JPH0830303B2 - Ethylene / vinyl alcohol copolymer-based conjugate fiber and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to an invention which solves various problems that occur in practical use of ethylene / vinyl alcohol copolymer-based conjugate fibers.

The present invention particularly relates to a composite fiber comprising a saponified polymer of ethylene vinyl acetate copolymer (A) and another heat-melting polymer (B) or a fabric containing the composite fiber, when the component A is subjected to dry heat treatment and hot water treatment. The present invention relates to a technique for obtaining a composite fiber having excellent heat resistance stability that does not cause sticking or adhesion due to the above. The present invention also relates to a technique for preventing coloring of the composite fiber during acetalization. The present invention also relates to a technique for preventing discoloration of a dyed product during heating after acetalization. Further, the present invention relates to a technique for preventing shrinkage and deterioration at the time of dyeing and dyeing without impairing the texture and the appearance of the dyed product.

(Prior Art) Composite fibers of a saponified product of an ethylene-vinyl acetate copolymer and a hydrophobic thermoplastic resin such as polyester, polypropylene and polyamide are disclosed in JP-B-56-5846 and JP-B-55-13.
No. 72, etc.

(Problems to be Solved by the Invention) Fibers of ethylene / vinyl alcohol copolymer have hydroxyl groups in the molecule, and thus are superior in characteristics such as hydrophilicity, antifouling property, and antistatic property to conventional melt-spun synthetic fibers. have. However, since it has a low melting point and a low softening point, it has a drawback that it is inferior in heat resistance stability especially to high temperature hot water and steam. For this reason, an attempt to impart dimensional stability and the like by using an ethylene / vinyl alcohol copolymer as a heat-melting polymer having better heat stability than that and a composite fiber is disclosed in the above-mentioned patent publication. is there. However, the ethylene / vinyl alcohol copolymer-based component exposed on the fiber surface due to high-temperature high-pressure dyeing, sewing or steam iron in use still partially causes softening or microgluing, and as a result, the texture is hardened. However, there is a problem that the appearance is deteriorated. For example, in order to dye without causing such a problem, the dyeing temperature must be as low as 90 ° C. or lower, and if the dyeing temperature is exceeded, the ethylene / vinyl alcohol copolymer component will be softened and fused, and the desired I can't get the product. On the other hand, in the case of other components that are complex, dyeing cannot be sufficiently performed at 90 ° C or lower,
In the end, it is not possible to find a condition in which both components can be dyed as a composite fiber, and the fiber does not have dyeability.
In addition, there remains a problem in that ironing during sewing and steam ironing during use cause a noticeable change in appearance. Due to such a fatal problem, it is considered that this seed fiber has not reached industrialization.

The present invention is intended to solve the above problems and provide a composite fiber having excellent heat resistance stability which does not cause sticking or adhesion due to the saponified polymer (A) of ethylene vinyl acetate copolymer, and a method for producing the same. Is.

Still another object of the present invention is to provide a treatment method for solving coloring during acetalization, fading of a dyed product after acetalization, shrinkage during dyeing, deterioration and the like.

(Means for Solving the Problems) That is, the present invention is a composite comprising a saponified polymer (A) of an ethylene vinyl acetate copolymer having an ethylene content of 30 to 70 mol% and another hot melt type polymer (B). A fiber, wherein the component A is exposed on at least a part of the surface of the conjugate fiber, the component A is acetalized with a compound represented by the following general formula [I], and the melting point of the component A is There an ethylene-vinyl alcohol copolymer composite fiber characterized in that it satisfies the following formula _{[II], OHC-CnH 2 n-CHO} ...... [I] n = 0~10 -1.524 × (Et% ) +234 <Ma ...... [II] However, Et% = ethylene content in the A component (mol%) Ma = melting point of the A component (° C) Preferably, in such a fiber, the non-crosslinking aldehyde group is formed by NaHSO _3. -CnH ₂ nCHO · NaHSO ₃ adduct and whether the summer, Oh There are non-crosslinked aldehyde groups are oxidized, an ethylene-vinyl alcohol copolymer composite fiber and summer with a carboxylic acid and or carboxylates.

Further, the present invention comprises a saponified polymer (A) of an ethylene-vinyl acetate copolymer having an ethylene content of 30 to 70 mol% and another heat-meltable polymer (B), wherein the A component is at least a part of the fiber surface. Exposed composite fibers in the form of fibers or in the form of threads or fabrics with strong acid concentration (N)
At a concentration (C) in the range of 0.002 mol / l to 5 mol / l in the range of temperature (T) of 15 ° C. to 135 ° C. A method for producing an ethylene / vinyl alcohol copolymer-based conjugate fiber, which comprises acetalizing under the condition of satisfying the following formula [III], wherein N ≦ 0.548−0.576 × logC−6.3 × 10 ⁻³ × T. [III] However, N = strong acid concentration (normative) C = dialdehyde concentration (mol / l) T = acetalization temperature (° C.) Preferably, the ethylene / vinyl alcohol copolymer-based conjugate fiber is used at the fiber stage or in the yarn. This is a method of heat-treating in the form of a strip or cloth at a temperature of 100 ° C. or higher at a temperature lower than the melting point of the component A and then acetalizing the solution, and in a solution containing a salt of a strong acid or a strong base having a bath concentration of 5 g / l or more. Is the method of acetalization described above. After Le of, prior to being exposed to temperatures above 140 ° C. after staining before or stain, or treating fibers with a solution or a dispersion mixture of NaHSO _3, or after the acetalization, dyed before or after the above 140 ° C. staining It is a method of treating the fiber with an oxidizing agent before being exposed to the temperature, and when dyeing after the above-mentioned acetalization, a salt of a strong acid or strong base having a temperature of 95 ° C or higher and a bath concentration of 5 g / l or higher, Or the bath concentration
This is a method of dyeing in an aqueous solution containing 10 g / l or more of boric acid, or in a dyeing bath containing both 1 g / l or more of a strong acid / strong base salt and 5 g / l or more of boric acid.

