JP2775996B2 - Pearl-like composite fiber - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention is a pearl-like composite fiber in which a single fiber is dyed in a different color consisting of fluorescent whitening and chromatic color, and is different from a conventional iridescent dyeing. It is about.

[Prior Art] Conventionally, as a method for changing the appearance of the hue of a cloth as a beetle-like cloth depending on the viewing direction, fibers having different dyeing properties are arranged on one of a warp yarn and a weft yarn and then dyed separately. By using a unique dyed yarn,
It was performed by arranging either the warp yarn or the weft yarn.

However, these fabrics are mainly chromatic colors, and the effect of achromatic colors is hardly expected. In addition, it is difficult to cope with a knitted fabric by these methods.

Further, a fiber spun with a polyamide represented by nylon 6 or nylon 66 and a sulfonated aromatic dicarboxylic acid-modified polyester as described in JP-B-34-10497 is treated with a cationic dye and an acid dye. It is also possible to dye different colors. However, when the structure of this composite fiber is dyed with chromatic dyes even when the structure of the side-by-side type, or concentric or eccentric core-sheath composite type, or when dyed with white and chromatic dyes, It becomes an intermediate color of the color possessed by the dye, and does not exhibit the effect of different color dyeing.

[Problem to be Solved by the Invention] The present invention provides a fluorescent whitening agent while maintaining the fluorescent whiteness.
It is an object of the present invention to provide a pearl composite fiber that emits a light chromatic color depending on the degree of a curved surface created by a product fabric.

[Means for Solving the Problems] In order to solve the above problems, the present invention has the following configuration. That is, a composite fiber in which a polyamide is disposed on a sheath portion, a sulfonated aromatic dicarboxylic acid-modified polyester is disposed on a core portion, and a dye is dyed with a cationic type fluorescent brightener and an acidic colored dye as a dye. The dyeing ratio of the type fluorescent whitening agent is 10% or less of the dyeing ratio of the cationic type fluorescent whitening agent in the core, and the dyeing ratio of the acidic colored dye is 0.002 to 0.05% owf with respect to the sheath polyamide. It is a pearl composite fiber characterized by the following.

Polyamides referred to in the present invention are typically poly-ε-capramide (nylon 6) and polyhexamethylene adipamide (nylon 66), but other polymerizable monomers such as laurolactam, sebacic acid, para A polyamide obtained from xylylenediamine, isophthalic acid, or the like, or a copolymerized polyamide thereof may be used. Also, a modified polyamide in which a compound having a sulfone group is bonded to a part of a polyamide chain or a terminal, or a compound having a sulfone group.During polyamide polymerization, the sulfonated aromatic dicarboxylic acid is converted into a free acid state or an alkyl ester. It may be a modified polyamide obtained by adding and copolymerizing in the state.

Representative examples of the sulfonated aromatic dicarboxylic acid include 5-sulfoxyisophthalic acid represented by the following chemical formula [I] or a salt thereof.

From the viewpoint of obtaining the effect of modification while maintaining the mechanical properties inherent in the base polyamide, the copolymerization of the sulfonated aromatic dicarboxylic acid is preferably about 0.25 to 3 mol% based on the monomers of the base polyamide.

This modified polyamide may contain a matting agent such as titanium oxide.However, in order to sufficiently transmit the color of the core polyester and obtain excellent coloration, a matting agent or other pigment is required. Are preferably not substantially contained.

In addition, these polyamides may contain an antistatic agent, a heat-resistant agent, a light-resistant agent, and the like as long as they do not significantly reduce the light transmittance.

The modified polyester used for the core in the present invention is a modified polyester in which a compound having a sulfone group is contained in a part of a chain or a terminal of the polyester.
No. 34-10497. This modified polyester is a modified polyester obtained by copolymerizing a sulfonated aromatic dicarboxylic acid or a salt thereof with polyethylene terephthalate, polybutylene terephthalate, or a copolymer polyester containing these as a main component.

