JP3182275B2 - Composite fiber with unique color effect - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite fiber comprising two or more polymers having different coloring properties. More specifically, the present invention relates to a composite fiber comprising two or more polymers having different refractive indices and exhibiting an iridescent color effect.

[0002]

2. Description of the Related Art It is one goal for a person involved in the production of garment fibers to develop an iridescent effect or a two-color effect in a single fiber, and several proposals have been made. For example, an example of man-Made Fibers, which aimed for dichroism by side-by-side structure with acrylic fiber,
Science and Technology, Vol. 1 (1961).

[0003] However, polyester fibers have a number of excellent characteristics as clothing fibers, and despite being widely used, fibers having an iridescent effect consisting of single fibers are still listed on the market. It has not been. In order to give a single fiber a dichroic effect, (1) a composite fiber composed of two or more polymers having different dyeing properties;
(2) It is a necessary condition that the difference in dyeing properties can be sufficiently discerned by the naked eye, and as a material for clothing, (3) it is necessary that the comfort performance represented by the word "feel" is not impaired. . It is very difficult to satisfy such conditions with a polyester fiber, especially (2),
The fact is that practical fibers satisfying the condition (3) have not yet been proposed.

[0004] The composite fiber composed of two kinds of polyesters having different dyeing properties, which is the condition of the above (1), is usually a side-by-side type composite fiber, and the composite fiber has latent crimping property. The dichroism disappeared due to the crimping, and in many cases, it was possible to determine only a mixed color with the naked eye. Furthermore, since the color tone is similar between the two combinations of polyesters, it is very difficult to provide dichroism that can be discerned by the naked eye, and the iridescent effect cannot be obtained unless some optical action is applied. It does not become a presenting fiber.

[0005]

The present invention relates to the above (1)
An object of the present invention is to provide a polyester composite fiber exhibiting an iridescent effect, which satisfies all the conditions of (3) to (3). The present inventors have devised such a point, and as a result, have found that polyethylene terephthalate obtained by copolymerizing a specific compound has a lower refractive index than polyethylene terephthalate, The present invention has been reached.

[0006]

According to the present invention, in a composite fiber comprising at least two kinds of polymers, ethylene terephthalate is used as a main repeating unit, and a compound represented by the following formula (I) is used. 1 to the diol component
A layer composed of polyester A obtained by copolymerizing 20 mol% and / or a compound represented by the following formula (II) with 1 to 20 mol% with respect to a dicarboxylic acid component, and a B layer composed of another component polymer B Have a cross-sectional structure of three or more alternating layers, and the difference in birefringence between the polyester A and the polymer B satisfies the following formula (III).

[0007]

Embedded image (In the formula, m represents 0, 1 or 2.)

[0008]

Embedded image (Wherein, R represents a lower alkyl group or a hydrogen atom, n
Represents 0, 1 or 2. )

[0009]

(Equation 2) (In the formula, ΔnA indicates the birefringence of polyester A, and ΔnB indicates the birefringence of polymer B.)

In the composite form of the composite fiber in the present invention, it is necessary that the polyester A and the other component polymer B are laminated in three or more alternate layers.
FIG. 1 shows a specific example of “alternate layer structure of three or more layers”. (A) to (c) are forms in which three or more layers are laminated alternately in a round cross section, (d) are forms laminated alternately in the long side direction in a flat cross section, and (h) are circularly alternate forms in a round cross section. In the modified cross section, the チ to 形態 are alternately laminated along the modified cross section. In addition, a random composite cross section composed of polyester A and polymer B can be said to be a composite configuration in which three or more layers are alternately laminated, and are included in the composite configuration of the present invention. The layer A made of polyester A is preferably exposed on the fiber surface, and the layer A made of polyester A and the layer B made of polymer B are preferably exposed on the fiber surface alternately. However, even when the fiber surface is covered with the layer A, the iridescent effect, which is the effect of the present invention, is exhibited.

The polyester A is a polyester containing ethylene terephthalate as a main repeating unit and copolymerized with a compound represented by the following formula (I) and / or (II).

