JPS5928672B2 - modified polyester fiber - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to textile products made of modified polyester fibers, and particularly to textile products that are pressure-dyed with basic dyes.

Conventionally, when manufacturing interior products such as carpets and blankets, dyeing is done in the form of cotton or spun yarn.

The so-called dyeing method has been used. However, recently it has become more popular, and there are more value-added, latest trends and fashion O.
Anti-dyeing, a post-dyeing method that can handle this problem, has begun to attract attention.

In the case of reverse dyeing, it is difficult to dye under high pressure, so it is an important requirement that the fiber material be dyed under normal pressure.

On the other hand, many attempts have been made to modify polyester so that it can be dyed with basic dyes, and for example, a method of copolymerizing dimethyl isophthalate having a metal sulfonate group is known.

However, when using this known technique to copolymerize, for example, ethylene isophthalate, it is necessary to copolymerize 4.5 mol% or more in order to obtain fibers with sufficient color development by normal pressure dyeing. Highly copolymerized polyester is bulky and has a high heliquidity rate, and it is impossible to obtain a copolyester of 9% or less.

In addition, the dyed product's color fastness to sunlight is significantly reduced, and due to reverse dyeing, it becomes severely bent, resulting in a significantly low commercial value.

Furthermore, when ethylene isophthalate having a metal sulfonate group is copolymerized multiple times, the raw material cost naturally increases significantly.

As a result of extensive research, the present inventors have developed a modified polyester fiber that can be dyed under normal pressure even with a relatively low amount of ethylene isophthalate copolymerized with a relatively small amount of metal sulfonate, and that also has sufficient performance as a polyester fiber. This led to the invention of a textile product.

That is, the present invention provides A(CnH2nO)mH (A is CI
H2l+10 or OH,l = 1~10, n=2~
5, m = 2 to 100) and isophthalic acid (S mol %) containing a metal sulfonate group are 1.8≦S≦3.2.
・・・・・・・・・・・・・・・(1)2-
0.58≦M≦7-0.28 (2)
It is copolymerized so as to satisfy the relationships (1) and (2) of value measured using a type viscometer) is 0
．． We would like to provide a textile product made of polyester fiber with a dyeing capacity of 38 to 0.55 dl/g, which can obtain sufficiently excellent coloring properties by normal pressure dyeing, and which has a small heckling rate during dyeing. It is something to do.

In the present invention, if the amount of isophthalic acid S containing a metal sulfonate group is 1.8 mol or less, dyeing under normal pressure cannot be achieved unless the amount of polyalkylene glycol M is extremely increased.
Furthermore, when the M content becomes extremely large, the polyester no longer functions as a polyester, and the fiber properties deteriorate significantly.

Moreover, the dyed product cannot have a clear color tone.

Moreover, when S exceeds 3.2 molar ratio, due to the thickening effect due to the copolymerization of metal sulfonate groups, the stirring effect becomes poor and the polymerization rate decreases when polymerizing the polymer.
In order to spin a polymer with a degree of polymerization required for fibers, the melt viscosity is high, making spinning difficult.

Moreover, the increase in sulfonic acid groups increases hydrophilicity and increases boiling loss.

Furthermore, the stretchability is markedly reduced, and even if the stretching method is improved, the intrinsic viscosity is low and the EPC is 0.42 or less.

Therefore, when it is used as a carpet pile yarn and anti-dyed, it has a large amount of stiffness and is not a good quality product.

As a result of further research, the present inventors found that even if the amount of copolymerized isophthalic acid containing metal sulfonate groups that have affinity for basic dyes is small, polyalkylene glycol M (2-0,5S) It has been found that by copolymerizing above the weight ratio, even normal pressure dyeing shows the same dyeing properties as high pressure dyeing at 120°C.

The fact that such atmospheric pressure dyeing is possible by copolymerizing polyalkylene oxide, which has no affinity for basic dyes, is truly remarkable.

゛When M exceeds (7-0, 28), heat resistance decreases,
Since the Young's modulus is also low, the carpet becomes stiff and has a large bend due to the dyeing process.

