / styrene / butadiene weight ratio of 15/35/50. A treatment solution having a concentration adjusted to that of Table 1 by adjusting water was used. Otherwise, the same dipping treatment as in Example 1 was performed.

(Comparative Example 1)
In Example 1, a 1100 dtex, 190 filament polyethylene terephthalate raw yarn (intrinsic viscosity 0.88 dl / g, strength 8.3 cN / dtex) obtained by a known method in which the raw yarn is not surface-activated with an epoxy compound was used. Other than that, the dipping process similar to Example 1 was performed.

(Comparative Example 2)
The treatment liquid shown in Table 2 was used as a representative example of the RFL prescription containing no blocked isocyanate and epoxy, and the dip treatment was performed in the same manner as in Example 1 except that.

(Comparative Example 3)
The treatment liquid shown in Table 3 was used as a representative example of the carrier + RFL formulation containing no blocked isocyanate and epoxy, and the dip treatment was performed in the same manner as in Example 1 except that.

(Comparative Example 4)
The same yarn as in Example 1 was used, the treatment liquid shown in Table 4 was used as the first treatment liquid, and then the treatment liquid shown in Table 1 was applied to the cord as the second treatment liquid. The same dip treatment was applied.

(Comparative Example 5)
In the treatment liquid of Example 1, diphenylmethanebis-4,4′-carbamoyl-ε-caprolactam (solid content 29%) was used as the water-dispersible blocked isocyanate in the first treatment liquid and the second treatment liquid. Otherwise, the same dipping treatment as in Example 1 was performed. The total resin adhesion rate of the treated cord was 7.9% by weight.

  Table 5 shows the processing conditions and code properties of Examples 1 to 6 and Comparative Examples 1 to 5. Examples 1 to 6 of the present invention are Comparative Example 1 using a raw yarn that is not surface-active with an epoxy compound, Comparative Examples 2 and 3 not containing a blocked isocyanate, and Comparative Example 5 using a dispersible isocyanate. Compared with, heat resistant adhesiveness is remarkably improved.

  In addition, compared with the comparative example 4 which is a conventional example, the cord hardness is remarkably flexible, and the fatigue resistance which can be evaluated by the strength retention after tube fatigue and the tube fatigue is remarkably improved. Recognize.

(Example 7)
In the treatment of Example 1, the relaxation rate at the time of drying and heat treatment after application of the second treatment liquid was changed to -1.0%. The normalizing tension at this time was 8.1 N / cord (0.37 cN / dtex). Other than that, the dip treatment was performed using the same raw cord and treatment liquid as in Example 1.

(Example 8)
In the treatment of Example 1, the relaxation rate during drying and heat treatment after the application of the second treatment liquid was changed to 0%. The normalizing tension at this time was 10.6 N / cord (0.48 cN / dtex). Other than that, the dip treatment was performed using the same raw cord and treatment liquid as in Example 1.

Example 9
In the treatment of Example 1, a raw cord having a twist number of 33 × 33 (t / 10 cm) was used, and the relaxation rate during drying / heat treatment after application of the second treatment liquid was changed to 0%. The normalizing tension at this time was 14.1 N / cord (0.64 cN / dtex). Other than that, the dip process was performed using the process liquid similar to Example 1. FIG.

(Comparative Example 6)
In the treatment of Example 1, the relaxation rate at the time of drying and heat treatment after the application of the second treatment liquid was changed to -4.0%. The normalizing tension at this time was 3.5 N / cord (0.16 cN / dtex). Other than that, the dip treatment was performed using the same raw cord and treatment liquid as in Example 1.

(Comparative Example 7)
In the treatment of Example 9, the relaxation rate during drying and heat treatment after the application of the second treatment liquid was changed to -6.0%. The normalizing tension at this time was 3.1 N / cord (0.14 cN / dtex). Otherwise, the dipping process was performed using the same raw cord and processing liquid as in Example 9.

Table 6 shows the number of twists, dip conditions, and treated cord properties of Examples 1 and 7 to 9 and Comparative Examples 6 and 7.
From the comparison of Examples 1, 7, and 8, it can be seen that by increasing the normalizing tension, the intermediate elongation is lowered, that is, the elastic modulus is increased.
In Example 9, by reducing the number of twists, the normalizing tension under the same relaxing condition is increased, and the intermediate elongation is further decreased.
In Comparative Examples 6 and 7, since the normalizing tension is low, the intermediate elongation is increased and the elastic modulus is insufficient.

  According to the present invention, when it is exposed to high temperature for a long time when it is embedded in a rubber compound and has a high elastic modulus, the heat-resistant adhesiveness under a high temperature atmosphere is remarkably improved, and fatigue resistance and It is possible to provide a polyester cord for rubber reinforcement whose cord hardness has been improved to a practically no problem level from the viewpoint of molding processability of rubber-reinforced products, and a method for producing the same. Tire, hose, conveyor belt, V-belt, power transmission belt It can be used for a wide range of rubber product applications such as rubber containers, and in particular, can be used for tire cap ply cords, which have recently been on a growing trend, and contributes greatly to the industry.