1 to 7 show typical examples of cross-sections of the conjugate fiber of the present invention, in which the shaded portion is A.
It is a component, and the part without hatching is the B component.
Fig. 8 shows the vertical axis as acid concentration (N standard) and the horizontal axis as dialdehyde concentration (C mol / l) at 15 ℃, 75 ℃, 135 ℃.
It is the figure which illustrated the suitable density | concentration range at the time of each acetalization temperature of 0 degree C by the shaded part.

The conjugate fiber of the present invention is a conjugate fiber comprising the A polymer component and the B polymer component, wherein the A polymer component is exposed on at least a part of the surface of the conjugate fiber, that is, the whole or a part of the fiber surface. Have a fiber structure such as concentric or eccentric core-sheath fibers in which the A polymer component constitutes the sheath component, or a structure in which bimetallic bonding is performed, a multilayer composite structure, a non-uniform mixing structure, etc. It has a fiber structure in which the polymer component A is partially exposed on the fiber surface. Such a composite fiber may be a spun yarn obtained by high-speed spinning, a drawn yarn obtained from ordinary spinning, or a false twisted yarn.

In the present invention, such a composite fiber is subjected to acetalization. In this case, formaldehyde, monoaldehydes such as benzaldehyde are preferred, and dialdehydes represented by the above formula [I], for example, glyoxal, It is acetalized with a dialdehyde such as malonaldehyde or glutaraldehyde, and the acetalization raises the melting point of the component A considerably higher than before the acetalization. These dialdehydes may have a branched chain. In the case of hot water in an atmosphere such as high temperature dyeing exceeding 90 ° C., for example, high temperature dyeing under 130 ° C. which is adopted for polyester, because hot water resistance becomes excellent due to the melting point increase due to the acetalization of the component A. In this case, the melting point which could be raised does not substantially lower the melting point even after the hot water treatment, and surprisingly it was possible to completely prevent the softening fusion. Further, in the present invention, when the obtained acetalized product is subjected to a dry heat treatment in a step before dyeing, the melting point is lowered so as to be less than 1 ° C., that is, the dry heat treatment is performed below the melting point of the obtained acetalized product. Is preferred. The dry heat-treated product thus obtained can completely prevent softening fusion even in the above-mentioned high temperature dyeing at 130 ° C. In this case, if the heat treatment is performed above the melting point of the A component after the acetal, that is, the above-mentioned Ma, the hot water resistance of the A component is lowered, which is not preferable.

As an additional effect of the conjugate fiber of the present invention obtained as described above, the cross-linked acetalization enhances the water swelling property and maximizes the swelling effect of the A polymer. In the case of No. 2, the woven wave can be made large, and a natural bulge can be imparted to the woven fabric to obtain a texture having a natural bulge. Also, from the viewpoint of product consumption performance, ironing at the time of sewing,
Even when used with a steam iron, softening fusion can be prevented, and an ethylene / vinyl alcohol copolymer-based conjugate fiber having practical heat resistance stability can be obtained.

By the way, in the case of the above-mentioned composite fiber obtained by the prior art which is not acetalized, the above-mentioned high-temperature dyeing at 130 ° C. causes a problem that the A polymer component is softened and fused and the fabric is cured, so that only a commercial product having no commercial value can be obtained. There is a point.

After the acetalization, the melting point (Ma) of the component A must be within the range shown by the above formula [II],
When Ma is -1.524 x (Et%) + 234 or less, the above-mentioned excellent effect due to acetalization cannot be obtained. Also Ma
When is greater than -1.524 x (Et%) + 263, the preferred range of Ma is -1.524 x (Et%) + 234 <Ma <-1.524 x (Et%) + 263 due to coloring during acetalization. .

For acetalization, the general formula [I] as described above is used.
The compound represented by the formula (I) is used, but in the case of a compound in which n exceeds 10 in the general formula [I], it is difficult to acetalize, and even if the acetalization is possible, the heat resistance of the obtained fiber is high. The water stability is insufficient and the effect of acetalization is not exhibited.

In the present invention, the acetalization is carried out in a strong acid such as sulfuric acid, formic acid, hydrochloric acid, etc., but sulfuric acid is preferably used from the viewpoint of efficiency of the acetalization reaction. The concentration of the strong acid used is 0.05 normal or more and 2 normal or less. The acetalization reaction temperature is preferably 15 ° C. or higher and 135 ° C. or lower, and the concentration of the dialdehyde of the compound represented by [I] is 0.002 mol / l or more and 5 mol / l or less under the above-mentioned formula. [II
It is performed under the condition that satisfies [I]. In this case, when the concentration of the strong acid used is less than 0.05 N, it is not possible to obtain a satisfactory conjugate fiber having excellent heat resistance stability, which is the effect of the present invention. Further, if the concentration of the strong acid used exceeds 2 N, the composite fiber becomes brittle, which is not preferable. When the acetalization reaction temperature is lower than 15 ° C, even if the formula [II
Even if the treatment is carried out under the condition satisfying I], the acetalization reaction rate is so slow that a satisfactory conjugate fiber having excellent heat resistance stability cannot be obtained. Further, even if the acetalization reaction temperature is higher than 135 ° C. and the treatment under the condition satisfying the formula [III] is carried out, the cloth made of the composite fiber is discolored and brittle, which is not preferable. When the dialdehyde concentration is less than 0.002 mol / l, the formula [II
The degree of acetalization is extremely small even if the treatment is carried out under the condition satisfying I), so that it is possible to obtain a composite fiber having excellent thermal stability that can withstand dry heat treatment and high temperature dyeing, etc. which are received during the processing step of polyester. Can not. When the aldehyde concentration exceeds 5 mol / l, the fibers are colored during acetalization and discolored during dyeing. More preferably, the aldehyde concentration is 0.01 to 1.0 mol / l. Further, in the formula [III], the range of the dialdehyde concentration (C) is
When 0.002 to 5 mol / l and the acetalization temperature (T) range is 15 ° C to 135 ° C and the formula [III] is not satisfied,
For example, if the strong acid concentration (normal) N is less than 0.05, the acetalization reaction rate becomes very slow, and it becomes impossible to obtain a satisfactory conjugate fiber having excellent heat resistance stability, which is not preferable. Further, the strong acid concentration (normal) N is 0.5 expressed by the formula [III].
When it is larger than the value obtained from 48-0.576 x log C-6.3 x 10 ^-3 x T, the acetalized conjugate fiber becomes brittle and yellows, which is not preferable.