Preferably (6-0,58), more preferably (4-O
, 5S) or less.

Furthermore, in the present invention, it is necessary that there be no heckling during dyeing, and therefore the intrinsic viscosity [η] of the fiber used is 0.38.
~0.55 dl/fj or EPC is 0.42
~0.65 is required.

Here, the intrinsic viscosity [η] is a value measured using a constant-temperature mixture of phenol and tetrachloroethane as a solvent using an Usoperode viscometer in a constant temperature bath at 30°C, and EPC is an elastic performance
Abbreviation for Coefficient, which is W, J, H
amburger [Text.

Res, J, 18102' (1948)], and is a value measured by repeatedly applying an elongation load at the initial 5% elongation load and taking the 100th cycle as a conditioning cycle.

Carpets that do not meet the above conditions may sag due to anti-dyeing or have poor compressive fatigue resistance as a carpet.
This is undesirable as it significantly lowers the commercial value.

More preferably, the EPC is 0.45 to 0.65.

The above-mentioned fibers can be obtained, for example, by the following fiber manufacturing method.

That is, the above-mentioned polyalkylene glycol and isofucuric acid containing a metal sulfonate group are combined into the above-mentioned formula (L
A polyester copolymerized to satisfy the relationship L(2) is polycondensed by a normal method, and the intrinsic viscosity [η] is 0.35.
~0.55 d17g-polymer.

In this way, by using a polymer with a lower intrinsic viscosity than in the production of normal polyester fibers,
In addition, it is important to use the fiber as a fiber with a low intrinsic viscosity in order to avoid denting of the subsequent product.

Either the polymer is once formed into chips and remelted in an extruder, or the polycondensed polymer is extruded as it is from a nozzle, and the draft (the value obtained by dividing the winding speed by the polymer injection speed from the nozzle) is 20 to 300. Transfer to obtain undrawn yarn.

The undrawn yarn is bundled to a density of 100,000 to 4,000,000 denier, and
It is heated in a water bath at 0 to 100°C or on a heated roller at 60 to 150°C and stretched 2 to 6 times.

Two-stage stretching is preferable, and the stretching distribution ratio (1 stage/2 stages) is preferable.
The number of steps) is preferably 2 to 10.

The drawn yarn is attached with a necessary finish or crimped, and then subjected to a relaxation heat treatment or a limited shrinkage heat treatment at 110 to 150°C for 1 to 30 minutes.

Alternatively, the undrawn yarn (100 to 10,000 dr) may be stretched 2 to 6 times (obtained by drawing) a filament drawing method using a pin plate, a roller plate, or a roller roller preheated to 70 to 200°C. .

The polyalkylene glycol referred to in the present invention is one that satisfies the following formula (% formula %), for example, CH3(C2H40)m
HHO(C2H40) m H or diethylene glycol, etc., and more preferably those with a molecular weight of 1000 to 500
0 methoxypolyethylene glycol.

The isophthalic acid containing a metal sulfonate group referred to in the present invention is a metal sulfoisofucuric acid, its dialkyl ester, or di-β-hydroxyethyl ester, and the metals include Li, Na, Ca, M
There are n, etc.

Preferred is sodium 3.5 di(carbomethoxy)benzenesulfonate.

The polyester referred to in the present invention means at least 8 constituent units.
00 mol% ethylene terephthalate, and in addition to the above-mentioned polyalkylene glycol and inphthalic acid containing a metal sulfonate group, 5 mol% or less, preferably 3 mol% or less of other components may be copolymerized.

In addition to the copolymerization components mentioned above, we also contain ordinary transesterification catalysts, polymerization catalysts, side reaction inhibitors such as phosphorus compounds and alkali metal salts, matting agents such as titanium dioxide, coloring inhibitors, oxidative decomposition inhibitors, etc. May contain.

