JP2836892B2 - Durable hydrophilic / antistatic fabric and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial application field) The present invention is made hydrophilic and has excellent antistatic properties, and furthermore, its hydrophilicity and antistatic properties have excellent durability. The present invention relates to a fabric having excellent performance, that is, a fibrous structure.

(Prior Art) Polyester fibers are excellent in chemical and physical properties and can be expected to grow in the future due to the recent differentiation and expansion of applications. However, since polyester fibers have a surface gloss unique to synthetic fibers, there is a drawback that when dyed, it is difficult to obtain deeper color and deeper color than natural fibers. In addition, since polyester fibers are hydrophobic, they also have a disadvantage that they do not have the properties of natural fibers such as water absorption, moisture absorption, and antistatic properties.

Hitherto, many methods for imparting hydrophilicity and antistatic property to synthetic fibers such as polyester have been proposed. These can be roughly divided into two methods. One is a method of modifying the fiber itself, specifically, a method of adding a hydrophilic substance, or an antistatic substance, or both to the polymer constituting the fiber, an antistatic polymer to the core, There is a method of forming a core-sheath type composite fiber by using ordinary polyester for the sheath portion.

Fibers obtained by this method are hydrophilic or antistatic,
The hydrophilic antistatic property is semi-permanent, but this method requires that a sufficient amount of a hydrophilic substance or an antistatic substance be added to the polymer to obtain the antistatic property and hydrophilicity. There are drawbacks such as poor physical properties and difficulty in spinning, or poor light resistance. Among them, a particular problem is that the hydrophilicity and antistatic substance leak in the alkali weight reduction step at the time of post-processing, resulting in a decrease in hydrophilic antistatic performance and a decrease in darkness. In the case of the core-sheath type composite fiber, it has antistatic properties but lacks hydrophilicity. The second is a method of applying a hydrophilic substance or an antistatic substance or both by post-processing after forming a woven or knitted fabric. However, although these methods can impart initial performance, they have the drawback that washing durability is extremely poor, and there is a problem that water-dried portions of the woven or knitted fabric remain as water spots (water spots). May be. There is also a method of performing low-temperature plasma treatment after post-processing. In this case, the washing durability is improved depending on the amount of the hydrophilic substance and the antistatic substance and the mixing ratio of the two in the case where both are used. I can't do anything I can.
Another problem is that the water spot remains. Other methods include grafting a vinyl compound such as acrylic acid or methacrylic acid with a polyester fiber to impart hydrophilicity. However, these methods have disadvantages such as poor light fastness, low monomer efficiency and high cost.

(Problems to be Solved by the Invention) The present invention is to provide a polyester fabric with a semi-permanent hydrophilic / permanent antistatic property and obtain a polyester fabric having washing durability.

(Means for Solving the Problems) That is, the present invention comprises, as a core component, a polyester-based polymer containing 1 to 7% by weight of a polyalkylene glycol compound and 0.1 to 5% by weight of sodium alkylbenzene sulfonate, and substantially comprises the above compound. The present invention relates to a fabric comprising a core-sheath type conjugate fiber having a polyester polymer as a sheath component, the fabric comprising a binder (A) comprising a compound having the following groups (1) and (2) and a polyester ether: When the total amount of (A) and (B) is 2.6% by weight or less (based on the weight of the fabric), (A) is 0.3% by weight or more and 1.0% or more.
% By weight (based on fabric weight) and (A) / (B) is 1 /
Cloth characterized by being attached in an amount ratio satisfying 3 to 1/1 (weight ratio) (However, a and b are integers of 0 to 60, and both a and b are 0.
Never be. ), And as a production method, a polyester-based polymer containing 1 to 7% by weight of a polyalkylene glycol compound and 0.1 to 5% by weight of sodium alkylbenzene sulfonate as a core component, and a polyester-based polymer substantially free of the above compound. A fixing agent (A ') comprising a compound having the following groups (1) and (2) and a vinyl group at a terminal and a polyester ether-based hydrophilizing agent (B) are added to a fabric containing a core-sheath type composite fiber as a sheath component.
Is not more than 2.6% by weight (based on fabric weight) in the total amount of (A ') and (B), (A') is not less than 0.3% by weight and not more than 1.0% by weight (based on fabric weight), and (A ') / (B) is 1/3 to 1/1
(Weight ratio), and then reacting the terminal vinyl group.

