JPH04352813A - Fiber and filament stretched from polymer mixture - Google Patents

Abstract

PURPOSE: To obtain fibers and filaments improved in drawing ability and strength and comprising a polymer blend mainly containing an aliphatic polyamide or a polyalkylene terephthalate to be generally used and containing a specific amount of a polyalkylene sulfide. CONSTITUTION: The polymer blend containing (A) at least 90 wt.% aliphatic polyamide such as polyamide 6 and polyamide 66 to be generally used or polyalkylene terephthalate such as polyethylene terephthalate, (B) 0.1-10 wt.% polymer containing polyarylene sulfide (for example; poly-p-phenylene sulfide) represented by the formula [wherein Ar is a (substituted) arylene] as a main unit and optionally (C) up to 30 wt.% general auxiliaries and additives based on components A+B is melt spun and drawn by a draw ratio of 1:2-1:10 to obtain the objective fibers and filaments improved in drawing ability and strength.

Description

[Detailed description of the invention]

[0001] The present invention is directed to the use of polyarylene sulfide.
．． It relates to polyamide and polyester fibers with improved properties obtained by addition of amounts of 1 to 10% by weight, preferably 0.3 to 5% by weight, subsequent spinning and conventional fiber post-treatment.

Thermoplastic polyamides (eg PA6 and 6
6) and polyesters (e.g. polyethylene terephthalate) for the production of fibers are known [e.g. Dictionary of Polymer Science and Engineering, 2nd Edition, Wiley Inter-science.
e, John Wiley & Sons, New
York)].

These fibers have generally known good properties such as high tensile strength/breaking strength, elongation at break, wearing comfort,
and has a good appearance.

They are used in textile applications such as carpet yarns, tire cords, finishing backings, and other applications.

It would then be desirable for a wide range of applications if its already fundamentally good properties, especially its strength, could be further improved.

It has now surprisingly been discovered that by using small amounts of certain polymers, the drawability and strength of polyamide and polyester fibers can be significantly improved, with additional benefits in terms of hardness and heat resistance. Ta.

The present invention therefore comprises: 1) at least 90% by weight of a commonly used aliphatic polyamide or polyalkylene terephthalate; and 2) as the main unit (I).

[0008]

[C4]

0.1 to 10% by weight of a polymer containing [wherein Ar is a substituted or unsubstituted arylene group] and optionally 3) customary auxiliary and additive substances, A) + B) The present invention provides drawn fibers from polymer mixtures containing up to 30% by weight based on.

Polymers 2) are arylene sulfide homopolymers and copolymers. The preferred one is poly-p-
Phenylene sulfide (PPS) (II)

[0011]

[C5]

[0012] Polyarylene sulfides 2) are used which are directly condensed in solution to high molecular weights in one operation without subsequent oxidative molecular weight increase. This manufacturing method is known. See, for example, European Patent No. 171,021.

Corresponding polyarylene sulfides are available, for example, under the trade names Tedur® and Photron (
Fortron®).

[0014] Melt viscosity of about 5 to 500 Pa·s (320
It is possible to use polymers 2) having a temperature of 0.degree. C. and 100 S-1). In particular, the melt viscosity should be between 10 and 200 Pa·s.

Suitable polyamides 1) are the polyamides (PA) commonly used for the production of fibers by melt spinning, such as P
A6, 66, 46, 1212, 6T6, 6T16, and various copolyamides or mixtures of these polyamides. Polyamide is preferred over polyester.

PA6, PA66 and mixtures thereof or copolyamides based thereon are preferred. PA6 and copolyamides based on PA6 are particularly suitable.

Suitable polyesters 1) are the customary melt-spun polyesters based on terephthalic acid and aliphatic glycols, such as polyethylene terephthalate, polybutylene terephthalate and poly-(1,4-cyclohexylene dimethylene terephthalate).

Polyethylene terephthalate is preferred.

Polyesters 1) may also contain, in addition to terephthalate and glycol, varying amounts of other monomers such as isophthalic acid, adipic acid and diethylene glycol.

Particularly preferred components 1) are PA6, PA66,
mixtures containing these, and copolyamides thereof.

[0021] To produce fibers according to the present invention,
Polymers which can be produced in various ways, for example by kneading (e.g. using a kneader or extruder), by producing polyamides or polyesters in the presence of polymer 2), or by mixing granules and subsequent spinning. A mixture is used.

Production of the actual fibers (for the purposes of the present invention, fibers should be understood to mean all types of fibers, such as filaments, monofilaments, wires, staple fibers, bulky continuous filaments, etc.) ) is carried out by a conventional method, preferably by melt spinning. All conventional post-treatment methods can be used, such as stretching, fixing, crimping, dyeing, etc.

The drawn fibers for the purpose of the present invention are
For example, fibers that have been drawn and oriented by draw-twisting, draw-winding in the case of filament yarns, by roll or calendar drawing in the case of towing, or by spin-drawing, for example as part of a high-speed spinning process. Essentially any other stretching method is also suitable. Such drawn fibers exhibit increased orientation and crystallinity compared to standard injection molded or extruded materials.

