JPH0345738A - Fatigue-resistant and readily adhesive polyester multifilament - Google Patents

Abstract

PURPOSE:To provide polyester multifilament yarn having excellent fatigue-- resistance and easily adhesive property by combining an adhesive-treated fiber bundle with an adhesive-non-treated fiber bundle in a specific ratio, the fiber bundles comprising polyester fibers containing an ethylene terephthalate unit as a main structural unit and having a difference between the lengths thereof. CONSTITUTION:A polyester containing an ethylene terephthalate unit as a main structural unit is extruded from a spinneret 1, cooled and solidified in a quenching chamber 2, oiled on an oiling roll 3 and subsequently drawn between a pre-tension roll 5 and the first godet roll 6, etc. One part of the fiber bundle is oiled with an adhesion-facilitating oil between the third godet roll 8 and the fourth godet roll 9A and subsequently gathered with the other of the fiber bundle in an interlacer 11 to provide polyester multifilaments comprising <=50wt.% of the adhesive-treated fiber bundle and >=50wt.% of the adhesive-non- treated fiber bundle, suitable for reinforcing rubbers and having a difference wherein the fiber length of the adhesive-treated fiber bundle is longer by >=2.5% than that of the adhesion-non-treated fiber bundle.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a polyester mulch yarn that is suitable for use as rubber reinforcement and has excellent fatigue resistance and easy adhesion.

(Prior Art) Polyester fibers have been used for many purposes in recent years because they have excellent practical properties as fibers for reinforcing rubber, such as strength, elongation, shrinkage, and fatigue resistance. However, it is also true that there is a problem with the adhesive strength with rubber.

Techniques disclosed to improve this point include, for example, Japanese Patent Publication No. 4B-11251 and Japanese Patent Publication No. 42-1992.
Publication No. 1, Special Publication No. 19922-1992, Special Publication No. 1972
-44345, Japanese Patent Publication No. 47-49768, Japanese Patent Publication No. 55-4845, etc. are known.

However, the technique described in Japanese Patent Publication No. 4E3-11251 has the drawback that the processing agent used for bonding polyester and RFL is expensive, and it is difficult to use in commercial production.

Although a two-bath treatment apparatus is desirable for the bath treatment, it still has the drawback of requiring extremely expensive equipment. Also, Japanese Patent Publication No. 42-19921, Publication No. 43-19922
Publication No. 47-44345, Special Publication No. 47-44345, Publication No. 47-44345
In the technique described in Japanese Patent Publication No. 49768 and Japanese Patent Publication No. 55-4845, etc., in which an epoxy compound is applied to the surfaces of all fibers in a fiber bundle to achieve adhesion to rubber, the treatment IIN cord made of the fibers is (hereinafter referred to as dip cord) had the disadvantage of becoming stiff and reducing fatigue resistance.

(Problems to be Solved by the Invention) This invention solves the problem that fatigue resistance decreases when the easy-adhesion treatment is applied in the prior art, and sufficiently improves the fatigue resistance before the easy-adhesion treatment. The present invention provides a polyester mulch yarn that has adhesion performance comparable to or better than that of conventional yarns while maintaining its properties, that is, it satisfies both adhesion and fatigue resistance, which were not achieved with conventional techniques, and is suitable for rubber reinforcement. be.

(Means for solving problems) Means for solving the above problems, that is, the present invention.

A mulch yarn made of polyester having ethylene terephthalate as its main structural unit, and the mulch yarn is composed of a fiber bundle (A) that has been subjected to an easy-adhesion treatment and a fiber bundle (B) that has not been subjected to an easy-adhesion treatment, and 50% by weight or less of the mulch yarn is The easily adhesive fiber bundle (A
) is a fatigue-resistant vJtim polyester multi yarn characterized by having a yarn length difference of 2.5% or more -L from the fiber bundle (B).

The polyester component forming the polyester fiber of the present invention is mainly composed of repeating ethylene terephthalate units.
It is usually a copolyester or homopolyester containing 95 mol% or more of ethylene terephthalate units, or a polyester mixture thereof.

Copolymerization components other than terephthalic acid and ethylene glycol include isophthalic acid, 2,8-natutalendigalphonic acid, adipic acid, sebacic acid, oxalic acid, diethylene glycol, propylene glycol, cyclohexane dimetatool, and p-oxybenzoic acid. , 3,5-di(carbomethoxy)benzenesulfonic acid metal salts, or derivatives thereof, but are not limited to the following specific examples. The thickness of the multi yarn of the present invention is not particularly limited, but it is preferably in the range of 125 denier to 3000 denier as a suitable range for rubber reinforcement. If it is less than 125 denier, it is not preferable because when it is made into a rubber reinforcing multi yarn, the fatigue resistance effect aimed at in the present invention cannot be obtained. way 300
If it exceeds 0 denier, it is not preferable because there are many problems such as a low strength utilization rate when used as a tire cord.