(However, a and b are integers of 0 to 60, and both a and b are 0.
Never be. The polyester-based polymer referred to in the present invention is an aromatic dicarboxylic acid such as terephthalic acid, naphthalene-2,6-dicarboxylic acid, an aliphatic dicarboxylic acid such as adipic acid or sebacic acid, or an ester thereof, and ethylene glycol.
It is a product synthesized from a diol compound such as diethylene glycol, 1-4 butanediol, neopentyl glycol, dichlorohexane-1,4-dimethanol. In particular, polyesters in which 80% or more of the repeating structural units are ethylene terephthalate units or butylene terephthalate units are preferred.

In order to impart antistatic properties in the present invention, a polyalkylene glycol compound and sodium alkylbenzene sulfonate (surfactant) are added to the core polymer which becomes the core-sheath fiber at the stage of polymer production or before spinning. I do. The molecular weight of the polyalkylene glycol compound to be added is suitably from 1,000 to 20,000. If the molecular weight is less than 1000, the viscosity is too low and spinning is difficult, and bleeding to the fiber surface is fast. If the molecular weight is more than 20,000, the viscosity is high, so that it is difficult to obtain a material having stable performance due to difficulty in uniform dispersion during spinning.

The addition amount of the polyalkylene glycol compound is 1 to 7 wt.
%. If it is less than 1 wt%, sufficient antistatic properties cannot be obtained. If it exceeds 7% by weight, not only the antistatic property is saturated, but also a cause of trouble during polymerization and spinning.

The polyalkylene glycol compound may be a homopolymer of polyoxyethylene glycol or a polymer obtained by copolymerizing oxyethylene units and oxypropylene units in a random or block manner. However, depending on the composition ratio of oxyethylene units and oxypropylene units, the hydrophilicity with respect to water may decrease, so that
It is preferred that the oxyethylene unit be the main component as long as the object of the present invention is not hindered. Further, as the polyalkylene glycol, a mixture of polyoxyethylene glycol and polyoxyethylene-polyoxypropylene copolymer or a mixture of polyoxyethylene glycol and polyoxypropylene glycol may be used. The terminal of the polyoxyalkylene glycol may be a hydroxyl group or may be blocked with another group.

The addition amount of sodium alkylbenzene sulfonate is 0.1 to 5
wt%. If it is less than 0.1 wt%, sufficient antistatic performance cannot be imparted, and the polyalkylene glycol compound does not serve as an auxiliary. If it exceeds 5% by weight, the spinnability becomes poor as in the case of adding 7% by weight of polyalkylene glycol.

As alkyl benzene sulfonate sodium, a general formula (Where R is an alkyl group having 8 or more carbon atoms), and a preferred specific compound is sodium dodecylbenzenesulfonate.

The core-sheath conversion (weight ratio) of the core-sheath type composite fiber is preferably core / sheath = 1/4 to 1/1. When the ratio of the core portion is higher than this range, the polyalkylene glycol compound or sodium alkylbenzene sulfonate contained in the core portion is eluted when the alkali weight is reduced due to eccentricity of the core-sheath type composite fiber, and the performance of the core component is reduced. There is a problem that the color of the dyed cloth becomes brownish due to cavities due to elution. When the ratio of the sheath is higher than the above range, elution of the components of the core can be prevented, but the antistatic performance becomes insufficient.

There are various types of core-sheath type conjugate fibers, such as a single-core sheath, a multi-core sheath, and a single-core concentric sheath, an eccentric core-sheath, and the like. . Further, the cross-sectional shape need not be a perfect circle, but may be an ellipse or another irregular shape.

The core-sheath type composite fiber as described above can maintain the antistatic property semipermanently, and almost no leakage of the antistatic agent occurs even in post-processing such as alkali weight reduction. A fabric is formed using at least a part of such a core-sheath type composite fiber. Preferably, 30% or more of the fabric weight is the above-mentioned core-in-sheath type conjugate fiber.