Suitable additive substances 3) are all substances customary for the production of fibers, such as matting agents (among others Ti
O2), UV stabilizers, pigments, dyes, nucleating agents, antioxidants, fluorescent agents, whitening agents, dyeing aids, sizes, etc.

The polyamide or polyester 1) may contain units which improve the dyeability of the fibers as copolymerized units. Such monomers are known.

Alloys of polyamides or polyesters and polyarylene sulfides are known. The applicant's unpublished patent applications LeA Nos. 26,662 and 26,89
See No. 4.

WO 86/3212 describes polyamide 46
describes a polymer alloy made from at least 5% by weight of polyarylene sulfide and said to have very good mechanical properties. The patent application discloses that polyamides 6 and 66 are not sufficiently compatible with polyphenylene sulfide to obtain good mechanical properties. Control Example 3 contains 15% polyamide 6 and PPS.
It has been shown that alloys manufactured from the There is. The patent application does not in any way refer to the use of molding compositions for the manufacture of fibers.

US Pat. No. 4,292,416 describes polyarylene sulfide as a nucleating agent, ie, an additive to increase crystallinity to polyamide, which is similar to terephthalic acid and C10 diamine. Exemplified only for special polyamides produced from mixtures. Addition of PPS generally reduces tensile strength and bending modulus. Elongation at break and scoring impact strength are usually significantly increased. This combination of extreme and unusual effects applies to any polyamide. The above patent application does not contain any mention that the extensibility or strength of fibers based on aliphatic polyamides (in particular PA6 and copolyamides based on PA6) is significantly increased by the addition of PPS. A decrease in strength would have been expected, especially from US Pat. No. 4,292,416.

When polymer multicomponent systems, especially partially crystalline polymers, are used for the production of fibers, attempts to increase drawing as well as orientation usually give rise to segregation phenomena. This is associated with poor phase bonding of the fibers and worse mechanical properties.

The present invention is based on the surprising discovery that in order to achieve a clear improvement in the properties of the fibers (extensibility, strength) by the addition of polyarylene sulfite, only a narrow range of the addition of the former is suitable. Based on. This range according to the invention is preferably from 0.3 to 5.0%, particularly preferably from 0.5 to 3.0%, especially from 0.6 to 2.5%. According to the invention, within this narrow range the extensibility and strength of, for example, PA6 fibers increases. For example, the strength of PA6 fibers can be increased by 25-30%, which can be accompanied by improvements in hardness and heat resistance. The extensibility of the fiber remains essentially unchanged. The above-mentioned effects forming the basis of the present invention are unexpected and do not originate from past technology. In particular, the improvement in the properties of the fibers according to the invention is due to PA6
and WO which teaches that it is difficult to produce homogeneous mixtures from 66 and PPS due to their insufficient affinity and that such alloys exhibit significantly poor strength and hardness values. This is surprising in light of No. 86/3212.

The fibers according to the invention can generally be produced by conventional methods via the melt. All conventional post-processing methods can be used. Regarding the manufacture of fibers, see Dictionary of Polymer Science and Engineering, 2nd edition, Wiley Interscience, Inc., and also H. Klare, Engineering and Chemistry of Synthetic Fibers from Polyamides, VEB Tech
nik, Berlin), 1954. Here, melt spinning can be carried out not only above but also below the melting point of the polymer 2).

The fibers according to the invention represent a useful addition to technology because of their very good properties. The present fibers can be used alone or optionally in combination with other natural or synthetic fibers. It is suitable for all applications of polyamide and polyester fibers, especially those requiring high strength.

The following examples contain typical starting materials in typical amounts and are illustrative of the invention without limiting it.

[0034]

【Example】

Examples 1 to 4 (not according to the present invention) LeA No. 26,
Preparation of PA6/PPS compositions according to No. 662 Polyamide 6 (ηrel=4.0; 1 in m-cresol
%, 25 °C) under a production rate of 250 °C and 30 kg h-1, PPS (39 Pas, 310 °C, 1000 s-1
) 1, 2 and 5% by weight or without PPS were compounded in a twin-screw extruder (ZSK53). The viscosity and extruder energy consumption values are shown in Table 1.

Examples 5 to 8 (not according to the invention) L
Preparation of PA6/PPS compositions according to eA No. 26,894 Caprolactam and water (0.5 liters without PPS; 0.6 liters with PPS) and further P
PS100, 200 or 500g (caprolactam and P
The total weight of PS is always 10 kg) (melt viscosity: 306°C
and 1000S-1 at 31 Pa·s) was placed in a 25 liter autoclave. After purging with nitrogen three times,
The contents were heated to 200°C and kept under autogenous pressure for 1 hour. The contents were then evacuated to atmospheric pressure and 40 liters of nitrogen per
Time passed and the temperature was raised to 270℃ at the same time (PP
(280° C. in the presence of S1 and 5%), the reaction time was 4-7 hours until the desired melt viscosity was achieved.

