JPS6245718A - Polyester yarn - Google Patents

Abstract

PURPOSE:To obtain polyester yarn having high modulus of elasticity and improved wear resistance, by subjecting a polyester showing anisotropy in melting to melt spinning. CONSTITUTION:An aromatic polyester showing anisotropy in melting is subjected to melt spinning and prepared yarn has >=0.1mm, preferably >=0.3mm, more preferably >=0.5mm diameter when the thickness of the yarn is calculated as a section of circle and >=300g/d modulus of elasticity in tension. To make the yarn more elastic, the spun yarn can be heat-treated and/or drawn. USE:Useful for rope, cable, FRP, FRTP, speaker cone, safety clothes, tension member, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to poly:stell fibers having a larger diameter and higher modulus than ordinary fibers.

(Prior art) Synthetic fibers, along with natural fibers, are indispensable materials for clothing and industrial applications, and among the materials used for various purposes, polyester/l/ (a typical example is polyethylene terephthalate) Nylon is preferred due to its spinning speed of over 8000 m/min, stability of spinning, and low price.

It is the most used of the eight major fibers including acrylic. This polyester has a strength of 8-10? Although it has physical properties such as /d9 elastic modulus of 25 to 150 r/d, it is still not sufficient.

That is, in the industrial world, thick fibers with high strength or high elastic modulus have been desired for cores of cables and ropes, overhead wires, wire substitutes, etc. For example, when metal wires are used, their conductivity causes noise and overcurrent to flow through the instrument, and when composite materials are used, the adhesion at the interface between the base material and the reinforcing material can be difficult!
or when making a thin denier rope,
There were problems with the processing process and wear during processing.

(Problems to be Solved by the Invention and Means for Solving the Problems) In view of the current situation, the present inventors have
As a result of extensive investigation using aromatic polynisdel which exhibits anisotropy in J, we have arrived at the present invention relating to 210 wire having a large diameter and high elastic modulus〇In other words, the present invention exhibits anisotropy when melted. A fiber obtained by melt-spinning aromatic polyester, whose cross-sectional area is expressed as a perfect circle, and the diameter of the perfect circle is 0.
．． 111 m or more, tensile modulus is 80 Of/d
This relates to a polyester fiber characterized by the above characteristics.In the present invention, the polyester exhibiting anisotropy when melted is placed on a heated sample stand between two orthogonal polarizing plates. It means something that has the property of being able to transmit light in the temperature range where it can flow when the powder is placed and heated.

As such aromatic polyester,
The aroma shown in No. 18016 and No. 55-20008, etc.:
If group dicarboxylic acids, aromatic diols and/or aromatic hydroxydicarboxylic acids, or derivatives thereof, optionally combined with ring dicarboxylic acids, pentacyclic dicarboxylic acids, I'L' , aliphatic diols and copolymers with these derivatives are also included. Here, the aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, 4,4'-dicarboxydipheny/'%
2.6-dica-poxynaphthalene, 1.2-bis(4-
Examples thereof include carboxylic phenolic V) ethane, and derivatives thereof with alkyl, aryl, alkoxy, and halogen groups substituted on the nucleus.

Aromatic diols include hydroquinone, resorcinol,
4,4'-Dihydroxydipheny, 4,4-dihydroquine benzophenone, 4,4-dihydroxydiphenylethane, 4,4'-dihydroxydiphenylethane, 2,2-bis(4-hydroxyVpheny/L/) Propane, 4,4'-dihydroxydiphenyl ether, 4
．． 02-Hydroxy, including 4-dihydroxydiphenylsulfone, 4,4-dihydroxyphenylsulfide, 2,6-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, etc., and nuclear substituted products of these with alkyl, aryl, alkoxy, and halogen groups. Naphthalene-6-carboxylic acid, 1-hydroxynaphthalene-5-carboxylic acid, etc., and conversion of their alkyl, aryl to alkoxy, or halogen groups into the nucleus 1d are unsuccessful.