The method of using the core-sheath type composite fiber is not particularly limited, and a warp yarn or a weft yarn of a woven or knitted fabric, or both a warp yarn and a weft yarn may be used. Needless to say, the yarn may be blended, blended, or twisted with other fiber yarns.

In such a fabric, the above-mentioned base (1),
(2) and a fixing agent (A ') comprising a compound having a terminal vinyl group and a polyester ether-based hydrophilizing agent (B). The compound (A) is obtained by reacting the terminal vinyl group of the fixing agent (A '). Used in the present invention. Preferred fixing agent compounds (A ') include compounds represented by the following general formula.

(However, a, b, c, and d are integers of 0 to 60, and may be the same or different. Note that not all of them are 0 at the same time.) It has a high affinity, a bisphenol part that expresses high adhesiveness, an ethylene oxide and propylene oxide part that expresses wettability and antistatic properties, and a methacryl group that enables high polymerization and high crosslinking. Each of these parts has a configuration in which roles are highly divided.

The hydrophilizing agent (B) used in the present invention includes dicarboxylic acid such as terephthalic acid, isophthalic acid, sodium sulfoisophthalate, adipic acid and polyethylene glycol,
It is a linear polyester ether compound obtained by condensation from a polyalkylene glycol such as polypropylene glycol and, if necessary, ethylene glycol, propylene glycol, tetramethylene glycol and the like. As the polyalkylene glycol, those having a molecular weight of 500 to 50,000 are generally used, and polyethylene glycol is generally used. The degree of condensation polymerization is preferably in the range of 1 to 20. An example of such a hydrophilizing agent is SR-10.
Compounds commercially available under the names of 00 (manufactured by Takamatsu Oil & Fats) and Permallow T (manufactured by ICI) are exemplified.

Such a hydrophilizing agent is a polyester resin,
Since it is of the same quality as the polyester fiber, it has a good affinity with the fiber and a good adhesive property.

The adhesion amount of the fixing agent (A) and the hydrophilic agent (B) is not more than 2.6% by weight (based on fabric weight). If it exceeds 2.6% by weight, the hydrophilicity is saturated, the hand becomes hard, and the surface of the woven or knitted fabric tends to slip abnormally.

Also, the ratio of (A) and (B) to be attached [(A) /
(B)] is 1/3 to 1/1 by weight. When the ratio of (A) is higher than this range, the feeling becomes harder,
(B) is wrapped in (A), impairing hydrophilicity.

When the ratio of (A) is less than the above range, it is difficult to protect the hydrophilizing agent, and the initial performance can be imparted, but the washing durability decreases. And (A)
It is necessary to be 0.3% or more and 1% or less (based on fabric weight). If it exceeds 1%, the feel becomes hard and the affinity is insufficient. If it is less than 0.30% by weight, the protection of (B) cannot be performed, resulting in poor washing durability. The roles of (A) and (B) are as follows.

(A) plays an auxiliary role of (B), and in the semipermanent hydrophilicity according to the present invention, (B) greatly contributes to hydrophilicity,
(A), which has an affinity for the polyester having a certain degree of hydrophilicity, is protected (B) by wrapping it appropriately.

As described above, the above-mentioned (A) is obtained by reacting the terminal vinyl group of the fixing agent (A ′). As a means for the reaction, there is also a method of simply performing a heat treatment, but preferably using a low-temperature plasma. This is a method of reacting, whereby it is possible to prevent (A) and (B) from falling off from the fiber surface. Low-temperature plasma is a method in which a gas is introduced under vacuum, a voltage is applied between electrodes using a high-frequency power source under a certain degree of vacuum, and glow discharge is generated.
Non-polymerizable gas (for example, O ₂ , H ₂ , Ar, He,
Co, N ₂ etc.). Among them, oxygen or a gas containing oxygen is more preferable in consideration of imparting a hydrophilic group to the fiber surface to crosslink the resin. Processing vacuum is 0.01 to 10 Torr
The range is preferably 0.1 to 1 Torr in consideration of the processing efficiency.
Is desirable. The processing time is usually from 1 to 300 seconds, but more optimally from 5 to 120 seconds. If it exceeds 120 seconds, the texture of the fabric may be impaired. If the time is less than 1 second, crosslinking of the resin is insufficient and washing durability is poor.