FIG. 8 shows a suitable range in the present processing in relation to the above processing conditions and the formula [III].
In [I], the abscissa represents the dialdehyde concentration logC, the ordinate represents the acid concentration N, and the hatched line shows a suitable range for the acetalization treatment with the acetalization temperature T as a parameter.

The present invention provides an ethylene / vinyl alcohol copolymer-based composite fiber with improved heat resistance stability only by acetalization within the preferred range described above. In order to impart it to the fiber, in the above-mentioned acetalization, in the form of cotton, yarn or cloth of the composite fiber, it is at least 100 ° C. or more and less than the melting point of the component A in a stress-free state or It is preferable to carry out dry heat treatment under tension. When it is carried out in the form of a fabric composed of the conjugate fiber, the tension-free fabric is used in order to make the yarns of the conjugate fiber constituting the fabric into a bulk and to increase the woven wave to bring about a swelling texture. It is preferably carried out in the state. Also in the case of fibers or yarns, it is preferable to perform in a tension-free state in terms of crimp developability.

As described above, the melting point increase of the A component by acetalizing the fiber obtained by the heat treatment is remarkable as compared with the melting point increase of the A component after the acetalization when not heat-treated, Surprisingly, it has a remarkable effect on the improvement of hot water resistance. In order to bring about the remarkable increase in melting point, it is preferable that the heat treatment temperature is within a temperature range of -5 ° C to 10 ° C below the melting point of the component A before acetalization, and the lower limit temperature range is preferably 100 ° C or higher. However, if the heat treatment temperature is lower than 100 ° C., the melting point increase due to the acetalization referred to in the present invention is not observed, and there is no remarkable effect on the improvement of hot water resistance, which is not preferable. In the present invention, the heat treatment means heating the cloth using a dry set, microwave heating or superheat of steam,
It means radiant heating by infrared rays. According to the present invention, as described above, the heat treatment before the acetalization gives a sufficient improvement in the heat resistance stability of the ethylene-vinyl alcohol copolymer-based composite fiber after the acetalization. It has been found that the composite fiber tends to be colored during aging. Therefore, the present invention is also to solve this point, as a solution to the problem, when acetalization under the acetalization conditions, a bath concentration of 5 g / l or more of a strong acid / strong base salt is contained. The above inconvenience is solved by acetalization with an aqueous solution.

Examples of the strong acid / strong base salt used here include sodium sulfate, potassium sulfate, sodium chloride, potassium chloride and the like, but sodium sulfate is preferable.

If the bath concentration of strong acid / strong base salt is less than 5 g / l, the effect is not sufficient. However, conversely, even if the bath concentration exceeds 50 g / l, the reaction rate of acetalization becomes slow. Therefore, the bath concentration should be determined in the range of 5 g / l to 50 g / l, and the more preferable range is 10 g / l to 30 g / l.

The above-described acetalization achieves a sufficient improvement in heat resistance stability and coloration prevention, but the present invention more preferably employs the following method after acetalization.

That is, after acetalization, before dyeing and / or after dyeing
Treating the fibers with a solution of NaHSO ₃ or a dispersed mixture thereof before being exposed to temperatures above 140 ° C., or
After acetalization and before dyeing and / or after dyeing and before exposure to temperatures of 140 ° C or higher, an aqueous solution of an oxidizing agent such as permanganate, hydrogen peroxide, silver oxide, nitric acid, hypochlorous acid, sodium perborate, etc. Treat with gas.

Regarding the purpose of the above-mentioned treatment, acetalization with a dialdehyde may leave a non-crosslinking type free aldehyde in addition to the crosslinking type reaction, and this aldehyde may cause discoloration of the dyed product during heating. This is to prevent this. That is, therefore, with NaHSO ₃ -CnH ₂ nCHO-NaHSO ₃ adducts such as R
The aldehyde is blocked by changing to the form of —CH (OH) SO ₃ Na, or the aldehyde is oxidized to form a carboxylic acid or a carboxylic acid salt.

Furthermore, in the present invention, when the component B of the conjugate fiber is a polyester polymer, high temperature dyeing performed under high temperature hot water conditions is essential as a dyeing step in order to dye the polyester polymer side. There is no problem with A component even in high temperature dyeing,
The following method was found.

That is, when dyeing after acetalization, a temperature of 95 ° C or higher, a bath concentration of 5 g / l or more of a strong acid / strong base salt, or a bath concentration of 10 g / l or more of an aqueous solution containing boric acid, or a strong acid / strong base of A method for producing an ethylene / vinyl alcohol copolymer-based conjugate fiber, which comprises dyeing in a dyeing bath containing both salt 1 g / l or more and boric acid 5 g / l or more.

In the above treatment, when a cloth containing the above-mentioned composite fiber in which the A polymer component is partially and / or entirely exposed to the fiber surface is dyed at a high temperature of 95 ° C. or higher, it is acetalized with a dialdehyde. It is intended to prevent shrinkage and deterioration at the time of dyeing of a yarn by the ethylene / vinyl alcohol copolymer component which is the A polymer component so that the yarn can be dyed without impairing the feeling and the appearance of the dyed product.

According to the conventional dyeing method, for example, high temperature dyeing at 130 ° C. is adopted for ordinary polyester fibers. However, it is possible to dye the polyester side of a fabric containing a composite fiber composed of the above-mentioned A polymer component, which is the premise of the method of the present invention, and a B polymer component using a polyester-based polymer, particularly polyethylene terephthalate which is a normal polyester. When dyeing under high temperature dyeing, a very large shrinkage due to the A polymer component constituting the fabric and a whitening phenomenon of the fabric at the time of dyeing due to deterioration of the A polymer component caused by high shrinkage appear. In some cases, it may not be of commercial value.