Representative examples of the sulfonated aromatic dicarboxylic acid include 5-sulfoxyisophthalic acid represented by the above formula [I] or a salt thereof.

These dicarboxylic acids are added during the polymerization of the polyester in a free acid state or an alkyl ester state and are copolymerized to produce a modified polyester. The copolymerization amount of the sulfonated aromatic dicarboxylic acid is preferably about 0.5 to 6 mol% based on terephthalic acid. If the copolymerization amount is too low, it is difficult to obtain the desired effect of the modified polyester. On the other hand, if it is too large, the crystal structure of the modified polyester is disturbed, and undesired phenomena such as a significant decrease in mechanical properties occur.

In addition, these modified polyesters may contain an antistatic agent, a light-proofing agent, a heat-resistant agent, a matting agent, and the like.

The cation type fluorescent whitening agent referred to in the present invention is a fluorescent whitening agent which selectively dyes a sulfonic acid group or a carboxylic acid group, for example, Uvitex BAC (manufactured by Nippon Ciba Geigy Co., Ltd.), Hostalux NR (Hoechst Japan Co., Ltd.
Mikawhite ACR liq (manufactured by Nippon Kayaku Co., Ltd., manufactured by Mitsubishi Kasei Kogyo Co., Ltd.), and the like, but are not limited thereto.

The acid dye referred to in the present invention includes Diacid (manufactured by Mitsubishi Kasei Kogyo Co., Ltd.), Kayacyl, kayanol (manufactured by Nippon Kayaku Co., Ltd.),
Dyes having a crown name such as Mitsui Nylon (manufactured by Mitsui Toatsu Chemical Co., Ltd.) are exemplified, but not limited thereto.

The conjugate fiber referred to in the present invention is a core / sheath composite yarn forming a core / sheath, and the sheath component is the polyamide as described above, and the core component is the modified polyester as described above.

The composite ratio of the core and the sheath can be arbitrarily set as long as the effect of the present invention is not lost, but it is easy to form a uniform and stable coating, and the whiteness of the core polyester is sufficient to obtain a desired whiteness. From the viewpoint, the polyamide ratio is preferably 20 to 75% by weight.

The arrangement of the sheath polyamide and the core modified polyester,
A concentric core-sheath shape may be used, but an eccentric core-sheath shape is preferable because the hue change is larger. The cross-sectional shape of the single fiber of the core-sheath composite fiber is preferably a triangular or polygonal cross section rather than a round shape, and more preferably a flat cross section. However, if the sheath becomes too thin due to the irregular cross section, the sheath may be broken. Therefore, it is necessary to consider the thickness of the sheath when setting the core-sheath composite ratio. Preferred examples are shown in FIGS. 1 (a) to 1 (f).

From the viewpoint of obtaining sufficient whiteness, preventing the yellowing phenomenon, and preventing the decrease in whiteness caused by the contamination by the colored dye incorporated in the fluorescent whitening agent, dyeing of a cationic type fluorescent whitening agent The ratio is preferably from 0.2 to 2.5% owf, more preferably from 0.4 to 1.4% owf, based on the core-modified polyester.
Here, the unit of% owf of the dyeing ratio means the amount of the dyed cationic type fluorescent whitening agent with respect to the core-modified polyester in the single fiber.

A small amount of cationic fluorescent whitening agent may be dyed on the polyamide of the sheath, but the dyeing rate is 10% of the cationic fluorescent whitening agent dyed on the modified polyester of the core.
% Or less. Cationic fluorescent brightener
If the sheath polyamide is dyed or contaminated in an amount exceeding 10%, the pearl tone effect, which is the object of the present invention, is not sufficiently exhibited.

The dyeing rate of the acidic chromatic dye to be dyed on the sheath polyamide is 0.002 to 0.05% owf with respect to the sheath polyamide. If the dye dyeing rate is higher than this range, it is difficult to say that the color is a pearly tone based on white, and it is close to a chromatic fluorescent dye dyed product. On the other hand, if the amount is too small, the change in color appearance is poor, and the object of the present invention cannot be satisfied. Here, the unit of% owf of the dyeing ratio means the amount of the dyed acidic chromatic dye with respect to the sheath polyamide in the single fiber.

