JPS60162811A - Fine unevenness part-forming polyester fiber - Google Patents

Abstract

PURPOSE:To obtain the titled fibers having improved coloring properties, feeling and water absorbing properties of fine unevennesses on the fiber surface, by melt incorporating a polyester such as polyethylene terephthalate with a specific polyester, melt extruding the resultant mixture, and eluting the melt extruded polyester filament yarn. CONSTITUTION:(B) A polyester obtained from >=80mol% terephthalic acid (derivative) and 3-15mol% 5-(alkali metal) sulfoisophthalate (derivative) as a dicarboxylic acid component and >=80mol% ethyleneglycol, 0.1-20% polyalkylene based glycol having 160-4,000 average molecular weight and 1-10mol% diethylene glycol as a glycol component in the respective copolymerization ratios satisfying the following relation of melting point depression; alpha(a+b+c)-2.4alpha(a+b+ c) [a is the copolymerization ratio of the 5-(alkai metal) sulfoisophthalate (derivative); b is the copolymerization ratio of the polyoxyalkylene glycol; c is the copolymerization ratio of the ethylene glycol; alpha is the weight ratio B/(A+B) between the polyester (B) and the total of the polyester (B) and a polyester (A)] is melt incorporated with the polyester (A) consisting essentially of an alkylene terephthalate as a main repeating component at 0.05-0.50 mixing weight ratio (alpha).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to polyester fibers capable of forming fine quarters on the fiber surface. It also relates to polyester fibers that can have improved color development, texture, and water absorption.

Aromatic polyesters represented by polyethylene terephthalate are widely used in fibers, films, and other molded products because of their excellent mechanical performance, light resistance, and chemical resistance. However, aromatic polyester fibers
Compared to other fibers such as acetate, rayon, wool, and silk, it has the disadvantage that it is difficult to obtain deep color effects because the fiber surface is smooth, and it also has the disadvantages of having a slimy feel and lack of water absorption. .

Conventionally, methods for improving the coloring properties of polyester fibers include forming a thin film of a component with a refractive index smaller than that of polyester fibers on the fiber surface to lower the reflectance, or adding inert fine particles to the fibers after spinning. A known method is to apply elution treatment to impart fine gate protrusions to the fiber surface to increase the efficiency with which light enters the fiber. However, the former has the disadvantage of poor durability against bending and peels off when subjected to massaging action, while the latter, although improved in color development, has the disadvantage of increasing back pressure during melt spinning and causing wear of the running yarn guide. It had problems such as insufficient dyeability and low water absorption.

The inventors of the present invention have made intensive studies to eliminate the above-mentioned drawbacks, form fine concave portions on the fiber surface to create a deep color, and to obtain a polyester fiber with improved texture and water absorption. The present invention has now been completed. That is, the present invention comprises a polyester (4) containing alkylene terephthalate as a main recurring component, 80 mol or more of terephthalic acid or its ester-forming derivative as a dicarboxylic acid component, and 5-(alkali gold 14) sulfoisophthalic acid or its ester-forming component. polyester (H ) and (A) 10) = 0.05 to 0.50 (weight ratio), obtained by melt-mixing and spinning, and having a melting point that satisfies the following formula (I). It is a fine four-part engraving polyester fiber.

MP(A-α(a+b+c)≧MP≧MP(A)-2,
4α(m+b+e) (I) The main acid component of the polyester (A) used in the present invention is terephthalic acid or its ester-forming derivative, and the main glycol component is ethylene glycol, but the acid component is 20 mol%. The following oxalic acid, malonic acid, maleic acid, glutaric acid,
Aliphatic dicarboxylic acids such as adipic acid, sebacic acid, 1,4-cyclohenosandicarboxylic acid, 2,5-norbornanedicarboxylic acid, or their ester-forming derivatives, phthalic acid, isophthalic acid, 5-( Aromatic dicarboxylic acids such as alkali metal) sulfoisophthalic acid, siphenic acid, 1,4-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 1,2-bis(phenoxy)ethane-P, P'-dicarboxylic acid, or These ester-forming derivatives can be included as copolymerization components. It can also contain 20 mol% or less of the acid component of an oxycarboxylic acid such as p-(2-hydroxyethoxy)benzoic acid or an ester-forming derivative thereof.

