JPS5828374B2 - Polyester material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to copolyester fibers with high shrinkage properties, particularly specific shrinkage properties, and a method for producing the same.

Shrinkable fibers 6 are mixed or blended with non-shrinkable fibers and then heat treated at the yarn or fabric stage to produce bulky yarns or bulky woven or knitted fabrics.

As a conventional method for obtaining shrinkable polyester fibers, a method is well known in which a copolyester obtained by copolymerizing polyethylene terephthalate with a third component is used and yarn is spun under specific conditions to obtain shrinkable fibers.

However, in conventionally known shrinkable fibers obtained using copolyester copolymerized with the third component, most of the shrinkage occurs during submersion treatment or dyeing, and the shrinkage rate is not high enough or the shrinkage is not high enough. Even if the ratio is sufficiently high, there is a drawback that sufficient bulkiness cannot be obtained because the fibers that have previously shrunk are elongated due to the influence of the process tension in the higher processing stage after dyeing.

In order to eliminate this drawback of insufficient bulkiness, ■ Japanese Patent Application Laid-Open No. 46-6458, % No. 49-72418 reduces the shrinkage rate in hot water and increases the shrinkage rate in hot air. In JP-A-48-18518, the boiling water shrinkage rate measured without load is 10% or more, and the shrinkage rate in hot air at 180°C measured without load after boiling water treatment is 1.
Methods have been proposed to make it 0% or more.

However, by any of these methods, it is difficult to obtain sufficient shrinkage and sufficient bulk required for the final product.

For example, in method (2) above, the shrinkage rate in hot water is reduced and the shrinkage rate in hot air is increased, but in order to reduce the shrinkage rate in hot water, the resulting total shrinkage rate is The problem is that it does not become large.

In addition, in the method (2) above, each shrinkage rate value is a value measured under no load, and in the actual process, a considerable amount of tension is applied, so sufficient shrinkage does not occur. No.

Furthermore, this method has a fatal flaw in that the cost increases due to the use of alkyl-substituted aromatic dicarboxylic acids.

The object of the present invention is to eliminate the disadvantages of the high shrinkage copolyester fibers obtained by the above-mentioned known techniques, and to produce copolyester fibers that have sufficient shrinkage to exhibit the bulkiness required as a final product. The object of the present invention is to provide a copolyester fiber having a high shrinkage rate in hot air and a high shrinkage rate in hot air after shrinking in hot water at 100°C.

Another object of the present invention is to provide a method for producing the above-mentioned highly shrinkable copolyester fibers with good productivity and at low cost.

That is, the first invention of the present invention provides 2,2-bis (4'-
β-hydroxyethoxyphenyl)propane from 2 to 12
It is made of copolyester fibers copolymerized in mol%, and the shrinkage rate (A Sw ) in hot water of the fibers is 8 to 2 at 100°C.
0%, 13-26% at 120℃, shrinkage rate in hot air after shrinking in 100℃ hot water (, (Sd) is 3-10% at 160℃, 5 at 180℃ ~13%, 200
It is a highly shrinkable copolyester fiber having a shrinkage stress of 7 to 16% at 100°C and a shrinkage stress of 0.15 f/d or more when measured in hot water at 100°C.

The first feature of the highly shrinkable copolyester fiber of the present invention is that the shrinkage rate (lSw) in hot water (described later) is 8 to 20% at 100°C, preferably 10 to 18%, and 13 to 18% at 120°C.
26% preferably in the range of 15-23%, and the shrinkage stress measured in hot water at 100°C is 0.1.5 y
/d or more.

If the JSw is less than 8% at 100°C and less than 13% at 120°C, the fiber is made into a blended yarn with low shrinkage fiber, and after forming this into a knitted fabric, it is soaked in hot water at 100°C or 120°C. Even if the material is put into a container and processed, sufficient shrinkage does not occur, and the bulkiness is therefore unsatisfactory.

On the other hand, those whose ASw exceeds 20% at 100℃, 120
If it exceeds 26% at ℃, the quality of the thread deteriorates significantly, and after shrinking in hot water at 100℃ or 120℃, hot air
This is undesirable because shrinkage is reduced when treated at 60° C., 180° C. or 200° C., or fibers shrunk by hot water treatment are elongated by hot air treatment.