This core-sheath type composite fiber is made by a conventional method,
The product may be dyed according to the present invention.

First, a polyamide and a modified polyester are separately melted, guided to a spinning pack section, formed into a composite stream by a conventional method so as to form a core-sheath structure, and spun from a nozzle.

The spun filament yarn is taken up and refueled at a predetermined speed, and then wound up into a package. Next, the wound yarn is stretched as usual using a draw twister so that desired strength and elongation can be obtained. This stretching may be performed continuously without winding after winding the spun yarn, and winding may be performed.
Alternatively, a method of obtaining desired fiber performance at a stroke at a high speed of 4000 m / min or more may be adopted.

As a direct spin drawing method, for example, the spun yarn is 100 to 500
A method of taking at 0 m / min, successively stretching, and heat-stretching at 3500 to 5500 m / min.

The dyeing rate of the sheath or the core is determined by the following method.

<Dyeing ratio of sheath part> Products such as dyed conjugate fibers or their fabrics are
A fixed amount (200 mg) is weighed and immersed in 30 ml of a 88% solution of formic acid at 30 ° C. for 3 minutes to dissolve the sheath polyamide and the dye dyed therein, and then use a colorimeter “Spectro Photometer” U-3400 ( The absorbance at the maximum absorption wavelength is measured by Hitachi, Ltd.). In addition, weigh a certain amount (200 mg) of the sample before staining, and
A predetermined amount (0.25 mg, 0.5 mg, or 1.0 mg) of the dye is dissolved in 30 ml of a 88% solution of formic acid at 30 ° C., and the absorbance is determined by a colorimeter. The relationship between the absorbance and the dyeing rate of this dye is determined. Plot as a calibration curve. From this calibration curve, the value of the amount of dyeing (a% owf) is determined from the value of the absorbance of the sheath polyamide in the actual dyeing described above.

<Dye Dyeing Rate of Core> First, after dissolving and removing the sheath polyamide in the conjugate fiber or its products, the dyed fiber of the core-modified polyester is obtained by washing with water. A certain amount (100 mg) of the dyed fiber is weighed, placed in 30 ml of a phenol / ethane tetrachloride mixed solution (weight ratio 3: 2), and completely dissolved at about 60 ° C., and then maximally measured by the same colorimeter as described above. Measure the absorbance at the absorption wavelength. Further, using the modified polyester fiber taken out from the sample before dyeing, a calibration curve showing the relationship between the absorbance and the dyeing rate was obtained in the same manner as described above, and from this calibration curve, the core modification in the actual dyeing described above was obtained. The value of the amount of dyed polyester (b% owf) is determined.

From the dye dyeing amount (a% owf) of the sheath portion and the dye dyeing amount (b% owf) of the core portion, the dyeing ratio of the sheath portion to the core portion is calculated by (a / b) × 100. calculate.

The following three-stage evaluation was performed for the pearl-like discoloration effect based on the sensation judgment by four panelists.

 ：: good, Δ: slightly good, ×: bad Hereinafter, examples will be described in more detail.

[Example] A polyethylene terephthalate raw material composed of ethylene glycol and terephthalic acid was added with a catalyst and 5
-Sulfoxyisophthalic acid to terephthalic acid 1.5
Mol%, polymerized, and modified polyethylene terephthalate with an intrinsic viscosity of orthochlorophenol IV: 0.64 (hereinafter, referred to as
(Modified polyester) was obtained.

This modified polyester and nylon 6 having a sulfuric acid relative viscosity of 2.62 substantially containing no titanium oxide were subjected to an extruder-type composite spinning machine, and each was separately melted. Is formed into a composite flow so that the core and nylon 6 become a sheath, and is discharged, taken up at a speed of 1500 m / min, subsequently heat-set with a drawing hot roller at 160 ° C., and wound up at 4000 m / min. Denier 24
A drawn filament was obtained. The core-sheath conversion rate of the composite fiber is
1/1.