As described above, the polyester A contains terephthalic acid as a main dicarboxylic acid component and ethylene glycol as a main diol component, but other dicarboxylic acids other than terephthalic acid include isophthalic acid and phthalic acid.
Naphthalenedicarboxylic acid, biphenyldicarboxylic acid,
4,4'-diphenyletherdicarboxylic acid, 4,4 '
-Diphenylmethanedicarboxylic acid, 4,4'-diphenylsulfonedicarboxylic acid, 4,4'-diphenylisopropylidenedicarboxylic acid, 1,2-diphenoxyethane-4 ', 4 "-dicarboxylic acid, anthracenedicarboxylic acid, 2,5 -Aromatic dicarboxylic acids such as pyridine dicarboxylic acid, diphenyl ketone dicarboxylic acid and sodium sulfoisophthalate; aliphatic dicarboxylic acids such as malonic acid, succinic acid, adipic acid, azelaic acid and sebacic acid; decalin dicarboxylic acid, cyclohexane dicarboxylic acid and the like An alicyclic dicarboxylic acid; β-hydroxyethoxybenzoic acid,
hydroxycarboxylic acids such as p-oxybenzoic acid, hydroxypropionic acid, hydroxyacrylic acid; or carboxylic acids derived from their ester-forming derivatives,
Aliphatic lactones such as ε-caprolactone can be mentioned, and these aromatic dicarboxylic acid units may be contained only in one kind or in two or more kinds, in a proportion of 10 mol% or less based on all dicarboxylic acid components. .

The diol components other than ethylene glycol include trimethylene glycol, tetramethylene glycol, hexamethylene glycol, neopentyl glycol, diethylene glycol, polyethylene glycol and the like. Aliphatic diols; hydroquinone, catechol,
Naphthalene diol, resorcinol, bisphenol A,
Aromatic diols such as ethylene oxide adduct of bisphenol A, bisphenol S, and ethylene oxide adduct of bisphenol S; and alicyclic diols such as cyclohexane dimethanol. These diols may be used alone or in combination of two or more, and may be contained in a proportion of 10 mol% or less based on all diol components.

The polyester A of the present invention may further comprise a polycarboxylic acid such as trimellitic acid, trimesic acid, pyromellitic acid, and tricarballylic acid within a range where the polyester is substantially linear; glycerin, trimethylolethane, and the like. And polyhydric alcohols such as trimethylolpropane and pentaerythritol.

When only the compound represented by the formula (I) is copolymerized, its copolymerization amount is 1 to 20 mol%, preferably 2 to 1 mol%, based on all the diol components constituting the polyester.
The range is 5 mol%. When only the compound represented by the formula (II) is copolymerized, its copolymerization amount is in the range of 1 to 20 mol%, preferably 2 to 15 mol%, based on all dicarboxylic acid components. When the compounds of the formulas (I) and (II) are used as the copolymerization component, the copolymerization amount thereof is 1 to 20 mol%, and 2 to 15 mol%, based on the total dicarboxylic acid component. Is preferably within the range.

When the copolymerization amount of the compound represented by the formula (I) and / or the compound represented by the formula (II) is less than 1 mol%, the crystallinity of the polyester A decreases, the refractive index decreases, and the fiber Is insufficient in the birefringence upon orientation, and the composite fiber with polymer B has a small heterochromatic effect and an iridescent effect. On the other hand, when the copolymerization amount of the compound is 20 mol%
If the temperature exceeds the above range, it is difficult to obtain a crystalline resin, and even if it is obtained, its melting point is low and it does not satisfy the heat resistance required for polyester fibers. Further, as the copolymerization amount of the compound represented by the formula (I) or the compound represented by the formula (II) increases, the crystallinity and melting point of the polyester decrease.
Since the different color effect and the iridescent effect of the conjugate fiber composed of B are improved, the copolymerization amount may be changed in consideration of the heat resistance, the different color effect, the iridescent effect and the like required for each fiber application.

The intrinsic viscosity of the polyester A according to the present invention [phenol / tetrachloroethane (weight ratio 50/5)
0) measured at 30 ° C. using a mixed solvent] is preferably in the range of 0.4 to 1.5 from the viewpoint of fiber-forming properties.