Further, as glycol components, propylene glycol, diethylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexane dimetatool, 20 mol% or less,
1.10-decamethylene glycol, 4.4'-dihydroxybisphenol, 1,4-bis(β-hydroxyethoxy)benzene, 2゜5-naphthalene diol, glycol obtained by adding ethylene oxide to these glycols, polyethylene glycol, etc. can be included.

Also in the polyester (B) of the present invention, the main acid component is prephthalic acid or its ester-forming derivative,
It also contains 3 to 15 mol% of 5-(alkali metal) sulfoisophthalic acid or its ester-forming derivative. 5-
(Alkali metal) Examples of the alkali metal of sulfoisophthalic acid or its derivatives include lithium, sodium, potassium, and rubidium, but sodium is the most common. In addition, aliphatic and/or aromatic dicarboxylic acids or ester-forming derivatives thereof, such as those exemplified as the base component of polyester (4), can be included within a range that does not impair the effects of the present invention. The glycol components of the polyester include 80 mol% or more of ethylene glycol and 0.1 to 20 mol% of polyoxyalkylene alcohol with an average molecular weight of 160 to 4,000.
and diethylene glycol 1 to 10 mol%,
Among these, polyoxyalkylene glycols include
polyethylene glycol, polypropylene glycol,
Random or block copolymer of ethylene oxide and propylene oxide, polytetramethylene glycol, block copolymer obtained by adding ethylene oxide to polytetramethylene glycol, the following general formula (2)
Examples include glycols shown in .

no+cl HJ o+mR-0(-Cj&j O9H
(10 In general formula (6), R is a divalent aliphatic hydrocarbon group or aromatic hydrocarbon group having 4 to 20 carbon atoms. Specific examples include +CHz+i, +CH2+s, +CH*+1
o %H3 Ha CH3 Q CH.

Q.CH.

Examples include aromatic hydrocarbon groups.

In the general formula (6), 11j is the same or different integer and is 2 to 4, and msn is the same or different integer of 0 or more and 2≦m+n≦15. If the molecular weight of the polyoxyalkylene glycol is less than 160, it is not preferable because distillation becomes 5 during polyester polymerization. Molecular weight is 40
When it exceeds 00, reactivity during polyester synthesis decreases.

Among polyoxyalkylene glycols, general formula (6
) is a particularly preferable glycol from the viewpoint of light resistance of the fiber obtained by mixing polyester (4) and polyester (B), and 11j are both 2 and 3≦m≦n≦ 10 is more preferable. Diethylene glycol may be added to the reaction system together with other glycols during the synthesis of the polyester (provided), or it may not be added and the amount produced as a by-product during the reaction may be controlled by, for example, adding an alkaline compound. In addition to the above-mentioned glycols, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, 4,4'-dihydroxy may be used as glycols for polyester (B) within a range that does not impair the effects of the present invention. Bisphenol, 1,4-bis(β-hydroxyethoxy)benzene, 2,5-s7talediol, etc. can also be used. 1. Method for producing polyester (4) and ω) using each of the above raw materials is not particularly limited, and can be carried out according to a normal polyester manufacturing method.

In order to obtain the fine four parts of the present invention, it is preferable to select a mixing method and mixing conditions depending on the type of polyester η) and proviso). (2) method of mixing polyester (B
) (or polyester French)) to polyester (A)
(or polyester ω)), melt-mixes the mixture, and supplies it to the spinning process as it is or in the form of chips; (3)
Examples include a method in which polyester (A) and polyester (A) are mixed in a molten state, mixed using a static mixer, an extrusion screw, etc., and fed as is or in the form of chips to the spinning process.

In producing polyester fibers by melt spinning a mixture of polyester (A) and polyester (B), basically any conventional melt spinning method for polyester fibers may be employed.

What should be noted is that during the process of melt mixing and spinning polyester (4) and polyester (B), a transesterification reaction occurs between the polyester and polyester (B). This transesterification reaction must be carried out so that the melting point of the obtained fiber as determined by a differential scanning calorimeter satisfies the equation (1)'Jk. If the transesterification reaction is low, many fine grooves will be formed on the fiber surface after the fiber is eluted with an alkaline aqueous solution. The quality of the textile product becomes unstable due to a significant change in the ester exchange reaction.As the transesterification reaction progresses, fine depressions are formed on the surface of the eluted fibers. When MP(3)-2,4α(a+b+) is lower than MP(3)-2,4α(a+b+.), the fine recesses formed on the fiber surface after elution treatment become unclear, or even no recesses are observed at all. By controlling the esterification reaction so that the melting point is as shown by the formula (2) of the invention, it is possible to obtain stable and evenly distributed fine particles on the fiber surface after elution treatment, which is a suitable method. This provides color development, texture, and moisture absorption.In order to perform an appropriate transesterification reaction, the kneading temperature, time, and shape of the extruder for kneading must be selected depending on the type of polyester. is necessary.