In the above-mentioned treatment method of the present invention, surprisingly, even under the conditions of high temperature hot water employed in the case of high temperature dyeing of polyester fibers, a salt of strong acid / strong base or boric acid alone or both It has been found that the presence of the mixture makes it possible to prevent the shrinkage of the fabric based on the A polymer component part, the incidentally the A polymer component does not deteriorate, and the whitening phenomenon at the time of dyeing disappears. .

As a more preferred embodiment of the above treatment method, a strong acid
The strong base salt and boric acid may be used in combination, but each may be used alone. When the strong acid / strong base salt used in this method is used alone, the bath temperature is 5 g / l or more,
Similarly, in the case of using boric acid alone, a range of 10 g / l or more is applied as the concentration, but in order to maximize the intended effect of the present invention, it is necessary to use a strong acid / strong base salt alone. In this case, a bath concentration of 15 g / l or more is preferable. Similarly, when boric acid is used alone, it is preferably 20 g / l or more. If the bath concentration of the salt of strong acid / base is less than 5 g / l and the bath concentration of boric acid is less than 10 g / l, the above effect cannot be observed, which is not preferable. When a salt of a strong acid and a strong base is used in combination with boric acid, the bath concentration is preferably 1 g / l or more of the salt of a strong acid and strong base and 5 g / l or more of boric acid. If the bath concentration of the salt of strong acid and strong base is less than 1 g / l, and the same concentration of boric acid is less than 5 g / l, the above effect cannot be observed, which is not preferable.

Examples of the strong acid and strong base salt used in the present invention include sodium sulfate, potassium sulfate, sodium chloride, potassium chloride and the like, and sodium sulfate is preferable.

In the composite fiber used in the present invention, which is composed of the A polymer component, that is, a saponified polymer of an ethylene vinyl acetate copolymer having an ethylene content of 30 to 70 mol%, and the B polymer component, that is, another hot melt polymer, If the amount exceeds 70 mol%, the content of vinyl alcohol component will decrease, and properties such as hydrophilicity will decrease due to the decrease of hydroxyl groups. Conversely, if the ethylene content becomes lower than 30 mol%, vinyl alcohol will decrease. When the content of the component is too large, the melt moldability is deteriorated, and the spinnability becomes poor at the time of forming the composite fiber with the heat-meltable polymer, so that single yarn breakage and yarn breakage increase, which is not preferable. Therefore, the ethylene content in the saponified ethylene vinyl acetate copolymer is 30.
Those of up to 70 mol% are suitable. The saponification degree is preferably 98 mol% or more from the viewpoint of hot water resistance. Further, the composite fiber in the present invention means the A polymer component and B constituting the composite fiber.
The polymer component and the B
A structure in which a polymer component is joined along the length of a single filament in a shape that does not completely surround the A polymer component, or a side-by-side type or further B
It includes a structure such as a core-sheath type in which the polymer component is completely surrounded by the polymer component A, and indicates, for example, a conjugate fiber having a cross section as shown in FIGS. 1 to 7. The conjugate fiber in the present invention is not limited to the one illustrated in the figure, and does not have to be a perfect circle, for example, an ellipse, a rectangle, a triangle, a polygon,
Of course, even if it is multi-lobed, it does not matter. In addition, when the A polymer has a cross-sectional shape such that it is completely covered with the B polymer, excellent properties of the A polymer, such as hydrophilicity, antifouling property, antistatic property, etc., are exhibited. I can't get it.

As the B polymer component in the present invention, that is, the other heat melting type polymer, a melt-spinnable polymer is usually used, but a polymer having a melting point higher than that of the ethylene-vinyl alcohol copolymer is preferable, for example, polyethylene terephthalate, 80 mol. % Or more is an ethylene terephthalate residue, and the acid component or the glycol component is terephthalic acid, a copolymerized polyester modified with a component other than ethylene glycol, polybutylene terephthalate, polyhexamethylene terephthalate and their copolymerized polyester, nylon 6, Nylon 66, nylon 12 and copolyamides thereof, polyester ethers, polyester amides, polyphenylene sulfides and the like are available. Particularly, from the viewpoint of heat resistance, a polymer having a melting point of 160 ° C. or higher is preferable, and it is desirable because it is suitable for the fields of clothing and various non-clothing applications. The area ratio of the cross section of the A polymer and the B polymer in the fiber is preferably 10:90 to 99: 1.

Incidentally, when the ethylene vinyl alcohol copolymer-based conjugate fiber of the present invention is a mixed knitted fabric of natural fibers such as cotton, silk and wool, the natural fiber has poor acid resistance,
Natural fibers may be deteriorated by the acids used during the acetal. Therefore, in the case of blending with natural fibers, or for the purpose of interwoven fabrics, the ethylene vinyl alcohol copolymer-based composite fibers are first acetalized in the form of threads such as ridges, threads, and cheese, and then natural fibers. It can be mixed-spun and mixed knitted.

Further, the ethylene-vinyl alcohol copolymer-based conjugate fiber which is the object of the present invention has a feature that a fabric having a soft texture can be obtained by itself, but the above-mentioned acetalization is performed on the conjugate fiber in the form of circular knit. By crimping, then unwinding the circular knit to obtain crimped yarn, and by weaving and weaving this crimped yarn alone, and by weaving and weaving this crimped yarn with natural fibers. Further, it is possible to obtain a fabric having an even more excellent soft feeling and having stretchability.

The present invention will be further described with reference to Examples. The evaluation of the heat resistance stability was carried out at high temperature and high pressure dyeing exceeding 100 ° C. or 170
Paying attention to the degree of curing of fiber aggregates such as cotton, yarn, and fabric at the time of drying at ℃ or setting, those having no inter-fiber sticking as a tactile sensation were regarded as good. On the other hand, in the ironing test, it was judged by the change in the texture of the cloth when the cloth was applied and steam ironed. In addition, the heat resistance and fastness of the dyed product is about 170 degrees C
Whether or not there was a change in color fading was examined by a finishing set for minutes, and the lack of color fading was evaluated by a visual inspection.