[0018] Other ingredients polymer -B according to the present invention, the birefringence △ n _B is the birefringence △ n _A and the following conditions are met polymer polyester A - limited to the type if Not something.

[0019]

(Equation 3)

If the difference in the birefringence between the polyester A and the polymer B does not satisfy the above conditions, the composite fiber does not exhibit the effects of the present invention, that is, the iridescent effect.

Examples of the polymer B include polyester, polyamide, polyolefin and the like.
Polyester is preferable in terms of adhesiveness to the polyester A and the like, and a polyester in which the compound represented by the above formula (I) and / or the formula (II) is not copolymerized, or the above formula (I) and / or the formula ( Polyesters which are not copolymerized with the compound represented by II) and which are obtained by copolymerizing the copolymer components described above are preferred. Of these, polyethylene terephthalate dyeable with a disperse dye and polyethylene terephthalate dyeable with a cationic dye are preferred.

These composite fibers of polyester A and polymer B can be produced by a known method for producing composite fibers. For example, in order to obtain fibers of the composite form shown in FIGS. 1 (e), 1 (h) and 1 (l), a three-layer concentric composite flow of a two-component polymer is formed before reaching the spinning nozzle introduction hole. It is obtained by discharging from a round hole nozzle, a triangle shaped nozzle, and a flat shaped nozzle. In addition, in order to obtain a composite form fiber shown in FIGS.
In the spin pack, the two-component polymer is passed through a static mixer with an arbitrary number of elements to form a two-component multi-layer composite flow. Obtained by: Further, in order to obtain the composite form fibers shown in FIGS. 1 (a) to 1 (d), a multi-layer laminating flow of a two-component polymer is formed before reaching the nozzle introduction hole and then discharged from the nozzle. Obtainable. By changing the shape of the nozzle, a multi-layer alternately laminated fiber having an irregular cross section can be obtained.

The polyester A and the polymer B are represented by the formula (III)
As long as the birefringence difference represented by is satisfied, there is no need to particularly limit the composite ratio, but A / B = 1/3 to 3/1.
(Weight ratio) is preferable, and outside of this range, it is difficult to sufficiently exhibit a heterochromatic effect and an iridescent effect. As the conjugate fiber of the present invention, those having a single fiber fineness of 5 denier or less and a total denier of 200 denier or less are usually used.

The reason why the conjugate fiber of the present invention exhibits a heterochromatic effect and an iridescent effect cannot be clearly explained at present, but can be presumed as follows. That is, the polyester A obtained by copolymerizing the compound represented by the formula (I) and / or the formula (II) is polyethylene terephthalate.
Since the refractive index is lower than that of
Transmission and reflection of visible light repeatedly occur at the interface between each layer of the layer A made of polyester A and the layer B made of polymer B, which satisfies the following condition. It is considered that a typical color effect is exhibited. When a polymer B which does not satisfy the formula (III) is used, an unusual color effect and an iridescent effect are not sufficiently exhibited, and only a mixed color of a color obtained by fiberizing and dyeing the polyester A and the polymer B is visually observed. can not see.

To lower the refractive index of the polyester,
It is effective to reduce the mutual induction of polarization in the direction of the fiber axis, and to reduce the number of benzene rings having conjugated double bonds in the main chain of polyester, particularly polyethylene terephthalate, or to reduce the orientation. Need to disturb,
There is also a method of introducing an aliphatic dicarboxylic acid or the like instead of terephthalic acid having a benzene skeleton, but in this method,
Since the glass transition temperature of the polymer is lowered, the heat resistance becomes poor, and not only the fiberization processability becomes poor, but also the performance of the fiber product is lowered. In the present invention, the compound represented by the formula (I) and / or the formula (II) is copolymerized as the polyester A, and an aliphatic cyclic skeleton is introduced into the main chain of the polyester to lower the glass transition temperature. Instead, it was possible to lower the crystallinity of the polyester and lower the refractive index of the polyester.