Example 1 2.5 mol% of sodium 3.5-di(carbomethoxy)benzenesulfonate, 2% by weight of methoxypolyethylene glycol with a molecular weight of 2000, and a polymer that produces sodium acetate for the purpose of suppressing the production of diethylene glycol. By adding 1500 pINI and polymerizing, a polyethylene tereftate melt with [η] = 0.45 dl/g was obtained, and this was heated at 285°C, 10,5φ×48
The yarn was spun using a No. H spindle to obtain an undrawn yarn with a single fiber of 52 denier.

The obtained undrawn yarn was drawn at a ratio of 4.0 times (stretching ratio 8) in two steps at 75° C. in one bath and 98° C. in two baths.

After performing steam preheating mechanical crimping treatment on the drawn yarn, 10
It was dried at 0°C for 1 minute, set at 135°C for 3 minutes, and then cut to obtain raw cotton measuring 15 dr x 152 cm.

The raw cotton [η] obtained was 0.45 d4/g, and the EPC was 0.52.

Using this raw cotton, W-1/2.5, 125 t/m
Make a spun yarn with a gauge of 5/32'' and 7 stitches/in.
A carpet was made with a pile length of 14M, a first base fabric of Tie Bar (trade name), and a second base fabric of Jute.

The carpet was coated with Astrazon Red BBL (2
%owf) as a dye at 98°C for 90 minutes.

The obtained carpet showed a very good bright color, had no sagging due to dyeing, and had a very high product reversibility.

Examples 2 to 5, Comparative Examples 1 to 7 Same as Example 1 except that the EPC was changed by changing the copolymerization amount of sodium 3.5-di(carbomethoxy)benzenesulfonate and methoxypolyethylene glycol and the fiber manufacturing conditions. Raw cotton and carpet were produced in the same manner.

Their performance is shown in Table 1.

Comparative Example 1, in which the amount of S is as low as 1.7 mol%, does not show sufficient color development in normal pressure dyeing even when copolymerized with 6% by weight of M, and D L
F is also bad.

In Comparative Examples 2 and 5, where M is larger than (6-0, 28), even if the fiber manufacturing conditions were devised, the pile of the carpet curled due to anti-dyeing, and the strength of the fibers decreased due to heat treatment. This resulted in a high degree of compression fatigue.

Comparative Example 3 had insufficient color development in normal pressure dyeing.

Even if S and M are within the range ζ of the present invention [η] or EPC does not satisfy the range of the present invention, comparative example 4 has a carpet with poor bending due to anti-dyeing, high compressive fatigue, and the product is not as good as the one in the field. It became low.

In Comparative Example 6.7, the color development of the dyed product was good, but the DLF was poor.
In addition, there was a large amount of residual dyeing solution, which required drainage treatment.

In addition, the flatness is large and the compressive fatigue value is insufficient.
be.

In contrast, good results were obtained in all of the inventions shown in the Examples.

Example 6 [η:]-0.50 dz/g polyethylene terephthanate was copolymerized with 2.7 mol% of sodium 3.5 di(carbomethoxy)benzenesulfonate and 5% by weight of diethylene glycol. Spun through a star-shaped nozzle to create an undrawn yarn with a cross-sectional shape and external shape, and stretched 3.75 times between a preheating roller at 80°C and a plate at 160°C to obtain a filament of 75d/48f. Ta.

The [η] of this filament is 0.50 dll! i+
and EPC was 0.44.

From this, make tack fabric and use it as dye for 5evr.
Atmospheric pressure staining was performed using on Br1ll Red B.

The fabric had a vivid color and good drapability.

Claims (1)

[Scope of Claims] 1 Inphthalic acid containing a metal sulfonate group (S
mol%) and polyalkylene glycol (
M weight %) is A (Cn H2n O) mH A:CIH21+10 or OH, J=1~10n =
2-5 m=2-100 Copolymerized to satisfy the relationships of the following formulas (1) and (2), 1.8≦S≦3.2 ......
・・・・・・・・・(1) 2-0.58≦M≦7-0.28
...(2) and the intrinsic viscosity [η] (value measured using an Utsperohde viscometer in a constant temperature bath at 30°C using a mixture of equal amounts of phenol and tetrachloroethane as a solvent) is 0. .38-0.55 dl/fl Pressure-dyed textile products consisting of polyester fibers.