This drawn yarn is used as a warp and a weft, and the plain fabric (warp density 11
8 yarns / inch and a weft density of 85 yarns / inch). 2 g of this plain woven fabric was added to “Sundet” G-29 (manufactured by Sanyo Chemical Co., Ltd.).
In a treatment bath containing 5 g of soda ash, 2 g / of “Detrol” WR-14 (manufactured by Meisei Chemical Industry Co., Ltd.), desizing and scouring were performed at 98 ° C. for 20 minutes, followed by drying and 170 ° C. The intermediate set was performed to prepare a dyeing sample fabric.

(Example 1) A bath of 0.5% owf (1% owf with respect to the core modified polyester) of a fluorescent brightener Uvitex BAC (manufactured by Nippon Ciba Geigy Co., Ltd.) and 0.5 cc / acetic acid as an auxiliary agent was applied to the above cloth. And 110
Stained for 30 minutes at ° C.

Next, Mitsui acid Mill. Turq. Blue 3G (manufactured by Mitsui Toatsu Dye Co., Ltd.) was applied to all the fabrics at 0.01% owf (0.02% owf for the sheath polyamide) (Example 1), and
0.1% owf (0.2% owf with respect to the sheath polyamide) (Comparative Example 1).
Stained for minutes.

The resulting fabric (Example 1, Comparative Example 1) was visually evaluated by four panelists for the presence or absence of a pearl-like discoloration effect. Further, the dyeing amounts of the core and the sheath were determined. Table 1 shows the results.

As can be seen from Table 1, when the amount of the colored dye in the sheath portion was large, the hue of the sheath portion was emphasized, and a different color effect was not recognized.

In Example 1, in which an appropriate amount of the colored dye was present in the sheath portion, depending on the viewing direction and the inclination of the cloth, a pale blue color appeared to emerge from pure white, and a calm and elegant pearl-like heterochromatic effect was observed.

This fabric was particularly prominent outdoors under strong ultraviolet light and under sunlight.

[Effect of the Invention] When the dyed conjugate fiber according to the present invention is used, a fiber product having a pearl-like heterochromic effect that changes from pure white to white including a pale chromatic color depending on the incident angle of light can be obtained. In addition, since the modified polyester layer is present in the core, it has excellent dimensional stability and anti-wrinkle properties, and has a moderate tension and waisted texture. Furthermore, it covers the low light fastness of fluorescent whitening of conventional polyamide fiber fabrics and the sheath is made of polyamide, so it has the same abrasion resistance and resin processability as polyamide fiber fabrics. Have.

Since the composite fiber according to the present invention has these properties,
It can be suitably used for outdoor sportswear such as blouses, skis, and tennis, and blousons.

[Brief description of the drawings]

1 (a) to 1 (f) are examples of preferred cross-sectional shapes of the pearl composite fiber of the present invention. In the figure, 1: sheath polyamide 2: core modified polyester

Continuation of the front page (56) References JP-A-63-112722 (JP, A) JP-A-1-139803 (JP, A) JP-A-56-37312 (JP, A) JP-B-58-22569 (JP) , B2) JP 43-14185 (JP, B1) (58) Fields investigated (Int. Cl. ⁶ , DB name) D01F 8/12-8/14 D06P 3/82-3/87

Claims (1)

(57) [Claims] 1. A composite fiber comprising a polyamide in a sheath and a sulfonated aromatic dicarboxylic acid-modified polyester in a core, and dyed with a cationic fluorescent whitening agent and an acidic colored dye as a dye. Is less than 10% of the dyeing rate of the cationic type fluorescent brightener in the core, and the dyeing rate of the acidic colored dye is 0.002 to Pearl-like composite fiber characterized by being 0.05% owf.