The polyester A is used as one component,
Further, a polymer having a specific birefringence was selected as the polymer B as another component, and a fiber exhibiting a different color effect and an iridescent effect, which had not been obtained conventionally, was obtained by compounding. .

In dyeing the conjugate fiber of the present invention, various dyes can be used. The polyester A and the polymer B may be dyed with the same type of dye such as a disperse dye and a cationic dye, or may be dyed with different types of dyes such as a disperse dye and a cationic dye. Further, the dyed yarn kneaded with the dye during spinning may be further dyed with a disperse dye or the like. In the composite fiber of the present invention, if necessary, an ultraviolet absorber, a fluorescent whitening agent, a matting agent, an antistatic agent, a flame retardant, a flame retardant auxiliary agent, and a lubricant within a range that does not impair the effects of the present invention. , A plasticizer, an inorganic filler, and the like.

[0028]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples. In addition, each physical property in an Example was measured by the following methods. (1) Copolymerization ratio (mol%) of compounds represented by formulas (I) and (II) Calculated based on the ¹ H-NMR measurement results of the polyester according to the present invention, using deuterated trifluoroacetic acid as a solvent. did.

(2) Intrinsic viscosity of polyester (dl /
g) Phenol / tetrachloroethane (weight ratio 50/50)
Was measured at 30 ° C. using a mixed solvent of

(3) Physical properties of polyester Glass transition temperature of polyester (hereinafter abbreviated as Tg)
(° C) and melting point (hereinafter abbreviated as Tm) (° C)
Scanning Calorimeter (Metra-TA3000, Par
Kinelmer Co., Ltd.), using a 10 mg sample, measuring the temperature while increasing and decreasing the temperature at a rate of 10 ° C./min while performing nitrogen replacement. This operation was repeated twice with the same sample, and the second measurement was performed. And The heat of crystal fusion (J / g) after the sample was heat-treated and sufficiently crystallized was measured by the above-mentioned apparatus, and the result was shown as the crystallinity.

(4) Birefringence: A 75-denier / 24-filament drawn yarn obtained by spinning and drawing polyester A and polymer B under the same conditions (drawing ratio is 0.7 times the cutting draw ratio). Was measured in α-bromonaphthalene with a polarizing microscope using a Na light source.

Example 1 Perhydrodimethanonaphthalenediethanol [Formula (I)
A compound having m = 1 in the compound of formula (1)] from a diol raw material consisting of 6.7 mol% and 93.3 mol% of ethylene glycol and terephthalic acid, the molar ratio of diol raw material: terephthalic acid is A slurry was formed by adjusting the ratio to 1.2: 1, and the slurry was pressurized (absolute pressure: 2.
5 kg / cm ² ) at a temperature of 250 ° C. and an esterification rate of 95
% To carry out an esterification reaction to produce a low polymer. Next, 350 ppm of antimony trioxide was added as a catalyst, and the pressure was reduced to 1.5 at 280 ° C. under a reduced pressure of 1 torr absolute.
Polycondensation of low polymer for a time, 0.65 dl / g intrinsic viscosity
Was produced. This copolymerized polyester resin was extruded from a nozzle into a strand shape and cut to produce a columnar chip having a diameter of 2.8 mm and a length of 3.2 mm.

The obtained copolyester chips were treated with ¹ H
The polyester was analyzed by NMR.
It was confirmed that hydrodimethanonaphthalenediethanol was copolymerized in 8 mol% of all dicarboxylic acid units.
Further, the Tg of the obtained copolyester chips was 83
° C, Tm were 232 ° C, and ΔH was 28 J / g. This copolymerized polyester is referred to as polyester A.

As the polymer B, polyethylene terephthalate obtained by copolymerizing 1.7 mol% of sodium 5-sulfoisophthalate is polymerized by an ordinary method and has an intrinsic viscosity of 5.5.
dl / g of pellets were obtained. Polyester A (A component)
And polymer-B (component B) at A / B = 1/1, and spun from a slit nozzle so as to have a flat cross section as shown in FIG. Then, it was stretched 3.2 times with a roller plate type drawing machine,
5 denier / 12 filament drawn yarn was obtained.

