JP2932508B2 - Polyester multi-yarn with improved fatigue resistance and adhesion - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a polyester multi-yarn suitable for being used for reinforcing rubber and having excellent fatigue resistance and adhesiveness.

(Prior Art) Conventionally, polyester fibers have been used in many applications in recent years because they have excellent practical properties as fibers of a rubber reinforcing layer, such as strength, elastic modulus, shrinkage, and fatigue resistance.
However, it is also a fact that there is a problem in adhesion to rubber.

Techniques disclosed for the purpose of improving this point include, for example, JP-B-46-11251, JP-B-42-19921, JP-B-43-19922, JP-B-47-44345, and JP-B
JP-A-47-49768 and JP-B-55-4845 are known.

However, the technique described in Japanese Patent Publication No. 46-11251 has the disadvantage that the treating agent used for bonding the polyester and RFL is expensive, and in industrial production, a so-called dip treatment two-bath treatment apparatus is used. However, there is a disadvantage that an extremely expensive device is required also in this aspect. JP-B-42-19921, JP-B-43-1
No. 9922, JP-B-47-44345, JP-B-47-49768
In the technique described in Japanese Patent Application Laid-Open Publication No. H10-207, for example, in which an epoxy compound is applied to all the fiber surfaces of a fiber bundle to improve the adhesiveness with rubber, a treatment code (hereinafter referred to as a dip code) made of the fiber becomes hard and resistant. There is a drawback that the fatigue property is reduced.

(Problems to be Solved by the Invention) The present invention solves the problem that the fatigue resistance is reduced by performing the adhesion improving treatment in the above-mentioned conventional technology, and sufficiently retains the fatigue resistance before the adhesion improving treatment. An object of the present invention is to provide a polyester multi-yarn having improved adhesion performance equal to or higher than that of the prior art, that is, satisfying both the adhesion and fatigue resistance, which have not been achieved by the conventional technology, and achieving rubber reinforcement.

(Means for Solving the Problems) Means for solving the above problems, that is, the present invention is a multi-yarn made of polyester having ethylene terephthalate as a main constituent unit, and the multi-yarn has an adhesion of 50% by weight or less. The fiber bundle (A) to which the fiber oil agent for improving treatment is applied and the fiber bundle (B) other than the fiber bundle for which the fiber oil agent for improving adhesion is not applied, and the fiber bundle (A) is a fiber bundle (B)
A polyester multi-thread with improved fatigue resistance and adhesion characterized by having a yarn length difference of 2.5% or more.

The polyester component forming the polyester fiber of the present invention contains ethylene terephthalate units as main repeating units and is usually a copolyester or homopolyester containing 95 mol% or more of ethylene terephthalate units or a polyester mixture thereof. Terephthalic acid, copolymerization components other than ethylene glycol, isophthalic acid, 2,8-naphthalenedicarboxylic acid, adipic acid, sebacic acid, oxalic acid, diethylene glycol, propylene glycol, cyclohexanedimethanol, p-oxybenzoic acid, 3, Examples thereof include 5-di (carbomethoxy) benzenesulfonic acid metal salts and derivatives thereof, but are not limited to the above specific examples. Although the thickness of the multi-thread of the present invention is not particularly limited, it is preferable that the multi-thread is used for rubber reinforcement.
5 denier to 3000 denier is preferred. In the case where the denier is less than 125 denier, it is not preferable since the fatigue resistance effect intended in the present invention cannot be obtained when the rubber reinforcing multi-thread is used. On the other hand, when it exceeds 3000 deniers, it is not preferable because there is a problem that a strong utilization rate is reduced when the tire cord is used.

The multi-yarn of the present invention is composed of a fiber bundle (A) that has been subjected to a direct-improvement fiber oil agent application treatment and a fiber bundle (B) that has not been subjected to an adhesion-improvement fiber oil agent treatment. Preferably, 40 to 10% by weight of the fiber bundle (A) must be easily bonded and the fiber bundle (A) has a yarn length difference of 2.5% or more than that of the fiber bundle (B).

Here, if the bonding treatment is not performed on 50% by weight or less of the filament, the desired bonding effect cannot be obtained, which is not preferable.

In addition, when the yarn length difference of the fiber bundle (A) is less than 2.5%, in the twisting step, the easily-adhered fibers having a long yarn length are arranged on the outer peripheral side of the cord to improve the adhesive effect. It is not preferable because the function and effect cannot be obtained.