The mulch yarn of the present invention is composed of a fiber bundle (A) that has been treated for easy adhesion and a fiber bundle (B) that has not been treated for easy adhesion, and 50% by weight or less, preferably 40 to 10% by weight of the whole mulch yarn The fiber bundle (A) is treated to facilitate adhesion and the fiber bundle (B)
Therefore, it is necessary to have a yarn length difference of 2.5% or more.

Here, if less than 50% by weight of the filament is not subjected to adhesion-facilitating treatment, it is not preferable because the desired adhesion effect cannot be obtained.

In addition, if the yarn length difference of the fiber bundle (A) is less than 2.5%, the easily bonded fibers, which have essentially long yarn lengths, are placed on the outer periphery of the cord during the twisting process, resulting in an adhesive effect. This is not preferable because the effect of raising the temperature cannot be obtained.

The adhesion-promoting treatment of the present invention is carried out during spinning and drawing stages by adding HL+ agent to 1-7. Processed by

Examples of fiber extractants for easy adhesion include treatment fl agents containing methylol compounds, incyanate compounds, epoxy compounds, and functional derivatives thereof. Particularly suitable epoxy compounds include reaction products of epichlorohydrin and aliphatic polyhydric alcohols such as glycerin, propylene glycol, ethylene glycol, hexanetriol, sorbitol, trimethylolpropane, polyethylene glycol, and polyglycerin, resorcinol, catechol, hydroquinone, Examples thereof include glycidyl ethers obtained from reaction products of phenyls such as 1.3.5-)lyhydroxybenzene and bis(4-hydroxyphenyl)methane with epichlorohydrin.

Next, a method for manufacturing the multi-thread of the present invention will be explained.

FIGS. 1 and 2 are examples of the fiber manufacturing apparatus of the present invention. The molten polyester is extruded from a gold plate, immediately cooled and solidified in the quench chamber 2, and then spun. The +b agent is applied by the oiling roll 3 and the circumferential speed B
It is sent to a britension roll 5 which rotates at oom/min. The spinning oil may be any conventionally known lubricant as the -L component, such as mineral oil, esters of higher fatty acids and higher alcohols (butyl stearate, oleyl laurate, instearyl palmitate, etc.),
Oil agents made of esters of dibasic acids and higher alcohols (dioctyl sebacate, dioctyl azelate, dioleyl adipate, etc.), esters of trihydric alcohols and higher fatty acids (glycerin trioleate, trimethylolpropane tridecanate, etc.) These include, but are not limited to.

It is stretched by 2 to 6% between the tension roll 5 and the first godet roll 6. The first godet troll is 90
℃, and is stretched approximately 4 to 4.5 times between second godet rolls 7 heated to 150°C. Further, the film is stretched 1.3 to 1.5 times between the second godet roll and 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 easy-adhesion oil to some of the fiber bundles.
) to be done. The fourth Godent rolls 9A and 9B are composed of two pairs, and the outer diameter of the large roll 9A is 5% larger than the outer diameter of the large roll 9B. The fiber bundles to which the adhesive agent has been applied are sent to the body roll 9A, and the other fiber bundles are fed to the body roll 9B, where they are given 3% and 8% relaxation, respectively. After that, it passes through an interlacer 11 to impart convergence, and then is wound up by a winder 12. FIG. 2 shows another example in which the difference in yarn length of the fiber bundle is imparted in the drawing section. 4 in FIG. 2 is an oiling roll that applies adhesive lubricant, and the yarn is divided using a guide so as to touch only a part of the yarn bundle.

In this way, making the fiber bundle to which the fiber oil for easy adhesion is applied has a yarn length difference of 2.5% or more with respect to other fiber bundles, it is necessary to use a technique to provide a difference in drawing ratio and/or a difference in relaxation rate. This can be achieved by applying technology that increases

As mentioned above, when applying the fiber oil for easy adhesion, it is necessary to divide the fiber bundles into fiber bundles to which the fiber oil for easy adhesion is applied and those to which it is not applied, but of course, fiber bundles to which the fiber oil for easy adhesion is not applied are Needless to say, a spinning oil agent such as a thread lubricant is added to the material. The fiber oil for easy adhesion may be applied before or after stretching, but if it is applied after stretching, it is necessary to apply the spinning oil to the fiber bundle prior to stretching.