Discharge output power to apply a voltage to 0.1~5W / cm ² C., electrode saw discharge sustained, from the discharge uniformity in electrode width direction 1K
Hz to 13.56 MHz is good. The electrode system is preferably an internal electrode in view of processing efficiency, and the shape of the electrode is preferably a parallel plate, a bar-plate, or the like, but other shapes can be used.
Crosslinking also occurs in heat treatment, but in this case, the degree of crosslinking is considerably smaller than that in low-temperature plasma treatment. To know the degree of crosslinking, dissolve the low-temperature plasma-treated cloth and the heat-treated cloth with trifluoroacetic acid, and remove the amount of insoluble matter. Understand from. It can be determined that the larger the amount of insoluble matter, the higher the degree of crosslinking, and the smaller the amount, the lower the degree of crosslinking.

The mechanism of the semi-permanent hydrophilicity and semi-permanent antistatic property obtained in the present invention is as follows. A woven or knitted fabric is formed by using a core-sheath type composite fiber containing an antistatic agent, and a fixing agent (A ') and a hydrophilic agent (B) are applied to the surface of the woven or knitted fabric. ) To semi-permanently impart hydrophilicity and antistatic properties.

Therefore, the reason why resin falling off due to washing can be suppressed is presumed to be largely related to the following three points. One is that polyalkylene glycol, which is a hydrophilic component in the core of the core-sheath type conjugate fiber, gradually oozes on the fiber surface to improve the adhesiveness with the resin. Second, when the fiber surface is roughened, when the resin is put on the fiber surface, the resin enters into the concave portion and is hardly peeled off. The third reason is that the resin layer is crosslinked by the low-temperature plasma treatment, so that the resin does not easily fall off.

As described above, in the present invention, it is preferable that fine irregularities are provided on the fiber surface. For this purpose, a method of adding inorganic particles to the polymer constituting the sheath component and reducing the alkali is used. Examples of the inorganic particles to be added include silica, alumina, and the like, and the particle diameter is preferably from 10 mμ to 100 mμ. As the particle size increases, the irregularities on the fiber surface become coarse and the color developability deteriorates. When the particle size is small, there is a problem of aggregation,
The spinnability becomes unstable.

The amount of inorganic particles added was 0.3
~ 5 wt% is preferred. If it is less than 0.3 wt%, the fiber surface cannot be sufficiently roughened after the alkali weight loss, so that no color developability can be obtained. If it exceeds 5 wt%, the rough surface structure of the fiber surface after the alkali weight reduction becomes too large, and the color developability deteriorates.
This rough surface structure serves to increase the washing durability of the resin.

When post-processing is performed regardless of resin processing or plasma processing, places that are wet with water dry and become stains (water spots). This is because unreacted monomers remain after processing. In the case of the plasma treatment, the resin may be partially decomposed at the same time as the crosslinking, and the water spot is remarkably exhibited. This can be prevented by providing a water washing step in the final step.

 Hereinafter, the present invention will be described by way of examples.

Example Polyethylene glycol (molecular weight) was used as an antistatic agent in the core.
10000) 5wt%, sodium dodecylbenzenesulfonate (DB
S) 2wt% addition, polyethylene terephthalate (PET),
The sheath is PET or inorganic particles (silica: particle size 50mμ) 2wt
% PET was used, and a core-sheath yarn 50dr / 24f having a core-sheath ratio of 1/1 was used as the warp yarn, and a polyester taffeta using PET50dr / 24f as the weft yarn was produced. This taffeta is descaled, scoured, alkali-reduced, and the woven fabric is dyed black.
E-1300 (Shin-Nakamura Chemical), SR-100 as hydrophilizing agent (B)
0 (Takamatsu oil and fat) Dip-Nip-100 ° C 1 minute Dry-150 ° C 1 minute Cu
Processed with re. After setting the treated cloth in the low-temperature plasma processing apparatus, the internal pressure was reduced to 0.01 Torr, and then N ₂ gas was supplied at 30 C.C./
Min and the internal pressure was maintained at 0.3 Torr. Then 13.56MH
1W / cm ² power using a high frequency power source of
The treatment was carried out for 0 to 120 seconds to react the fixing agent. Through the washing step as the final step, the wicking wicking length, frictional voltage, water spot, hand, and coloring of each washing cycle were evaluated. The results were as shown in Table 1.