For the melting point of the component A polymer, the endothermic peak temperature was determined by differential scanning calorimetry (hereinafter abbreviated as DSC) under the following conditions.

DSC measurement conditions Example 1 A-side polymer having a saponification degree of 99% and an ethylene content of
48 mol% ethylene vinyl acetate copolymer saponified product, 85
A chip having an intrinsic viscosity [η] = 1.1 dl / g measured at 30 ° C. using a% hydrous phenol was used. As the B-side polymer, a chip having an intrinsic viscosity [η] of 0.59 measured at 30 ° C. using a mixed solvent of polyethylene terephthalate and tetrachloroethane: phenol = 1: 1 was used. The composite ratio of the A side and the B side was set to 2: 3, and the composite polymer was spun at a temperature of 265 ° C. and the take-up speed was 1200 m / min so that the cross section thereof was a multi-layer composite fiber as shown in FIG. It was spun under the spinning conditions of. The spun yarn was drawn in a two-stage water bath with a first bath of 65 ° C and a second bath of 85 ° C (total draw ratio of 4.0), and crimped and cut according to a conventional method to form a staple fiber of 1.5d x 38mm. Obtained.

Next, glyoxal 0.07 mol / l, sulfuric acid 8 g / l, raw cotton is immersed in a bath containing a composition solution containing the coloring agent NaHSO ₃ 0.3 g / l, and after acetalization at 80 ° C for 120 minutes, alkali hot water is used. Was neutralized, washed with sufficient water, and after applying an oil agent, dehydrated and dried.

As Comparative Example 1, the above raw cotton which was not acetalized was used. Cotton was acetalized and non-acetalized cotton each separately blended with 50% cotton to give a spun yarn of each 30 ^'S.
Then, 1/1 plain weave was woven separately to finish the white fabric for shelter. The melting point of the polymer on the A side that did not acetalize was 159 ° C as a value determined from the endothermic peak temperature of DSC.
The fabric showed hardening at the stage of heat setting at 160 ° C., and the texture became worse in the iron test, but the acetalized one had a melting point of the polymer on the A side.
According to the same DSC measurement method, the temperature was 162 ° C., which was considerably higher than the melting point of the A-side polymer which did not acetalize, and which satisfied the above formula [II], and the acetalized fabric was acetalized. It had a soft texture without the problems that were seen in the case of suppleness.

Moreover, this product is not only conspicuous in oily stains such as burrs and sardines in the wearing test of sewn products, and is not only excellent in antifouling property but also comfortable to wear compared to conventional polyester / cotton blended sheer fabric. .

Examples 2 to 6 and Comparative Examples 2 to 7 A polyethylene terephthalate polymer (abbreviated as IPA-PES) obtained by copolymerizing 10 mol% of isophthalic acid as a B-side polymer and having an intrinsic viscosity of [η] 0.68 dl / g during spinning. The chip was used. As the A-side polymer, a saponified ethylene vinyl acetate copolymer (abbreviated as EVOH) having a saponification degree of 99% and an ethylene content of 46 mol% and a chip having an intrinsic viscosity [η] of 1.12 dl / g was used. The EVOH / IPA-PES composite ratio is 1/1, and the cross-section is EVOH as shown in Fig. 1 for the sheath layer and IPA-P.
The composite polymer is spun at a temperature of 260 ° C so that the ES becomes the core layer.
It was wound up under a spinning condition of a spinning speed of 1000 m / min. The resulting spun raw yarn was brought into contact with a 75 ° C. heat roller and a 120 ° C. heat plate by a normal roller plate type drawing machine to draw a draw ratio of 4.1 times to obtain a composite filament of 50 dr / 24f. It was

A taffeta was woven using this composite filament as a warp and a weft. The raw machine density is 97 warp threads / 88 inch weft threads /
It was hot. Actinol R-100 1g
After desizing at 80 ° C for 20 minutes at 80 ° C / l, each composition solution containing glutardialdehyde (hereinafter abbreviated as GA) shown in Table 1 is heated to a predetermined temperature and acetalized at that temperature for 50 minutes. (Hereinafter abbreviated as GA).

In Examples 2 to 5, the conditions for the GA reaction were set within the range defined by the present invention described above, but Comparative Example 2
Is an example in which GA is not performed, Comparative examples 3 and 4 are examples in which the GA concentration is out of the condition, Comparative examples 5 and 6 are examples in which the GA temperature is out of the condition, and Comparative example 7 is a prerequisite of sulfuric acid concentration. In the case where the condition is out of the lower limit of 0.05 to 2 stipulation, Comparative Example 8 is the sulfuric acid concentration [II
This is an example in which the condition of the formula [I] is not satisfied.

Table 1 shows these conditions and the results. Example 2
In Nos. 5 to 5, the melting point of the A-side polymer was shown in the range satisfying the above formula [II], the texture after ironing test was good, and there was no problem in the processing step.

Examples 6 to 9 and Comparative Example 9 A polyethylene terephthalate-based polymer (abbreviated as IPA-PES) obtained by copolymerizing 8 mol% of isophthalic acid as a B-side polymer and having an intrinsic viscosity during spinning of [η] of 0.65 dl / g. Was used. As the A-side polymer, a saponification product of ethylene vinyl acetate copolymer (EVOH) having a saponification degree of 99% and an ethylene content of 44 mol% and an intrinsic viscosity [η] of 1.10 dl / g was used. The EVOH / IPA-PES composite ratio is 1/1, and the cross section thereof is spun at 265 ° C at a spinning temperature of 265 ° C so that EVOH serves as a sheath layer and IPA-PES serves as a core layer as shown in Fig. 1. It was wound under a spinning condition of a speed of 1000 m / min. The obtained spun raw yarn was drawn by contacting it with a heat roller of 75 ° C. and a heat plate of 120 ° C. by a normal roller plate type drawing machine to obtain a composite filament of 50 dr / 24f.