In the thus obtained mulch yarn of the present invention, the fiber bundle (A) which has been subjected to the adhesion treatment has a longer yarn length than the fiber bundle (B) which has not been subjected to the adhesion treatment. Therefore, when the cord is twisted in the subsequent yarn twisting process, the fiber bundle which has been treated to be easily bonded and has essentially a long yarn length is arranged on the outer circumferential side of the cord. For this reason R
Even in dip cords treated with dip heat treatment using only FL (resorcinol-formalin-latex) treatment liquid, conventional Ji311P-clad polyester I! It exhibits adhesive properties equivalent to cords made of A-fiber. This is a natural result considering that only the surface of the deep cord comes into contact with the rubber. A disadvantage of conventional tire cords made of easily adhesive fibers is that the adhesive agent is applied to the center of the cord, which does not participate in adhesion to rubber, making the dip cord hard and poor in fatigue resistance. On the other hand, since the fibers located in the center of the multi-yarn cord of the present invention are not treated to facilitate adhesion, the dip cord does not become hard after heat treatment and has excellent fatigue resistance.

(Measurement method of fiber length difference) Apply a load of 0.05 g per denier to the fiber wipe, hold it vertically, and use a safety razor with the tip of the blade cut off with sandpaper to tE exactly 50 cm in length to all the single fibers. Put a red mark on it. Thereafter, the fiber is divided into single fibers, a load of 0.05 g per denier is applied to each single fiber, and the distance between the marks is measured in +n l'- positions to the first decimal place. The average value of the longest five lines is SLN The average value of the shortest five lines is S
Let it be s.

The m fiber length difference is determined by the following formula.

Fiber yarn length difference (%) = (SL/5g-1)xlOO(H
Measuring method of contact force) A sample cord is passed through the center of a rubber of 1 cm×1 c+s×1 c× in a mold and co-vulcanized, and after vulcanization, the pulling force of the cord from the rubber is measured. (Ii
kg/c) (Method of measuring disc fatigue) JIS L-1017゜eu*, 1.3.2.
Measured according to 2° disc fatigue strength (Gutdrich method).

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

Example 1 Polyethylene terephthalate with an intrinsic viscosity of 1.0 was
The melt was discharged from a two-hole spinneret, cooled and solidified with cooling air at 20°C, and after applying a spinning oil, the peripheral speed was 800 m/min.
A pretension roll of 5% is applied between the first godet (temperature 90'C) at a circumferential speed of 630 m/min, and the second godet is stretched 4 times and the circumferential speed is 2520 m/min.
Godet (temperature 150'C), further stretched 1.48 times and transferred to the third godet 8 temperature 2 at a circumferential speed of 3730 m/min.
20°C) and further adhesion treatment to the 63 filament.
Add 0.9% of l+ura agent to the total filament.
The 64 filaments and the remaining 128 filaments were given different relaxation rates (1 to 7%) and then converged by an interlacer to wind up a 1500 denier fiber. For comparison, when the relaxation rate difference is 0% and when all 192 filaments are treated with 0.3% adhesive treatment oil.
The yarns were wound up with 2 levels of 0.9% and without the adhesion oil. Epon 812 (made by Shell Chemical Co., Ltd., a combination of glycerin and epichlorohydrin) was added to an aqueous emulsion obtained by dissolving 70 parts of a spinning oil containing a fatty acid ester and a nonionic activator in 900 parts of water as an easy-to-adhesive extractant. An epoxy compound-containing treatment agent was used by dispersing 30 parts of the reaction product.

The obtained fiber is lower F? Both 8 (Z) and ply twist (S) are 40
The number of twists was t/10c+* to make a double yarn raw cord. The raw code is RFLJS, f”Jl by the usual method.
, t, dip cord and empty tire cord characteristics were measured.

Conclusion The results are shown in Table 1.

Margins below (Effects of the Invention) As is clear from this example, the rubber reinforcing cord made of multi-threads of the present invention is significantly superior to the tire cord made of uncured fibers according to the prior art. It exhibits fatigue resistance equivalent to adhesion properties, and is easy to adhere to.
It is possible to provide a tire cord that exhibits superior fatigue resistance and adhesiveness equivalent to that of tire hoods made of fibers made of fibers, and satisfies both adhesiveness and fatigue resistance that have not been achieved with the prior art.

[Brief explanation of drawings]

FIG. 1 shows an example of an apparatus for producing multi-yarn according to the present invention. FIG. 2 shows an example of an apparatus for producing multi-yarn according to the present invention other than that shown in FIG. 1. 1: Spinning ITI Gold 2: Quench Champer 3.4
: Euligroll 5 Nib tension roll 6: First Godetroll 7: Second Godetroll (8A, 8B): Third Godetroll (9A, 9B): Fourth Godetroll 1O guide 11: Interlacer: Winder

Claims (1)

[Claims] (1) A multi-thread made of polyester whose main constituent unit is ethylene terephthalate.
0% by weight or less consists of a fiber bundle (A) that has been treated for easy adhesion and a fiber bundle (B) that has not been treated for easy adhesion, and the easily adhesive fiber bundle (A) is 2.5% or more more than the fiber bundle (B). A fatigue-resistant and easily adhesive polyester multi yarn characterized by having a yarn length difference of .