In the case of the comparative example, a taffeta using PET or core-sheath antistatic PET as a warp yarn was destained, dyed black after scouring, and fixed to the woven fabric only (A ') or only the hydrophilizing agent (B). Alternatively, various performances (same items as in the example) were evaluated in the case where both were adhered by the same processing as in the example and in the case where a low-temperature plasma treatment (the same conditions as in the example) was performed. I showed it. BPE-1300 is a compound of the above general formula where b = c = 0, a + d = 13, a, d.

In Examples A-1 to A-3, the fixed substance (A) + hydrophilizing agent (B) (hereinafter represented by (A) and (B)) was 1.5 owf%,
/ (B) is the result of changing the low-temperature plasma treatment time after resin processing to 5 to 120 seconds under the condition of a ratio of 1/2, but Comparative Example A-1 (no resin processing or plasma treatment) Examples A-2 to A-5 [(A) processing only, (A) plasma processing after processing], Comparative Examples A-6 to A-9 [(B) processing only,
(B) Plasma treatment after processing], it is found that the initial performance of wicking and suction length and the performance after washing are superior. In addition, it can be seen that Examples A-1 to A-3 are superior to Comparative Examples A-1, A-2 to A-5, and A-6 to A-9 also in terms of frictional band voltage. Next, as for the water spot, Examples A-1 to A-3 show the results without the washing step, but no water spot was observed in Examples A-1 to A-2. This has resulted in the appearance of water spots. This is considered as follows. In Examples A-1 and A-2, plasma processing was performed for 5 seconds after resin processing,
Although no water spot was generated because the unreacted monomers were tightly cross-linked for 30 seconds, Example A-
In the case of No. 3, the resin is deteriorated along with the crosslinking by the plasma treatment, and when the deteriorated product drops water, it spreads together with the spread of the water, and after drying, remains as a stain. Comparative Examples A-2 to A-5
As a result, the same result as in the previous embodiment is obtained.
Comparative Examples A-6 to A-9 were also Comparative Examples A without plasma treatment.
Comparative Example A having a comparatively long plasma processing time of -6 and 120 seconds
At -9, a water spot is generated.

Example A-4 is a case where the resin processing was performed under the same conditions as in Examples A-1 to A-3 and the low-temperature plasma treatment was not performed, but this was compared with Comparative Examples A-2 and A-6. It can be seen that Example A-4 is superior in both the initial performance of the suction length and the washing durability. Comparative Example A-
The same can be said when compared with the cases where the low-temperature plasma treatments 3 to A-5 and A-7 to A-9 are performed. However, as compared with Example A-4 which was subjected to the low-temperature plasma treatment of Examples A-1 to A-3, Example A-4 was slightly inferior in washing durability. From this result, it can be seen that the resin layer is cross-linked only by heat treatment, but low-temperature plasma treatment is preferable if the cross-linking is to be made stronger.

In Examples A-5 to A-7, (A) + (B) was 2.5 ow%.
(A) / (B) is a result of a product obtained by treating the resin at a ratio of 2/3, changing the low-temperature plasma treatment time after resin processing to 5 to 120 seconds, and washing them with water. A-1, A
-2 to A-5, witking compared to A-6 to A-9,
It can be seen that the initial performance of the suction length and the performance after washing are excellent. The same can be said for the friction band voltage.
Examples of water spots are shown in Examples A-5 to A-7.
In the case of (1), since water washing is performed in the final step, even when plasma processing is performed for 120 seconds, water spots do not occur because deteriorated substances are washed off by water washing.

Example A-8 is a case where the resin processing was performed under the same conditions as in Examples A-5 to A-7 and the low-temperature plasma treatment was not performed, but this was compared with Example A-4 described above. The results are the same as those obtained by comparing Examples A-2, A-6, A-3 to A-5, and A-7 to A-9. Examples A-5
A-7 was compared. In the case, the result is the same as that obtained by comparing the embodiment A-4 described above with the embodiments A-1 to A-3.