As the alicyclic dicarboxylic acid, trans-1,4-dicarboxycyclohexane, eis-1,4-! 'carpogysicyclohexane, etc. and 16' conversion of their alkyl, aryl, and halogen groups are mentioned.
1,4-dihydroxycyclohexane, eim-1,4
-dihydroxycyclohexane, ethylene glycol,
1.4-butanediol, xylylene diol, etc. are available.

Among these combinations, preferred aromatic polyesters as objects of the present invention include (1) p-hydroxybenzoic acid residues 40 to 7Q; Mol% and aromatic diol residues 15
(2) copolyester consisting of terephthalic acid and/or isophthalic acid and chlorohydroquinone, phenylhydroquinone and/or hydroquinone color, (3) p-hydroxybenzoic acid residues 20 to 80%; Examples include copolyesters comprising 20 to 80 mol% of 2-hydroxynaphthalene-6-carboxylic acid residues.

These starting materials can be used as they are or as esters with aliphatic or aromatic monocarboxylic acids or their derivatives, aliphatic 7-coles, phenols or their derivatives, etc. A polycondensation reaction is carried out by chemical reaction.

As the polycondensation reaction, known bulk polymerization, solution polymerization, suspension polymerization, etc. can be adopted, and Sb, T, etc.
The polymerization can be carried out by adding polymerization catalysts such as I, Ge compounds, stabilizers such as phosphorus compounds, TiO2, CaC0), fillers such as talc, etc. O The obtained polymer can be used as is or as a powder. The sample is heat-treated in body form in an inert gas or under reduced pressure to prepare a sample for spinning.

Alternatively, the aromatic polyester used in the present invention may have a molecular weight range suitable for spinning, but depending on the composition and structure, a solvent that can be uniformly dissolved may be There are many problems such as lack of molecular weight measurement method and lack of accuracy of molecular weight measurement method, and it cannot be used as a specification for aromatic and dusty polyester suitable for the present invention. We introduced "flow temperature" as a physical property value. Using a flow tester CFT-500 manufactured by Shimadzu Corporation, a pressure of 100 Kv' was used with a nozzle with a diameter of 1 and a length of 10 mm.
The aromatic polyester sample was heated at 4°C/mi in the crA state.
7, the sample flows through the nozzle, and 48
．． As the temperature that gives an apparent viscosity of 000 pois@,
"flow temperature" was defined.

The present inventors have now produced aromatic polyesters of various compositions and have tried varying their flow temperatures, and have found that aromatic polyester 5- The flow temperature of the mol was found to be 280-880°C.

・When the flow temperature is lower than this temperature range, there are problems such as υ, IB, and fiber elongation which are difficult to obtain due to the tendency of reactions during storage. -'P crosslinking reaction is likely to occur, and the load on the device increases, which causes problems. As the device 11 for melt spinning in the present invention, a known Pfunger type or screw type extruder can be used. The possible zero spinning temperature is 280 to 420℃.
, preferably 300 to 400°C. If the temperature is lower than this range, the load on the apparatus becomes large9, and the sample agglomerates are not uniform0.Conversely, if the temperature is higher than this range, it may cause decomposition of the polymer.This invention As a method of obtaining a thick yarn, which is one of the requirements in Since the orientation due to shearing is large, the ratio of the land length to the diameter of the nozzle should be 0.5 or more, preferably 1 or more, and the nozzle should have a large diameter. In some cases, it is desirable to use a number of 8 or more.

According to the present invention, the fibers are spun as they are, or the fibers are attached and rolled up, and then the fibers are drawn down and the fibers to be obtained are Find it from the thickness. Cross section of f-meter fiber (depending on size, purpose and use, ¥4, 41
You can choose a ff circle or one with various unevenness.

To make fibers with these cross sections [side or r-'', r6J
, r+1. This can be achieved by using a nozzle with various discharge holes such as ``r〉<J, ``8''.

Although the resulting fiber can be used in its sweet form, it can be made even more resistant by heat treatment, stretching, or a combination of these treatments.