The adhesive treatment of the present invention is performed by applying an oil agent at the stage of spinning and drawing during yarn production.

Examples of fiber oils for improving adhesion include methylol compounds,
Examples of the treating agent include an isocyanate compound, an epoxy compound and a mechanical derivative thereof. Particularly preferred epoxy compounds include glycerin, propylene glycol, ethylene glycol, hexanetriol, sorbitol, trimethylolpropane, parylene ethylene glycol, reaction products of aliphatic polyhydric alcohols such as polyglycerin and epichlorohydrin, resorcinol, catechol, hydroquinone And glycidyl ether obtained from a reaction product of phenyls such as 1,3,5-trihydroxybenzene and bis (4-hydroxyphenyl) methane with epichlorohydrin.

 Next, a method for producing the multi-yarn of the present invention will be described.

FIG. 1 and FIG. 2 show examples of the fiber manufacturing apparatus of the present invention. The melted polyester is extruded from the spinneret, is immediately cooled and solidified in the quench chamber 2, and the spinning oil is applied by the oiling roll 3 and sent to the pro-retention roll 5 rotating at a peripheral speed of 600 m / min. The spinning oil agent may be any one containing a conventionally known leveling agent as a main component. Examples thereof include a favorite oil, an ester of a higher fatty acid and a higher alcohol (such as butyl stearate, oleyl laurate, and isostearyl palmitate). Consists of esters of acids and higher alcohols (such as dioctyl sebacate, dioctyl azelate, dioctyl azelate, and dioleyl adipate), and esters of trihydric alcohols and higher fatty acids (such as glycerin trioleate and trimethylolpropane tridecaneate). Examples include, but are not limited to, oils.

It is stretched by 2 to 6% between the pretension roll 5 and the first godet roll 6. The first godet roll is 90
C. and stretched 4 to 4.5 times between the second godet rolls 7 heated to 150.degree. Further, the second godet roll is stretched 1.3 to 1.5 times with the third godet roll 8 heated to 220 ° C. A guide 10 is used between the third godet roll and the fourth godet roll 9 to apply an adhesion improving oil agent to some of the fiber bundles. The fourth godet rolls 9A and 9B consist of two pairs, and the outer diameter of the large roll of 9A is 5% larger than the outer diameter of the large roll of 9B. The fiber bundle 9A to which the adhesion improving oil agent has been applied is sent to the godet roll of 9A, and the other fiber bundles are sent to the godet roll of 9B to be 3% and 8%, respectively.
% Relaxation is given. After passing through the interlacer 11 and converging, it is wound by the winder 12.
FIG. 2 shows another example in which the yarn length difference of the fiber bundle is provided in the drawing section. In FIG. 2, reference numeral 4 denotes an oiling roll for applying an oil for improving adhesion, which divides the yarn using a guide so that only a part of the yarn bundle is touched.

Making the fiber bundle to which the fiber oil agent for improving adhesion has a yarn length difference of 2.5% or more with respect to the other fiber bundles in this way requires a technique for giving a difference in draw ratio and / or a technique for giving a difference in relaxation rate. It can be realized by applying.

As described above, it is necessary to divide the fiber bundle to which the adhesion improving fiber oil agent is applied and the fiber bundle to which the adhesion improving fiber oil agent is not applied when applying the adhesion improving fiber oil agent. Needless to say, a spinning oil such as a leveling agent is provided. The fiber oil for improving adhesion may be applied before or after stretching, but when applied after stretching, it is necessary to apply a spinning oil to the fiber bundle prior to stretching.

In the multi-yarn of the present invention thus obtained, the fiber bundle (A) having been subjected to the adhesion improving treatment has a longer yarn length than the fiber bundle (B) which has not been subjected to the adhesion improving treatment. For this reason, when the yarn is twisted in the subsequent twisting process, the fiber bundle that has been subjected to the adhesion improving treatment having a substantially long yarn length is arranged on the outer peripheral side of the cord. For this reason, a conventional dip cord that has been subjected to a dip heat treatment with only an RFL (resorcinol-formalin-latex) treatment liquid shows the conventional easy adhesion. Considering that the dip cord is only the surface of the cord in contact with the rubber, this is a natural result. A disadvantage of the conventional tire cord made of the adhesion improving fiber is that the dip cord is hardened and the fatigue resistance is inferior because the adhesion enhancer is applied to the center of the cord which does not participate in the adhesion to the rubber. On the other hand, the cord composed of the multi-yarn of the present invention has a feature that the dip cord after the heat treatment is not hardened and the fatigue resistance is excellent because the fiber located at the center is not subjected to the adhesion improving treatment.