The contraction rate in hot water (lSw) described above is calculated by the load 2077
A fiber (single yarn) with a length of 1&/d was immediately put into hot water, and the shrinkage length was measured after 10 minutes and calculated as a percentage of the original yarn length.

The second feature of the highly shrinkable copolyester fiber of the present invention is that the shrinkage rate (JSd) in hot air after shrinking in 100°C hot water is 3 to 10% at 160°C, 180% It is to have a value within the range of 5 to 13% at ℃ and 7 to 16% at 200℃.

, (Sd is 3% at 160℃, 5% at 180℃, 200℃
If the fiber is less than 7%, even if the fiber is made into a blended yarn with low-shrinkage fiber and this is formed into a woven or knitted fabric and then treated with hot air at the above temperature, the shrinkage will not be sufficient and the bulk will be poor. It becomes insufficient.

On the other hand, (Sd is 10% at 1-60℃, 13% at 180℃
If the value exceeds 16% at 200° C., the shrinkage due to hot air treatment will be too large and the quality of the yarn will deteriorate significantly, which is undesirable.

As mentioned above.

(Sd is a fiber (single yarn) with a load of 20 cm/d.
The fibers were immediately placed in a hot air oven adjusted to temperatures of 60°C, 180°C, and 200°C, and the shrinkage length was measured after 10 minutes and calculated as a percentage of the yarn length.

In addition, the shrinkage stress affects the ease with which yarns and knitted fabrics shrink under restraint, so the higher the shrinkage stress, the more likely they are to contract even under restraint.

In order to make the yarn or woven or knitted fabric sufficiently bulky and to prevent the formation of cores that are likely to occur due to shrinkage fibers, the preferred shrinkage stress range is 0.16 to 0.40 f/d, and the preferred length is L<Gi.
O, 1.7 to 0.35 f/d.

The highly shrinkable fiber of the present invention has a shrinkage stress of O,1,5' when measured in hot water at 100°C. /d or more, the yarn or woven or knitted fabric made of the fibers will sufficiently shrink even under restraint.

In this case, if the shrinkage stress of the fibers measured in 100° C. hot water is less than 0.15 P/d, sufficient shrinkage will not occur in the constrained yarn or woven or knitted fabric.

The shrinkage stress is determined by placing the fiber, which is kept at a constant length by attaching the other end to a strain gauge and fixing the other end, into a hot water bath at 100°C, and recording the shrinkage stress that occurs on a recorder, and then calculates the maximum value. ('?/d) is calculated.

The copolyester constituting the highly shrinkable copolyester fiber of the present invention is polyethylene terephthalate copolymerized with 2 to 12 mol% of 2,2-bis(4'-β-hydroxyethoxyphenyl)furopane.

In this case, in addition to 2,2-bis(4'-β-hydroxyethoxyphenyl)propane, the other quaternary component is 10 mol%.
They may be copolymerized within a range not exceeding .

Examples of such a fourth component include difunctional carboxylic acids such as isophthalic acid, adipic acid, sebacic acid, and naphthalene dicarboxylic acid, trinotylene glycol, diethylene glycol, polyethylene glycol, and 4-cyclohexane dimetatool. The following diol compounds are mentioned.

In short, 2,2-bis(4'-β-hydroxyethoxyphenyl)furopane should be at least 2 mol%"-1, preferably 5 to 10%.
It is necessary to copolymerize mol%.

If the amount of copolymerized 2,2-bis(4'-β-hydroxyethoxyphenyl)furopane is less than 2 mol%, the desired large shrinkage performance cannot be obtained, and if it exceeds 12 mol%, sufficient thread quality cannot be obtained. Hateful.

Such copolyesters can be made by any method.

For example, terephthalic acid dimethyl ester and 2,2-bis(4'-β-hydroxyethoxyphenyl)furopane are transesterified with ethylene glycol, or terephthalic acid and 2,2-bis(4'-β-hydroxyethoxyphenyl)furopane are transesterified. It is produced by a first reaction in which ethoxyphenylfuropane and ethylene glycol are directly esterified to produce a low polymer thereof, and a second reaction in which this reaction product is polymerized.

