JPH0140137B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel knitted fabric made of a mixture of polyester fiber and polyurethane fiber. More specifically, as defined later, polyester fibers made of a homopolymer of polyethylene terephthalate and capable of being dyed under normal pressure with disperse dyes (hereinafter referred to as normal pressure dyeable polyester) are mixed with polyurethane fibers under normal pressure. This method provides a knitted fabric that can be dyed (hereinafter referred to as a mixed knitted fabric), and this mixed knitted fabric has good texture and mechanical properties that cannot be obtained by high-temperature and high-pressure dyeing. Conventional polyethylene terephthalate fiber is
Because it was a difficult-to-dye fiber that could only be dyed under high temperature and high pressure conditions of 120 to 130°C, there were restrictions on the production of mixed products with fibers such as polyurethane fibers whose mechanical properties significantly deteriorate under high temperature and high pressure conditions. Ta. For example, in the case of a knitted fabric made of a mixture of polyurethane fibers and polyethylene terephthalate fibers, a so-called yarn dyeing method has conventionally been used in which the polyethylene terephthalate fibers are dyed at high temperatures and pressures of 120 to 130°C to knit the fabric. When it comes to yarn dyeing of elastic fibers such as polyurethane fibers, it is extremely difficult to uniformly dye the fibers industrially, whether in the form of combs or cheeses, and in the yarn dyeing method, polyurethane fibers are used without being dyed. Therefore, when the knitted fabric is stretched after being made into a mixed knitted fabric, the undyed polyurethane fibers appear white, resulting in a so-called peeling phenomenon, which significantly reduces the quality of the product. In addition to these light dyeing methods, in some cases, the polyethylene terephthalate fibers are dyed without pre-dying and are dyed with a carrier such as o-phenylphenol, methylnaphthalene, chlorobenzene, or methyl salicylate after being patterned by a conventional method. After adding an accelerating dye called ``Dye Bath'' to a dye bath containing a disperse dye and dyeing at a temperature of around 100°C, other fibers were dyed using conventional methods. When using this carrier dyeing method, the dyeing density is inferior to high-temperature and high-pressure dyeing, staining spots called carrier spots caused by insufficient emulsification of the carrier may occur, and the carrier is irritating. It is harmful to the human body, which worsens the working environment of dyeing factories; it is difficult to treat dyeing waste water; and the light fastness of dyed products decreases because the carrier remains in the fibers and is difficult to remove. There is a risk of skin damage if the residue is worn, and carrier dyeing may cause changes in the mechanical properties of polyethylene terephthalate fibers, such as a decrease in strength.
Furthermore, most carriers for polyester have a more pronounced effect on polyurethane fibers than on polyester fibers, resulting in excessively deep dyeing of polyurethane fibers and a consequent decrease in color fastness. There were many drawbacks, such as deterioration of the physical properties of polyurethane fibers due to Furthermore, when a knitted fabric made of a mixture of polyester fibers and polyurethane fibers is dyed at high temperature and high pressure, the disperse dye for polyester is excessively adsorbed to the polyurethane fibers, resulting in a significant decrease in color fastness. Another problem is that the dyed polyurethane fibers become visible when the knitted fabric is stretched when worn, resulting in a lack of color consistency, since the color density does not match that of the polyester fibers. One way to improve these problems is to use a limited number of disperse dyes with specific dyeing properties, but this method only yields products with certain color densities. Also, as another method,
It is conceivable to remove the excessively dyed disperse dyes from the polyurethane fibers by repeating intensive soaping or reduction washing after high-temperature and high-pressure dyeing, but this requires a long process and also prevents the use of compound dyes. In the case of dyeing, each component dye is not removed in a well-balanced manner, resulting in problems such as markedly different hues.In the end, it is not possible to obtain a product that is economical, has good fastness, and has good color consistency between polyester and polyurethane fibers. That was the reality. Dyeing under normal pressure does not require a pressure-resistant dyeing machine, which is economically advantageous in terms of equipment and safety management. It also reduces energy costs and significantly reduces the time required for temperature rise and cooling. You can save money. In addition, polyester fibers with improved dyeability are known that are copolymerized with metal sulfonate group-containing compounds or polyether, but although these modified polyesters have improved dyeability,
In dyeing under normal pressure, i.e., below 100℃, the dye density is not necessarily sufficient, polymerization and spinning are difficult, the cost increases due to high raw materials, or the excellent mechanical properties of polyethylene terephthalate are difficult to achieve. reduce thermal properties,
Other drawbacks included poor color fastness. In the end, when chemically modifying a polymer to make it easier to dye as described above, a third component that can serve as a dyeing seat is mixed into the polymer, so it is inevitable that polyethylene terephthalate's original excellent heat resistance and mechanical properties will deteriorate. be. The present inventors completed the present invention as a result of research into a knitted fabric made of a mixture of polyurethane fiber and polyester fiber that overcomes the drawbacks of the prior art. That is, the present invention provides a knitted fabric made of a mixture of polyurethane fiber and polyester fiber,
The present invention is a knitted fabric made of a mixture of polyurethane fibers and polyester fibers, characterized in that the polyester fibers are essentially made of a homopolymer of polyethylene terephthalate and can be dyed under normal pressure with a disperse dye. The polyester fiber of the present invention, which consists essentially of a homopolymer of polyethylene terephthalate and can be dyed under normal pressure with a disperse dye, is a novel fiber and can be produced by the method described below. "Can be dyed at normal pressure with disperse dye" means disperse dye C.I. Disperse Blue 56 (CI Disperse Blue 56)
Disperse Blue56; e.g. Resolin Blue FBL
Using [Bayer GmbH product name of the Federal Republic of Germany],
100 in a dye bath with a dyeing amount of 3% owf, bath ratio 50 times, pH 6 (adjusted with acetic acid), and dispersant (e.g. Disper TL [product name of Meisei Chemical Industry Co., Ltd.]) content of 1 g/.