The mixing ratio of polyester (4) and polyester [F]) is as follows:
The fine recesses on the fiber surface obtained by elution treatment are unclear, and the depth of color, change in texture, water absorption, etc. are insufficient. In addition, if the amount is too large, the strength and light resistance of the fibers will be markedly reduced by treatment with the alkaline aqueous solution, so ω)/(to) solder) needs to be in the range of 0.05 to 0.50 in terms of weight ratio.

After the polyester fiber obtained by the above method is subjected to drawing heat treatment or false twisting as necessary, or after being made into a fabric, it can be easily treated with an aqueous solution of an alkaline compound to form fine depressions on the fiber surface. can be formed. Examples of the alkaline compounds used here include sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, sodium carbonate, and potassium carbonate. Among these, sodium hydroxide and potassium hydroxide are particularly preferred.

The concentration of the aqueous solution of the alkali-11 compound varies depending on the type of alkali compound, processing conditions, etc., but is usually 0.01.
The range from 0.1 to 4% by weight is preferred, especially from 0.1 to 4% by weight. The treatment temperature is preferably in the range of room temperature to 100°C, and the treatment time is usually in the range of 1 minute to 4 hours. Further, it is appropriate that the amount to be eluted and removed by treatment with this aqueous alkali compound solution is in the range of 2 to 30% by weight. By treating with an alkaline aqueous solution in this way, the above-mentioned fine recesses can be easily formed. The short axis of the recess to be formed is 0.05 to 1.0 microns, and the long axis is 0.1 to 3.
0 micron is common. Note that the cross-sectional form of the fiber may be solid, hollow, irregularly shaped solid, or irregularly hollow.

The fibers having fine concave portions obtained by the above-mentioned treatment of the polyester fiber of the present invention consisting of the #4 composition exhibit excellent water absorbency, and when dyed, have deep color development and vividness. Furthermore, it has a texture similar to natural fibers without a slimy feel.

Example 1. Comparative Example 1.2 1000 parts of dimethyl terephthalate, 133 parts of dimethyl 5-sodium isophthalate (8.0 mol% based on the total acid components), 735 parts of ethylene glycol, a glycol obtained by adding 6 moles of ethylene oxide to neopentyl glycol 170 parts (same, 8.0 mol%) were transesterified at elevated temperature from 150°C to 210°C using zinc acetate dihydrate as a catalyst, and then at 275°C using antimony trioxide as a catalyst. The polycondensation reaction was carried out under a reduced pressure of 0.1 u + Hf, and the content of diethylene glycol was 6.7 molti relative to the total glycol component, and the reduced viscosity η8p/c was 0.
．． 413 polyester (8) was obtained. This polyester (8110 parts) and 90 parts of polyethylene terephthalate (polyester (A)) having an intrinsic viscosity of 0.630 are mixed and melt-extruded and spun at a tip temperature of 300°C using a screw with two rows of pins in the metal ring area. Hit, next (a).

Three mixed methods (b) and (c) were adopted.

(a) The polyester (4) was charged from the inlet hopper of the extrusion spinning machine, and the polyester color (above) was fed in a fixed amount through another screw extruder to the leading edge of the screw of the extrusion spinning machine [7].

(b) Polyester (N and polyester Q3)'t
The chips were blended and introduced through the inlet hopper of the extrusion spinning machine.

(c) Polyester IA) and polyester () were stirred and mixed in a molten state for 120 minutes in a polymerization vessel preheated to 280°C to form chips, which were then introduced from the inlet hopper of an extrusion spinning machine.

The melt spinning carried out in this manner was carried out smoothly, and the increase in nozzle back pressure was less than 0.1 Kp/ad·hour in all cases. The obtained undrawn yarn was drawn according to a conventional method to obtain long fibers of 75 denier and 36 filaments. This was interlock knitted and scoured (treated under boiling conditions with a 2.10 f/l sodium hydroxide aqueous solution) to obtain knitted fabrics each having a weight loss of 20 strands.