Any known catalyst is used in the first and second stage reactions, and stabilizers such as phosphoric acid, phosphorous acid, trimethyl phosphate, triphenyl phosphite, and other additives are added as necessary. It may also be added.

In producing the copolyester, a monofunctional compound such as benzoylbenzoic acid, benzyloxybenzoic acid, methoxypolyethylene glycol, or an ester-forming derivative thereof may be copolymerized at the terminal end.

Furthermore, a trifunctional compound such as glycerin, trimellitic acid, pentaerythritol, trimesic acid or an ester-forming derivative thereof, or one of more polyfunctional compounds.
The species or species may be copolymerized in an amount not exceeding 10 mole percent, as described above.

The second invention of the present invention, that is, the method for producing the above-mentioned high shrinkage copolyester fiber, is based on 2.2 bis (4'-β
-hydroxyethoxyphenyl) 7” lopane from 2 to 12
The copolyester undrawn yarn copolymerized with mol% was heated at 75°C.
at a temperature of 75 to 95% of the cutting ratio of the undrawn yarn.
This is a method of stretching at a magnification of , and then drying at a temperature lower than the stretching temperature.

The characteristics of the method for producing such a highly shrinkable copolyester fiber will be described below.

The relationship between the shrinkage rate of a drawn yarn in 1.00°C hot water and the draw ratio for ordinary polyester is as follows: ■ Region A where the shrinkage ratio increases as the draw ratio increases as the draw ratio increases gradually from O.
, ■ Area B where the shrinkage rate decreases from the maximum value, and Area C where the shrinkage rate reaches the minimum value and then increases slowly or changes to a saturated value.
It can be divided into

However, the characteristics of the method for producing high-shrinkage copolyester fibers include a stretching temperature of 75°C or higher, more preferably 80 to 95°C, and a cutting ratio of undrawn yarn of 75 to 95°C.
A stretching ratio of 95%, more preferably 80 to 90% is employed, and stretching is performed in the above-mentioned region C.

(The obtained drawn yarn has a birefringence of 120×10-” or more and a density of 1.365 or more.) If the drawing temperature is less than 75°C, region C will appear even if the drawing ratio is increased to a ratio at which the undrawn thread is cut. Even if the shrinkage rate of the resulting drawn yarn in hot water is high, the drying shrinkage rate after hot water shrinkage (Hanawa) or in some cases, the hot water-shrinked fibers may not be able to withstand subsequent dry heat treatment. Extend with (
The desired shrinkage characteristics cannot be obtained because the material stretches (elongates).

Another feature of the highly shrinkable polyester fiber manufacturing method is that the drying temperature after stretching is lower than the stretching temperature, more preferably 5 to 35°C lower than the stretching temperature.

If the drying temperature is higher than the stretching temperature, the shrinkage rate at each temperature will decrease, making it impossible to obtain the desired shrinkage characteristics.

The high-shrinkage copolyester fiber of the present invention has a characteristic that the bulkiness due to the shrinkage generated in the dyeing process is added to the bulkiness due to the shrinkage generated in the finishing process, and as a result, it has an extremely uniform and good quality. It is useful for obtaining bulky woven or knitted fabrics.

An example of manufacturing a bulky woven or knitted fabric using the high shrinkage fiber of the present invention will be described.

First, the high shrinkage fibers of the present invention are processed through a carding process.
40%, 70-60% non-shrink or low shrink fibers
They are mixed and subjected to a spinning process to form a blended yarn.

When a woven or knitted fabric is made from the blended yarn by a conventional method and then subjected to carrier dyeing at 100°C or high-pressure dyeing at 120°C, the woven or knitted fabric shrinks significantly and becomes bulky.

Furthermore, when the woven or knitted fabric is subjected to a finishing treatment in hot air at 180°C, for example, shrinkage occurs and bulkiness increases.

Another feature of the high shrinkage fiber of the present invention is that the JSw of the fiber obtained by conventionally known methods decreases by 20 to 30% compared to the initial ASw when left at 40°C for one month. (
Sw hardly changes over time.