In Examples A-9 to A-11, (A) + (B) was reduced to 0.9 ow% and the total resin amount was reduced, and the ratio of (A) / (B) was reduced to 1/2 by low-temperature plasma after resin processing. The treatment time was changed to 5 to 120 seconds, and the results were obtained by washing with water. These were compared with Comparative Examples A-1, A-2 to A-5, and A-6.
It can be seen that the wicking, the initial performance of the wicking length, and the performance after washing are superior to those of A-9. The same can be said for the friction band voltage.

In Examples A-9 to A-11, a water washing step was performed last, and no water spot was generated. Next, regarding Comparative Example A-10 in which the amount of resin was increased, (A) +
(B) is 5owf% (A) / (B) is the result of the resin processed under low-temperature plasma treatment for 30 seconds after the resin processing under the condition of 2/3 ratio. In this case, wicking, suction length, etc. Although the product having good water absorbency, initial performance of frictional charged voltage and performance after washing can be obtained at the same time, there is a disadvantage that the texture of the fabric becomes too hard. In addition, since the amount of resin in the water spot is too large, uncrosslinked monomers remain despite the plasma treatment time, and water spots are generated.

The following is for Comparative Example A-11 in which the amount of resin was extremely reduced, and (A) + (B) was 0.05 owf%, and the ratio of (A) / (B) was 2/3. This is the result of the product subjected to the treatment for 30 seconds. In this case, only the product having poor wicking and suction performance can be obtained.

In Comparative Example A-12 in which the resin amount of (A) was increased, (A)
+ (B) is 2.5owf%, while (A) / (B) is the result of a low-temperature plasma treatment for 30 seconds after resin processing under the conditions of 4/1 and many (A). In this case, In this case, since the ratio of (A) is too high, (B) which is a hydrophilizing agent is hidden by (A), so that not only a product having good water absorption performance such as wicking and wicking length cannot be obtained, There is a problem that the feeling of the fabric becomes too bad.

In Examples A-12 and A-13, low-temperature plasma treatment was performed for 30 seconds after resin processing using the roughened yarn on the sheath portion of the core-sheath yarn,
Finally, the result of the product obtained by washing with water is shown in Comparative Example A-
Comparing the coloring properties with Examples 1 to A-12 and Examples A-1 to A-11, Examples A-12 and A-13 show very clear and deep black.

Continuation of the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) D06M 13/00-15/72 D01F 1/09 D01F 8/14

Claims (2)

(57) [Claims] 1. A polyalkylene glycol compound comprising 1 to 7
% By weight and 0.1% sodium alkylbenzenesulfonate
A polyester-based polymer containing up to 5% by weight as a core component,
What is claimed is: 1. A fabric comprising a core-sheath composite fiber having a sheath component comprising a polyester polymer substantially free of the above compound, wherein the fabric comprises a fixing agent comprising a compound having the following groups (1) and (2): A) and the polyester ether-based hydrophilizing agent (B) are not more than 2.6% by weight (based on the weight of the fabric) in the total amount of (A) and (B), and (A) is not less than 0.3% by weight and 1.0% by weight.
Below (to fabric weight) and (A) / (B) is 1/3 to 1/1
(Weight ratio). (However, a and b are integers of 0 to 60, and both a and b are 0.
Never be. ) 2. A polyalkylene glycol compound comprising 1 to 7
% By weight and 0.1% sodium alkylbenzenesulfonate
A polyester-based polymer containing up to 5% by weight as a core component,
An adhering agent (A ') comprising a compound having a group having the following groups (1) and (2) and a vinyl group at a terminal is added to a cloth containing a core-sheath type conjugate fiber having a polyester component as a sheath component and substantially not containing the compound. ) And a polyester ether-based hydrophilizing agent (B) in a total amount of (A ′) and (B) of not more than 2.6% by weight (based on the weight of the fabric), and (A ′) being not less than 0.3% by weight and not more than 1.0%.
Weight% or less (based on fabric weight) and (A ′) / (B)
A method for producing a fabric, characterized in that it is applied so as to satisfy 1/3 to 1/1 (weight ratio), and thereafter, the terminal vinyl group is reacted. (However, a and b are integers of 0 to 60, and both a and b are 0.
Never be. )