The following evaluations were performed on each of the above-mentioned fibers or silk fabrics obtained by employing the mixing methods (a) to (c), respectively.

The results are shown in Table 1. Moreover, the surface condition of each fiber after alkali weight loss is shown in FIGS. 1 to 3. 1 to 3 are Comparative Example 1. Example 2. 2 is an electron micrograph of the surface of the fiber obtained in Comparative Example 2, magnified 5000 times.

Evaluation method (1) Melting point: 1 olIv of undrawn yarn without oil was measured using a differential scanning calorimeter at a heating rate of 20° C./min, and the melting point was measured at the top of the main endothermic peak.

(2) Dyeing rate: knitted fabric metal that has been subjected to weight loss treatment, 4% OW water dispersion of Varanyl Brilliant Red 5BEL (dispersible dye of BASF), bath ratio 1:100, 90 minutes under boiling conditions. Staining 1. Thereafter, the dye exhaustion rate was determined by colorimetry of the remaining liquid.

(3) Bathochromic property: The knitted fabric that has been subjected to weight loss treatment is coated with 20% of Diamond
%owf aqueous dispersion at a bath ratio of 1:100. After dyeing for 60 minutes at 130°C, reduction washing was performed. Then, the L value of the dried silk fabric was measured using a Hunter type color difference meter.
The lower the value, the deeper the color tone.

(4) Water droplet absorption rate - J
The water droplet absorption rate was measured using the ISL-101,8A method.

A low value indicates high water absorption.

(5) Dry-Touch The knitted fabric subjected to the double weight loss treatment was evaluated by touching it with the hands.

Table 1 Comparative Example 2 ^ 254J 84 14.4 150 Note: Polyester (A) temperature is 261.0℃ 1st to 3rd
As is clear from the figure, the surface of the fiber obtained in Example 1 has fine and uniform depressions12, exhibits excellent dyeing rate, deep color and water absorption, and has a dry touch texture. [7Th
It turns out that On the other hand, it can be seen that in Comparative Example 1, the grooves are fine, and in Comparative Example 2, the recesses are unclear.

Comparative Example 3 1000 parts of terephthal dimethyl, 7 parts of ethylene glycol
When synthesizing polyester from 00 parts according to the polyester synthesis method of Example 1, at the end of the transesterification reaction, 30 parts'1 of fine silica powder with an average particle size of 40 mp was dispersed in 150 parts of ethylene glycol. A solid polyester containing finely powdered silica having an intrinsic viscosity of 0.62 was obtained.

This was spun using the same extrusion spinning machine as in Example 1 to form fibers. The nozzle back pressure increase at this time was 0.4 Kp/6 d@hour, which is a higher value than in Example 1.The obtained undrawn yarn was knitted into a 75 denier 36 filament using KL7 in the same manner as in Example 1. A friend who processes and evaluates weight loss. The bathochromic property and dry touch of this material were similar to those of the knitted fabric of Example 1, but the dyeing rate was as low as 42 cm, and the water droplet absorption speed was as high as 180 seconds. It was found that the properties were significantly inferior to that of the silk fabric of Example 10.

[Brief explanation of drawings]

1 to 3 are Comparative Example 1. Example 2. This is an electron micrograph of the surface of the fiber obtained in Comparative Example 2, magnified 5000 times. Patent applicant: Toyobo Co., Ltd.

Claims (1)

[Scope of Claims] Polyester (A) containing alkylene terephthalate as a main recurring component, 80 mol% or more of terephthalic acid or its ester-forming derivative as a dicarboxylic acid component, and 5-(alkali metal) sulfoisophthalic acid or its ester Obtained from 3 to 15 mol% of a forming derivative and 80 mol% or more of ethylene glycol as a glycol component, 0.1 to 20% of a polyoxyalkylene glycol with an average content of -T"ff of 1160 to 4000, and 1 to 10 mol% of diethylene glycol. It is obtained by melt-mixing and spinning polyester (B) so that ω)/(A)+(g))=O,OS~0.50 (weight ratio), and has the following formula (I). Fine depression-forming polyester fiber characterized by having a satisfactory melting point. MP(a)-α(a+b+c)≧MP≧MP(a>-2
,4α(a+b+c)(I)