Using the drawn yarn, a woven fabric having a warp density of 130 yarns / inch and a weft yarn density of 85 yarns / inch was obtained. Dyeing conditions were performed under the following conditions, and finishing was performed by an ordinary method. Dye Cathilon Blue CD-FBLH 1% owf Dianix Yellow F3G-E 2% owf Aid Na ₂ SO ₄ 1g / liter CH ₃ COOH 1% ow CH ₃ COONa 0.5% ow dia. : 1 Dyeing temperature 120 ° C Dyeing time 60 minutes

The woven fabric has a single yarn denier of 6.25 denier.
Despite being thick and thick, it was soft and swelled, and became a high-quality fabric with a silky touch with a dry touch. In addition, depending on the viewing direction, the image becomes yellow-rich or green-rich and has a unique iridescent tone.

Comparative Example 1 An 11-layer laminated conjugate fiber was spun and drawn in the same manner except that polyethylene terephthalate having an intrinsic viscosity of 0.65 dl / g was used as the component A. Weaved and dyed. The dyed fabric did not show any discoloration effect, and only the whole fabric appeared as a neutral yellow-green color.

Comparative Example 2 The component A and the component B used in Example 1 were spun using a side-by-side type composite slit type nozzle, and 3.7 times with a roller plate type drawing twisting machine. Stretched. The obtained drawn yarn had latent crimpability, and had a number of crimps of 8 pieces / inch, and when subjected to boiling water shrinkage treatment, had a number of crimps of 20 pieces / inch. Using this drawn yarn, a tubular knitted fabric was prepared and dyed in the same manner as in Example 1. However, no dichroism was observed, and only the entire knitted fabric was viewed as an intermediate yellow-green color. Was.

Examples 2 to 5 Composite fibers were spun and drawn in the same manner as in Example 1 except that polyethylene terephthalate obtained by copolymerizing the compounds shown in Table 1 was used as the component A to prepare a woven fabric. Staining was applied.
The woven fabric after dyeing had good feeling and had a unique iridescent tone.

Example 6 In Example 1, the composite form of the component A and the component B is shown in FIG.
Spinning and stretching were performed in the same manner as in (f) except that the fabric was prepared and dyed. The woven fabric after dyeing had good feeling and had a unique iridescent tone.

Comparative Examples 3 and 4 As the A component, polyethylene terephthalate obtained by copolymerizing the compounds shown in Table 1 was polymerized to produce a fiber. However, since the A component was amorphous, it was difficult to obtain a fiber at the time of stretching. Yarn breakage occurred frequently, and satisfactory conjugate fibers could not be obtained.

[0042]

[Table 1]

[0043]

The composite fiber of the present invention has a so-called beetle effect in which the composite fiber exhibits a different color depending on the viewing angle, and is useful for various fiber products because of the features not found in the conventional polyester composite fiber.

[Brief description of the drawings]

FIG. 1 is a preferred composite form of the composite fiber of the present invention.

[Explanation of symbols]

 A: Polyester A B: Polymer B

──────────────────────────────────────────────────続 き Continuation of front page (58) Field surveyed (Int.Cl. ⁷ , DB name) D01F 8/14 D01F 6/84 C08L 67/00-67/08 C08G 63/00-67/91

Claims (1)

(57) [Claims] 1. A composite fiber comprising at least two kinds of polymers, wherein ethylene terephthalate is a main repeating unit and a compound represented by the following formula (I) is
1 to 20 mol% based on the dicarboxylic acid component and / or 1 to 20 mol% based on the dicarboxylic acid component.
A consisting of polyester A obtained by copolymerization of up to 20 mol%
The layer and the layer B composed of the other component polymer B have a cross-sectional structure of three or more alternating layers, and the difference in birefringence between the polyester A and the polymer B satisfies the following formula (III). A conjugate fiber characterized by the above. Embedded image (In the formula, m represents 0, 1, or 2.) (Wherein, R represents a lower alkyl group or a hydrogen atom, n
Represents 0, 1 or 2. ) (Equation 1) (In the formula, ΔnA indicates the birefringence of polyester A, and ΔnB indicates the birefringence of polymer B.)