The analytical data of the samples are shown in Table 1.

[0037]

[Table 1] Table 1 PPS1) A
2) t/T extraction amount 3) ηr
el4) Example (weight%) (
A) (Time) (℃) %
1
-56-
-3.9
2 1
52 - -
3.8 3
2 49 -
-3.7
4 5
49-
- 3.6 5
- - 6.5
/270 14.0 3.8
6 1
-7.0/280
13.2 3.8 7
2-4.
0/270 13.8 3.
7 8 5
-4.5/270-85
11.5 3.7 1) Based on the mixture2) Energy consumption of the extruder in A3)
Methanol 4) 1% in m-cresol, time at 25 °C t = temperature T °C Examples 9 to 16 (according to the invention) In an extrusion spinning apparatus, the polyamides of Examples 1 to 8 were melted and spun into a plurality of filaments. spun. The spun material thus obtained was stretched.

The spinning conditions and fiber data are summarized in Table 2.

[0039]

[Table 2]

As the examples show, fibers modified with PPS exhibited improved properties, most particularly when added at 1-2%. The stretching ratio is generally 1:2 to 1:1
0, preferably 1:2.5 to 1:7.5, most preferably 1:3 to 1:6.

Features and aspects of the present invention are as follows.

1. A) At least 90% by weight of commonly used aliphatic polyamides or polyalkylene terephthalates
, and B) as the principal unit (I)

[0043]

[C6]

0.1 to 10% by weight of a polymer containing [wherein Ar is a substituted or unsubstituted arylene group] and optionally C) customary auxiliary and additive substances, A) + B) Fibers and filaments drawn from polymer mixtures containing up to 30% by weight.

2. Polymer B) is preferably poly-p-phenylene sulfide (PPS) (II)

[0046]

[C7]

The fiber according to the above 1. 3. The fiber according to 1 above, containing preferably 0.3 to 5.0, particularly preferably 0.5 to 3.0, especially 0.6 to 2.5% by weight of polymer B.

4. Fibers according to 1 above, which contain polyamides such as PA 6, 66 and mixtures thereof or copolyamides based thereon or polyesters such as polyethylene/terephthalate as polymer A).

5. Fibers according to 1 above, containing matting agents, UV stabilizers, pigments, dyes, nucleating agents, antioxidants, fluorescent whitening agents, dyeing aids, sizes, etc. as additive substances C).

6. Drawn fibers (filaments, monofilaments, wires, staple fibers, bulk continuous filaments, etc.) of 1 to 5 above of increased strength.

7. In order to produce drawn fibers of increased drawability and strength by melt spinning and drawing at a draw ratio of 1:2 to 1:10, A) the commonly used aliphatic polyamides, especially PA6, 66;
and their copolymers or polyesters, especially polyethylene terephthalate, at least 90% by weight, preferably 90% by weight
5 to 99.7% by weight, particularly preferably 97 to 99.5% by weight, especially 97.5 to 99.4% by weight, and B) as the main unit (I)

[0052]

[Chemical formula 8]

[0053] From 0.1 to 10% by weight, preferably from 0.3 to 5.0% by weight, particularly preferably from 0.5 to 5.0% by weight of a polymer containing [wherein Ar is an optionally substituted arylene group]
using a polymer mixture of 3.0% by weight, and in particular 0.6-2.5% by weight, and optionally C) up to 30% by weight based on A) + B) of customary auxiliary and additive substances. to do.

Claims (4)

[Claims] Claim 1: A) At least 90% by weight of a commonly used aliphatic polyamide or polyalkylene terephthalate.
, and B) 0.1 to 10% by weight of a polymer containing (I) as the main unit, wherein Ar is a substituted or unsubstituted arylene group, and optionally C) a conventional auxiliary agent. Fibers and filaments drawn from polymer mixtures containing up to 30% by weight based on A)+B) of and additive materials. 2. A fiber according to claim 1, wherein polymer B) is preferably poly-p-phenylene sulfide (PPS) (II). 3. Polymer B is preferably 0.3 to 5.0
, particularly preferably from 0.5 to 3.0, especially from 0.6 to 2.5
% by weight of the fiber of claim 1. 4. To produce drawn fibers of increased extensibility and strength by melt spinning and drawing at a drawing ratio of 1:2 to 1:10, A) a commonly used aliphatic polyamide, especially PA6; , 66
and their copolymers or polyesters, especially polyethylene terephthalate, at least 90% by weight, preferably 90% by weight
5 to 99.7% by weight, particularly preferably 97 to 99.5% by weight, especially 97.5 to 99.4% by weight, and B) as the main unit (I) [wherein Ar is optionally 0.1 to 10% by weight, preferably 0.3% by weight of a polymer containing a substituted arylene group]
~5.0% by weight, particularly preferably 0.5-3.0% by weight
and in particular from 0.6 to 2.5% by weight, and optionally C) up to 30% by weight, based on A) + B) of customary auxiliary and additive substances.