A taffeta was woven using this composite filament as a warp and a weft. The densities were 97 warps / inch and 88 wefts / inch. This raw taffeta with sodium carbonate 2g / l
After desizing at 80 ° C for 40 minutes and neutralizing with dilute acetic acid solution, 90% with a composition solution of GA concentration 0.05 mol / l and sulfuric acid concentration 0.3 N containing each concentration of sodium sulfate shown in Table 2 Table 2 also shows the degree of coloring (yellowness b ^* ) of the woven fabric after GA conversion, which was obtained by heating to ℃ and acetalizing for 120 minutes at that temperature, then neutralizing and washing with water.

In Examples 6 and 7, sodium sulfate was present in the GA reaction within the range specified by the present invention, and a satisfactory increase in the melting point of the A-side polymer was observed within the range specified by the present invention. And the degree of yellowing after GA was low.
Example 8 is an example in which sodium sulfate is not added to the GA composition solution, and Example 9 is an example in which the concentration of sodium sulfate is out of the condition. A satisfactory increase in melting point of the A-side polymer is observed, but GA conversion is observed. A little yellowing was seen later. Therefore, the woven fabrics having good whiteness as in Examples 6 and 7 are preferable conditions in that the dyed dyed products have a good color development and a high quality appearance.

Examples 10 to 13 Each taffeta obtained by the GA of Examples 6 to 7 was treated with H ₂ O ₂ (30
%) 5 cc / l solution was used as a post-treatment for 30 minutes at a bath ratio of 50: 1 at 80 ° C for 30 minutes to eliminate the non-crosslinked aldehyde groups that appeared during GA formation. Subsequently, presetting was carried out at 140 ° C. with a pin tenter, and high temperature jet dyeing was carried out under the dyeing conditions shown below.

<Dyeing conditions> Dye: Sumikaron Blue S-3RF 2% owf Dispersant: Nitsukasan Salt # 7000 0.5g / l Bath ratio 50: 1 115 ° C for 40 minutes, then Na ₂ S ₂ O ₄ 1 g / l, NaOH 1 g / l, amylazine 1 g / l, reduction washing with 20 minutes of reduction cleaning, running water washing, intermediate drying, then pintenter Using the Final Set 140
Drying heat treatment was carried out at 0 ° C., and the melting points of the A-side polymer in that case were 171 ° C. and 172 ° C., and dyed and finished products were obtained.

Each of the dyed and finished products was excellent without any fading even in the final set at 140 ° C. and without impairing the feeling.

Incidentally, as a carboxylic acid production confirmation test, Examples 10, 11
The cloth before and after the H ₂ O ₂ treatment was dyed with the cationic dye shown below, and the judgment was made by comparing the dyeing ratio. Note the melting point of the polymer of A side after H ₂ O ₂ treatment was the same as H ₂ O ₂ pretreatment of the melting point.

Cationic dye Dyeing conditions 90 ° C for 1 hour The dyeing rate in dyeing the fabric before H ₂ O ₂ treatment is 5%, whereas the dyeing rate in dyeing the fabric after H ₂ O ₂ treatment is 20%
Therefore, it is assumed that the H ₂ O ₂ treatment increases the number of carboxyl groups.

Examples 14 to 15 and Comparative Example 10 A polyethylene terephthalate polymer (abbreviated as IPA-PES) obtained by copolymerizing 8 mol% of isophthalic acid as a B-side polymer, and having an intrinsic viscosity during spinning of [η] of 0.65 dl / g. Was used. As the A-side polymer, a saponification product of ethylene vinyl acetate copolymer (EVOH) having a saponification degree of 99% and an ethylene content of 44 mol% and an intrinsic viscosity [η] of 1.10 dl / g was used. The EVOH / IPA-PES composite ratio is 1/1, and the cross section thereof is spun at 265 ° C at a spinning temperature of 265 ° C so that EVOH serves as a sheath layer and IPA-PES serves as a core layer as shown in Fig. 1. It was wound under a spinning condition of a speed of 1000 m / min. The resulting spun raw yarn is brought into contact with a heat roller of 75 ° C and a heat plate of 120 ° C by a usual roller plate type drawing machine, and a drawing ratio is obtained.
It was stretched 4.1 times to obtain a composite filament of 50dr / 24f.

Using this composite filament as warp and weft, Z twist 300 T / M twist is used for warp, and Z twist 2500 T / M, S twist 2 is used for weft.
Weaving a satin crepe in which weft inserts of two strongly twisted yarns such as 500 T / M were alternately inserted. The raw machine density is 164 warps /
Ichi, 97 wefts / Ichi

Example 14: Satin crepe for raw machinery as Example 14 in a tension-free state with a Shrink Suffer machine
A dry heat treatment at 150 ° C was performed. Then sodium hydroxide 1g /
l, Actinol R-100 0.5g / l liquid composition, scouring desizing treatment at 80 ℃ for 30 minutes, glutaraldehyde 0.05mo
1 / l, sulfuric acid 15g / l, sodium sulfate 20g / l composition liquid containing 50: 1 bath ratio, 90 ℃ 120 minutes acetalization (hereinafter GA
Abbreviated), followed by neutralization with dilute alkali and washing with sufficient water, and then H ₂ O ₂ (35%) 5c.c./
After oxidative post-treatment for 30 minutes at a bath ratio of 50: 1 and 80 ° C. with the liquor (1), 140 ° C. of the preset was subjected to high-temperature dyeing under the following dyeing conditions to perform the final set of 140 ° C. Further, the raw satin crepe used in Example 14 as Example 15 was subjected to scouring desizing, acetalization, post-oxidation treatment, pre-setting, and high temperature under the same conditions as in Example 11 without performing dry heat treatment at 150 ° C. Dyeing and final set.

<Dyeing conditions> Bath ratio 50: 1 120 ° C. × 40 minutes As Comparative Example 10, a squeezing desizing cloth which had been subjected to dry heat treatment at 150 ° C. of the above-mentioned raw machine satin crepe to be acetalized was similarly used, and a liquid stream high temperature of 120 ° C. was performed. Table 3 shows the results such as the hand after dyeing and the melting points obtained from the DSC measurement of the A-side polymer.