(Measurement method of fiber length difference) A fiber sample was held vertically by applying a load of 0.05 g per denier, and the entire fiber was cut to a length of exactly 50 cm using a safety razor with the tip of the blade dropped with sandpaper. Mark. Thereafter, the fiber is divided into single yarns, and a load of 0.05 g per denier is applied to each single fiber, and the distance between marks is measured to the first decimal place in mm. The average of the five longest
S _L, the shortest five average values and S _S.

Fiber yarn length difference (%) = (S _L / S _S -1) x 100 (Measurement method of H adhesive force) In a mold, a sample cord is passed through the center of 1cm x 1cm x 1cm rubber and co-added. After vulcanization, the pulling force of the cord from the rubber is measured. (Unit kg / cm) (Measurement method of disk fatigue) Measured in accordance with JISL-1017 ₍₁₉₆₃₎ 1.3.2.2. Disk fatigue strength (Goodrich method).

(Examples) Next, the characteristics of the fiber of the present invention will be specifically described with reference to examples.

Example 1 Polyethylene terephthalate having an intrinsic viscosity of 1.0 was melt-discharged from a 192 hole spinneret, cooled and solidified by cooling air at 20 ° C., fed with a spinning oil, and then fed to a pretension roll at a peripheral speed of 600 m / min. 1st godet / min (temperature 9
0%), stretch 4 times and send to the second godet (temperature 150 ° C) with a peripheral speed of 2520m / min, and further stretch 1.48 times to a peripheral speed of 3730m / min After passing through the third godet 8 at a temperature of 220 ° C, 0.9% of an adhesion improving treatment oil is further applied to 63 filaments (0.3% with respect to all filaments).
After giving different relaxation rates (1 to 7%) to the 64 filaments and the remaining 128 filaments, the filaments were bundled by an interlacer to wind up a fiber of 1500 denier. For comparison, the yarns were wound in the case where the relaxation rate difference was 0%, when the easy-adhesion treatment oil for all 192 filaments was applied at 0.3% s0.9%, and when no easy-adhesive was applied. Epon 812 (a reaction between glycerin and epichlorohydrin manufactured by Shechem Chemical Co., Ltd.) was used in an aqueous emulsion obtained by dissolving 70 parts of a spinning oil mainly composed of a fatty acid ester and a nonionic surfactant in 900 parts of water. (Product) 30 parts were dispersed and an epoxy compound-containing treating agent was used.

The obtained fiber is 40t / 10cm for both ply twist (Z) and ply twist (S).
To give a twin cord raw cord. The raw cord was subjected to RFL treatment by a conventional method, and the characteristics of the dip cord and the tire cord without were measured. The results are shown in Table 1.

(Effects of the Invention) As is clear from this example, the rubber reinforcing cord made of the multi-thread of the present invention has much better adhesiveness than the tire cord made of the fiber which has not been subjected to the fiber adhesion improving treatment according to the prior art. It shows the same fatigue resistance as that of the tire cord made of fiber that has been subjected to the adhesion improvement treatment.It shows the same excellent fatigue resistance and the same adhesiveness as the tire cord, and satisfies the adhesiveness and fatigue resistance that were not achieved by the conventional technology at the same time. Tire cords can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 shows an example of an apparatus for producing a multi-yarn according to the present invention. FIG. 2 shows an example of the apparatus for producing a multi-yarn according to the present invention other than the apparatus shown in FIG. 1: spinneret, 2: quench chamber 3, 4: oiling roll 5: pretension roll 6: first godet roll 7: second godet roll 8 (8A, 8B): third godet roll 9 (9A, 9B): fourth godet roll 10: Guide, 11: Interlacer 12: Winder

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) D02G 1/00-3/48 D01F 6/62 D01D 5/096

Claims (1)

(57) [Claims] 1. A multi-yarn made of polyester containing ethylene terephthalate as a main constituent unit, wherein the multi-yarn is composed of 50% by weight or less of a fiber bundle (A) treated with a fiber oil agent for improving adhesion, and other fibers being bonded. The fiber bundle (B) which has not been subjected to the fiber oil agent treatment for improvement, wherein the fiber bundle (A) has a yarn length difference of at least 2.5% from the fiber bundle (B). Polyester yarn with improved adhesiveness.