It is a perspective view of the peeling adhesion test piece implemented as an evaluation measure of the heat resistant adhesiveness of this invention.

Explanation of symbols

1: Tire rubber 2: Polyester fiber cord 3: Peeling surface cut

Claims (17)

  When the polyester fiber material, which has been preliminarily imparted with an epoxy compound in the yarn-making stage or the twisted-yarn cord stage, and imparts adhesiveness to rubber, (A) an aqueous solution of blocked isocyanate, (B) an epoxy resin dispersion And (C) the polyester fiber material is treated in a single stage or two or more stages by a treatment liquid containing three of resorcin-formaldehyde-latex (RFL) mixed liquid, and then 0.2 cN / dtex or more A method for producing a polyester cord for reinforcing rubber, which is subjected to a heat treatment under a normalizing tension adjusted to.   The method for producing a polyester cord for reinforcing rubber according to claim 1, wherein the solid content weight ratio of blocked isocyanate / latex in the treatment liquid is 0.20 / 1 to 1/1.   The method for producing a polyester cord for reinforcing rubber according to claim 1 or 2, wherein the (A) aqueous solution of blocked isocyanate is an aqueous solution containing at least trifunctional polymethylene polyphenyl isocyanate.   The method for producing a polyester cord for rubber reinforcement according to any one of claims 1 to 3, wherein (A) the blocked isocyanate has a thermal dissociation temperature of the blocking agent component of 100 to 200 ° C. The latex component of the (C) resorcin-formaldehyde-latex (RFL) mixed solution contains three components of vinyl pyridine, styrene and butadiene, and the composition ratio (weight ratio) is 25% of the sum of the vinyl pyridine ratio and the styrene ratio. The manufacturing method of the polyester cord for rubber reinforcement in any one of Claims 1-4 mix | blended so that it might become -55%, a vinylpyridine ratio might be 5%-20%, and a butadiene ratio might be 45%-75%. The manufacturing method of the polyester cord for rubber reinforcement in any one of Claims 1-5 whose normalizing tension | tensile_strength is 0.3 cN / dtex or more. The manufacturing method of the polyester cord for rubber reinforcement in any one of Claims 1-5 whose normalizing tension | tensile_strength is 0.4 cN / dtex or more. Polyester fiber material, manufacturing method of the rubber reinforcing polyester cord according to claim 1 is polyethylene terephthalate-based textiles treated with epoxy compound having a bifunctional or more epoxy groups in a spinning or post-process. The method for producing a polyester cord for rubber reinforcement according to any one of claims 1 to 8, wherein the polyester fiber material is a woven fabric obtained by weaving a cord obtained by twisting drawn yarn. Tire cap ply cord using the rubber reinforcing polyester cord which is produced by the method according to any one of claims 1-9. When the polyester fiber material, which has been preliminarily imparted with an epoxy compound in the yarn-making stage or the twisted-yarn cord stage, and imparts adhesiveness to rubber, (A) an aqueous solution of blocked isocyanate, (B) an epoxy resin dispersion And (C) a resorcin-formaldehyde-latex (RFL) mixed solution containing three components, processed in one or more stages, and the strength of the treatment cord is 4.5 cN / dtex or more The elongation at the time of 2.0 cN / dtex load is 5.0% or less, the Gurley cord hardness is 30 mN to 90 mN, and the rubber coverage after the initial vulcanization in the peel adhesion test at room temperature is 90 % Polyester cord for reinforcing rubber with a rubber coverage after overvulcanization of 80% or more. When the polyester fiber material, which has been preliminarily imparted with an epoxy compound in the yarn-making stage or the twisted-yarn cord stage, and imparts adhesiveness to rubber, (A) an aqueous solution of blocked isocyanate, (B) an epoxy resin dispersion And (C) a resorcin-formaldehyde-latex (RFL) mixed solution containing three components, processed in one or more stages, and the strength of the treatment cord is 4.5 cN / dtex or more The elongation at the time of 2.0 cN / dtex load is 5.0% or less, the Gurley-type cord hardness is 30 mN to 90 mN, and after the initial vulcanization in the heat peel adhesion test in a 150 ° C. atmosphere. A polyester cord for reinforcing rubber having a rubber coverage of 90% or more and a rubber coverage after overvulcanization of 80% or more. The polyester cord for rubber reinforcement according to claim 11 or 12 , wherein the treated cord has an elongation at a load of 2.0 cN / dtex of 4.0% or less. The polyester cord for rubber reinforcement according to claim 11 or 12 , wherein the elongation of the treated cord at a load of 2.0 cN / dtex is 3.5% or less. The polyester cord for rubber reinforcement according to any one of claims 11 to 14 , wherein the twist coefficient K of the treatment cord represented by K = T√D is 2500 or less.
Here, T is the number of twists of the cord (times / 10 cm), and D is the standard fineness (dtex) of the cord. A tire cap ply cord using the rubber-reinforced polyester cord according to any one of claims 11 to 15 . A pneumatic tire using the cap ply cord according to claim 16 .

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