In this example, the texture after high-temperature dyeing is good, and particularly when dry heat treatment is performed at a temperature below the melting point of the A component polymer prior to acetalization in the case of Example 14, the A component after acetalization is used. The effect of increasing the melting point of the polymer was recognized, the curing of the component A polymer in the subsequent high-temperature dyeing process was prevented, and the product was extremely soft and had a swelling texture, resulting in a high commercial value.

Examples 16 to 23 A polyethylene terephthalate polymer (abbreviated as PET) having a B-side polymer with an intrinsic viscosity of [η] of 0.71 dl /
Using a chip of g, as an EVOH polymer for the A-side polymer, a saponification product of ethylene vinyl acetate copolymer having a saponification degree of 99% and an ethylene content of 48 mol% has an intrinsic viscosity [η] of 1.10 dl / g.
The chip was used. The EVOH / PET composite ratio is set to 1/1, and the cross section of the composite polymer is such that EVOH is the sheath layer and PET is the core layer as shown in Fig. 1, and the spinning speed is 1000 m / min at a spinning temperature of 270 ° C. It was wound under the spinning conditions of The obtained spun raw yarn was drawn by bringing it into contact with a heat roller at 75 ° C. and a heat plate at 120 ° C. by an ordinary roller plate type drawing machine to obtain a composite filament of 50 dr / 24f.

A taffeta was woven using this composite filament as a warp and a weft. The raw machine density is 98 warp threads / 89 inch weft threads /
It was hot. This greige taffeta is Actinol R-100 1
Desizing was carried out at 80 ° C for 20 minutes at g / l. After the desizing, the melting point of the A-side polymer before GA conversion was 162 ° C. Next, for the cloth after desizing, glutardialdehyde 0.05 mol / l, sulfuric acid 15 g
An acetalization treatment was carried out with a composition liquid containing / l at a bath ratio of 50: 1 at 90 ° C. for 60 minutes, and after the treatment, presetting at 140 ° C. was performed. The melting point of the A-side polymer of this cloth was 165 ° C.

About this woven fabric, each dye liquor composition containing sodium sulfate and boric acid, which are the additives shown in Table 4, was used at 130 ° C x 4
Dyeing was performed for 0 minutes, and normal reduction washing was performed. The shrinkage ratio of the fabric width, the judgment of the change in the feeling, the appearance of the dyed product, etc., which appear at the time of each dyeing after each dyeing reduction cleaning treatment using each dyeing liquid composition were evaluated, and the A side polymer of each dyed product was evaluated. The melting point was measured by DSC.

<Dyeing conditions> Dye: Sumikaron Bule S-3RF 2% owf Dispersant: Nitsukasan Salt # 7000 0.5 g / l Ammonium sulfate 1 g / l PH modifier Acetic acid (48%) 1c.c./l Additive (No. 4) Compositions shown in the table) Bath ratio 50: 1 Dyeing temperature 130 ° C. Time 40 minutes Bath concentration (addition amount) of sodium sulfate and boric acid specified in the present invention as shown in Table 4 of Examples 16 to 19 above In some cases, when dyeing at a dyeing temperature of 130 ° C,
It is possible to suppress shrinkage at the time of dyeing, and it is possible to perform dyeing satisfying the texture and the appearance at the time of dyeing at a high value as a commercial value. On the other hand, in the case of Examples 20 to 23, it is not fatal as a commercial value, but the shrinkage at the time of high temperature dyeing becomes large.

Example 24 The same desizing of the same raw material used in Example 2 was followed by the same desizing, and then with a composition liquid containing 0.04 mol / l of glutaraldehyde, 15 g / l of sulfuric acid, and 20 g / l of sodium sulfate, a bath ratio of 50: 1 and 90 ° C. 50
It was subjected to acetalization treatment for 1 minute, and then pre-set at 150 ° C.

This fabric subjected to the same dyeing and reduction clearing as in Example 10, to allowed to eliminate non-crosslinked aldehyde groups expressed during acetalization at a 2% aqueous solution of NaHSO _3, bath ratio 50: 1,90 ° C. The post-treatment was performed for 30 minutes. The melting point of the A-side polymer for this fabric was 166 ° C.

The woven fabric was subjected to a final set treatment at 150 ° C., and the degree of fading at that time was judged by the b ^* size according to the L ^* a ^* b ^* colorimetric method. S before and after NaHSO ₃ treatment
Elemental analysis was performed for the content (%). The results are shown in Table 5.

After staining as shown in Table 5, provide satisfactory dyeings without fading the color of dyed product be subjected to Fuainaru excisional in the subsequent 0.99 ° C. and at was hot Doing treated with a solution of NaHSO ₃ I understand. Further, since the S content increases due to the NaHSO ₃ treatment, it is presumed that a NaHSO ₃ adduct is produced in the fabric as defined in the present invention. No detection of free aldehyde was found in the quantitative test of free aldehyde according to JIS-L-1041-83.

Example 25 The composite filament used in Example 14 was wound on cheese and scoured at 80 ° C. for 30 minutes with a composition liquid of Actinol R-100 (nonionic surfactant) 1 g / l in the shape of cheese. . After that, glutaraldehyde 0.05mol / l, sulfuric acid 15g
/ l, 20g / l sodium sulfate in a composition liquid containing 50:
After acetalization treatment at 1, 90 ° C. for 2 hours, the sulfuric acid in the cheese was sufficiently neutralized and washed with water. After that, oxidation treatment was performed with hydrogen peroxide (35%) at 100 c.c./l and a bath ratio of 50: 1 at 80 ° C for 30 minutes.

As a carboxylic acid production confirmation test, a dyeing test with a cationic dye was carried out in the same manner as in Example 11, and the dyeing rate was improved, and an increase in carboxyl groups was estimated.

The composite filament obtained by the above GA and oxidation was interwoven with a worsted yarn. The worsted yarn constituting the knitted fabric and the reduction rate of the tenacity and the elongation of the knitted fabric were 0%, and the texture of the natural fiber was fully utilized to form a knitted fabric. The melting point of the A-side polymer contained in this cross-knitted product was 172 ° C.