Thus, 41. of the present invention. T' fibers are obtained. In addition, in the case of fibers with an irregular cross section other than a perfect circle, the diameter of the thread should be 0.1W or more, preferably 0.1W (when considered in terms of the cross section of a perfect circle). A fiber having a length of 8 or more, more preferably 0.5 m11 or more provides a characteristic polyester/L' fiber.

(Function and Effect) Polyester v with a large diameter obtained by such method
lil fiber has a high elastic modulus and has a resistance of 1? ! It also has excellent abrasion resistance because it is thick.

The fibers obtained according to the present invention can be used for robes, cables, FRP, FRTP, speaker cones, safety clothing, city members, etc.

(Example) Examples and comparative examples are shown below to explain the present invention in detail, but these are merely illustrative and are not intended to be limiting.

In addition, the tensile test of the fiber in the example was carried out using Toyo Baldwin's Autograph 7M-500, with a sample interval of 50 cm,
The measurement was performed at a tensile speed of 51 m1n.

The optical anisotropy was measured by placing the sample on a heating stage, raising the temperature at 25° C./min under polarized light, and observing it with the naked eye.

Reference example 1 p-acetoxybenzoic acid 7.20! llr (407 μ), terephthalic acid 2.49-(15 mol), isophthalic acid 0.88 b (5 mol/L'), 4.4'-diacetoquine diphenyl/I 15.45 Kf (20,2 7) was charged into a polymerization tank equipped with a comb-shaped stirring blade, and the temperature was raised while stirring in a nitrogen gas atmosphere, and polymerization was carried out at 880° C. for 8 hours. During this time, the acetic acid produced is removed and polymerization is carried out with strong stirring.
After that, it was gradually cooled and the polymer was taken out of the system at 200°C. The yield of the polymer was 10.88KF, which was 97% of the theoretical yield.
．． 8% □ This was crushed with a hammer mill manufactured by Hosei Micron Co., Ltd. to produce particles of 2.5 W or less. □ When this was treated in a rotary kiln at 280°C under a nitrogen atmosphere for 5 hours, the "flow temperature" Optical anisotropy was observed above 0350°C, where the temperature was 826°C.Reference Example 2 Synthesis of copolyef, til consisting of 2,5-diacetoxybiphenyl and terephthalic acid using the same apparatus 6) as in Reference Example 1. It was seven years ago. The "flowing temperature" was 818°C, and optical anisotropy was observed above 840°C.Example 1 tSS Example 1 Using polyester/l/, melting was carried out using a screenie type extruder with a diameter of 30 mm. The O nostle used for mime spinning has a hole diameter of 8II11, a hole length of 86ILa, and a number of holes of 1.The discharge port has a circular shape. Polyester was charged from a hopper and spun at 365° C. The zero discharge amount and winding speed were changed. Stable spinning was carried out with various thread diameters, and pale yellow clear grade fibers were obtained.

The results of a tensile test when this fiber was treated in nitrogen at 820°C for 3 hours, and the fiber was wound 5 times around a stainless steel axle with a diameter of 80α, and the axle was rotated at 60 cm for 5 minutes.
The results of the tensile test after the fatigue test are shown in Table 1. It can be seen that the fiber of the present invention is superior to Comparative Example 1 of polyethylene terephthalate.

Comparative Example 1 Spinning was performed in the same manner as in Example 1 at 300C using Toyobo's polyethylene terephthalate RT-580. however,
In this case, at the 5th point under the nozzle, the discharged yarn was introduced into water, rapidly cooled, stretched 4 times at 0.150°C, and heat treated under tension at 185°C for 8 hours. 0 Example 2 showing the results of the tensile test after the fatigue test

Claims (1)

[Claims] A fiber obtained by melt-spinning polyester that exhibits anisotropy when melted, whose cross-sectional area is expressed as a perfect circle, and whose diameter is 0.1 mm or more, and whose tensile modulus is 300 g/ d or more.