Furthermore, another feature of the high shrinkage fiber of the present invention is that 2.2 bis (4'-β) is used as a modified component of polyethylene terephthalate.
-hydroxyethoxyphenyl)propane is used.

As a result, compared to other modified components, it is possible to obtain a high shrinkage rate with a low copolymerization rate, and it is advantageous in that there is little deterioration of yarn quality and little increase in cost.

In addition to polyester fibers, other synthetic fibers or natural fibers may be used as the low-shrinkage fibers used in combination with the high-shrinkage fibers of the present invention.

Further, when polyester fiber is used as the low shrinkage fiber, it is preferable to use anti-pilling fiber.

Next, the present invention will be specifically explained with reference to Examples.

Example 1 Modified polyethylene terephthalate copolymerized with 8 mol % of 2.2-bis(4'-β-hydroxyethoxyphenyl)propane was polymerized by a conventional method to form chips with an intrinsic viscosity of 0.50.

After drying this chip under reduced pressure at 150°C, 0.23 m
1200 m by discharging from a nozzle with mφ-300 hole
/mlyr and converged to form a 500,000 denier tow.

This tow was subjected to liquid bath stretching at a stretching temperature of 85°C and a stretching ratio of 3.65 (85% of the cutting ratio), and then mechanically crimped to 85°C.
Hot air drying was performed at 0° C. for 20 minutes.

Cut this tow using the usual method to an average of 1.02mm.
-L, a stable fiber with a single yarn fineness of 3 denier.

The performance of the obtained fibers was as shown in Table 1.

Comparative Example 1 The same unstretched tow as in Example 1 was subjected to liquid bath stretching at a stretching temperature of 73°C and a stretching ratio of 315 times (75% of the cutting ratio), and then mechanically crimped and stretched at 60°C for 20 Hot air drying was performed for a minute.

This tow was cut into a stable fiber having an average length of 102 by a conventional method.

The performance of the obtained fibers was as shown in Table 2.

As is clear from Table 2, when the stretching temperature and stretching ratio are low, l
Sw 100 becomes high, but on the other hand, Sd 180 becomes negative (elongation) after 00°C hot water treatment.

Example 2 Stable fiber with single yarn fineness of 3 denier obtained in Example 1 and 100°C hot water shrinkage rate of 0% obtained by another method
Single yarn fineness 3 with a shrinkage rate of 2% in hot air at 180℃
Stagle fibers made of polyethylene terephthalate having a denier and a cut length of 89 mm were mixed at a ratio of 60% of the former and 40% of the latter, and spun yarn of No. 7 and No. 48 was prepared by a conventional method.

When this spun yarn was treated in hot water at 1.00°C, the bulk increased significantly.

Subsequently, this was treated in hot air at 180°C, resulting in a spun yarn with increased bulk and good texture.

Comparative Example 2 Processing was carried out under the same conditions as in Example 1 except that the drying temperature after stretching was 95°C, and the single yarn fineness was 3 denier and the average fiber length was 102.
It was made into a stable fiber of m11L.

The properties of the obtained fibers were as shown in Table 3 below.

Claims (1)

[Scope of Claims] Consisting of a Shitaco polyester fiber copolymerized with 2 to 2 mol% of 12,2-bis(4'-β-hydroxyethoxyphenyl)furopane, the fiber has a shrinkage rate of 100 in hot water. ℃
8-20% at 120℃, 13-26% at 120℃, 100%
The shrinkage rate in hot air after shrinking in hot water at ℃ is 16
3 to 10% at 0°C, 5 to 13% at 180°C, 7 to 16% at 200°C, and the shrinkage stress measured in hot water at 100°C is 0.15 f/d or more. Features high shrinkage copolyester fiber. An undrawn copolyester yarn copolymerized with 2 to 12 mol% of 22,2-bis(4'-β-hydroxyethoxyphenyl)furopane was heated at 75°C or higher and at a cutting ratio of 75 to 95 of the undrawn yarn. %, and then drying at a temperature lower than the stretching temperature.