Example 26 The composite filament of 50dr / 24f used in Example 6 was formed into a circular knit of 28 gauge Tenjiku and scoured at 80 ° C. for 30 minutes with a composition liquid of Actinol R-100 1 g / l, and then glutar. Aldehyde 0.05mol / l, sulfuric acid 15g / l, sodium sulfate 20g / l
An acetalization treatment was performed for 90 minutes at a bath ratio of 50: 1 at 90 ° C. with a composition liquid containing After that, the sulfuric acid contained in the circular knit is sufficiently neutralized and washed with water, and the hydrogen peroxide solution (35
%) 10 c.c./l, bath ratio 50: 1, oxidation treatment at 80 ° C. for 30 minutes. Regarding the circular knitted fabric after the oxidation treatment, the production confirmation test of carboxylic acid by the same method as in Example 10 and JIS-
In the evaluation such as the quantitative test of free aldehyde by L-1041-83, increase of carboxylic acid and detection of aldehyde were not recognized. The composite filament was unwound from the circular knitted fabric obtained by such an acetalized oxidation treatment, and the unwound yarn was used to make a 28-gauge circular knitted fabric again.

The crimp elongation of the unwound yarn from the circular knitted fabric was 5%, and the knitted fabric knitted from the unwound yarn had excellent stretch backability and soft feeling. The melting point of the A-side polymer of this unwound yarn was 171 ° C.

 The crimp elongation rate was measured by the following method.

Method for measuring the crimp elongation rate Create a yarn and perform hot water treatment at 90 ° C for 30 minutes under an initial load of 1 mg / dr to remove the initial load of 1 mg / dr, and after air-drying the initial load (1 mg / dr ) Underneath measure length l ₁ . Then, a load of 100 mg / dr is applied on top of the initial load, the length l ₂ is measured, and the crimp elongation rate is determined by the above calculation formula.

Examples 27 to 28 and Comparative Examples 11 to 15 As the A-side polymer, chips of saponified ethylene vinyl acetate copolymer having a degree of saponification of 99% and varying the ethylene content shown in Table 6 were used. As the B-side polymer, a polyethylene terephthalate-based polymer obtained by copolymerizing 10 mol% of isophthalic acid, and a chip having an intrinsic viscosity [η] of 0.68 dl / g during spinning was used. The composite filament of EVOH / IPA-PES, its cross-section, spinning conditions, drawing conditions, etc. were made the same as in Example 2 and an attempt was made to produce a composite filament targeting 50dr / 24f.

The taffeta was woven as a warp and a weft for the filament that could be produced as a composite filament. The densities were 97 warps / inch and 88 wefts / inch. This raw taffeta was desizing and GA-ized under the same conditions as in Example 2.

Examples 27 and 28 are examples of GA-conjugated composite fibers that were obtained when the ethylene content of the A-side polymer was within the range specified by the present invention described above.

Comparative Examples 11 and 12 are examples in which the ethylene content is out, Comparative Example 1
3, 14, and 15 are examples in which GA was not applied after desizing of the raw taffeta used in Examples 27, 28 and Comparative Example 13. The results are shown in Table 6.

In this example, the melting point of the A-side polymer after acetalization was higher than the melting point of the polymer before acetal, which was a satisfactory increase, and the texture after ironing was good, and the composite fiber had good heat resistance. It was

[Brief description of drawings]

1 to 7 are typical cross-sectional views of the conjugate fiber of the present invention. FIG. 8 shows the relationship between the acid concentration and the dialdehyde concentration for each acetalization temperature.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Masao Kawamoto, 1621 Sakata, Kurashiki, Okayama Prefecture, Kuraray Co., Ltd.

Claims (6)

[Claims] 1. A composite fiber comprising a saponified polymer (A) of an ethylene-vinyl acetate copolymer having an ethylene content of 30 to 70 mol% and another hot melt polymer (B). The component A is exposed on at least a part of the surface, the component A is acetalized with a compound represented by the following general formula [I], and the melting point of the component A satisfies the following formula [II]. An ethylene / vinyl alcohol copolymer-based conjugate fiber characterized in that OHC-CnH ₂ n-CHO ...... [I] n = 0~10 -1.524 × (Et% ) + 234 <Ma ...... [II] However, Et% = ethylene content in component A (mol%) Ma = A Melting point of component (℃) 2. The acetalized conjugate fiber according to claim 1, wherein the non-crosslinked aldehyde group is oxidized to form a carboxylic acid and / or a carboxylic acid salt. Type composite fiber. 3. A saponified polymer (A) of an ethylene-vinyl acetate copolymer having an ethylene content of 30 to 70 mol% and another heat-meltable polymer (B), wherein the component A is at least a part of the fiber surface. In the fiber state of the exposed composite fibers or in the form of yarn or cloth, the strong acid concentration (N) is set to 0.05 normal to 2 normal, and in the temperature range (T) of 15 ° C to 135 ° C, the following Ethylene characterized in that the compound of the formula [I] is acetalized under a condition (C) in the range of 0.002 mol / l to 5 mol / l and satisfying the following formula [III]:
A method for producing a vinyl alcohol copolymer-based conjugate fiber. OHC-CnH ₂ n-CHO ... [I] n = 0 to 10 N≤0.548-0.576 x log C-6.3 x 10 ^-3 x T ... [III] where N = strong acid concentration (normative) C = dialdehyde Concentration (mol / l) T = acetalization temperature (° C) 4. An ethylene / vinyl alcohol copolymer-based composite fiber is heat treated at a fiber stage or in the form of a yarn or a fabric at a temperature of 100 ° C. or higher and below the melting point of the component A, and then acetalized. The method for producing the ethylene-vinyl alcohol copolymer-based conjugate fiber according to claim 3. 5. The ethylene / vinyl alcohol copolymer-based composite fiber according to claim 3, wherein the acetalization is carried out in an aqueous solution containing a salt of a strong acid or a strong base having a bath concentration of 5 g / l or more. Manufacturing method. 6. After acetalization according to claim 3, before or after dyeing and before being exposed to a temperature of 140 ° C. or higher,
A method for producing an ethylene / vinyl alcohol copolymer-based composite fiber, which comprises treating the fiber with an oxidizing agent.