After dyeing at ℃ for 120 minutes, the exhaustion rate of the dye attached to the fiber is 80% or more. Here, the dye exhaustion rate is expressed by the following formula. Dye exhaustion rate (%) = Amount of dye dyed on the fiber (weight) / Amount of dye added to the dye bath (weight) x 100 In addition, after dyeing under the above dyeing conditions, the dyed fiber was treated with 1 g of sodium hydrosulfite. /, sodium hydroxide 1g/aqueous solution, 50 times the bath ratio, 80
Reduction cleaning at ℃ for 20 minutes, washing with water, light fastness (according to JIS L-1044 carbon arc lamp method), friction fastness (according to JIS L-0849 crocmeter method), and sublimation fastness (JIS L-1044 carbon arc lamp method) (according to L-0854)
When measured, all showed grade 3 or higher. In conventional polyethylene terephthalate fibers, the dye exhaustion rate under the above conditions is 30 to 45%. However, under the above conditions, if the dyeing temperature is changed from 100℃ to 130℃, the conventional polyethylene terephthalate fiber will be 80%
Indicates a value of % or more. The mixed knitted fabric referred to in the present invention is a new knitted fabric, and is composed of polyester fibers and polyurethane fibers. For example, yarns that are mixed before knitting or mixed and twisted in the twisting process, yarns that are mixed in the same loop by being aligned and fed to knitting needles during knitting, and polyester yarns and polyurethane yarns that are used individually during knitting. There are those that are supplied to knitting needles and have their respective loops intermingled in the knitted fabric for mixed use, and those that are inserted in the warp direction or weft direction without forming loops during knitting and are used mixedly. The knitted fabrics of the present invention using a mixture of polyethylene terephthalate fibers (with and without bulk processing, and those using both at the same time) and polyurethane fibers can be dyed to the same density as conventional dyed fabrics even when dyed under normal pressure. Because it is possible,
A knitted fabric mixed with polyester fibers whose mechanical properties are severely degraded when dyed under high temperature and high pressure can be dyed by an economically advantageous piece dyeing method without using the conventional yarn dyeing method. The mixed knitted fabric of polyester and polyurethane fibers obtained by this piece dyeing method has superior texture and mechanical properties compared to those obtained by the conventional yarn dyeing method. be. In order for the polyester fiber made of a homopolymer of polyethylene terephthalate to maintain its mechanical performance as a clothing fiber, it is preferable that the initial modulus at 30°C is 55 g/d or more. In addition, in order for normal pressure dyeing to be possible with disperse dyes, the peak temperature (Tmax) of mechanical loss tangent (tanδ) at a measurement frequency of 110Hz must be 105℃ or less, and tanδ
It is preferable that the peak value ((tan δ) max) of is greater than 0.135. Note that this structural characteristic value applies to polyethylene terephthalate fibers that are not subjected to bulking processing, and polyethylene terephthalate fibers that have been subjected to normal false twisting processing, friction false twisting processing, and injection bulking processing [(tan δ)
max] is 0.08 or more, and (tanδ)max≧
It is preferable to satisfy the following relationship: (Tmax−105)×10 ⁻² . The above values of Tmax and (tan δ)max are appropriate as characteristic values expressing the structure of the amorphous region.
Tmax is usually located 50°C higher than the glass transition temperature, and (tan δ)max is related to the amount of molecular chains in the amorphous region with activated thermal motion at temperature Tmax.
In the present invention, Tmax and (tan δ)max refer to values related to mechanical absorption (αa absorption) caused by micro-Brownian motion of molecular chains inside the amorphous region. The Tmax of conventional non-bulking polyethylene terephthalate fiber is 130℃ or more,
(tan)max is 0.13 or less. In addition, conventional polyethylene terephthalate fibers that have been bulk-processed
Tmax is 135°C or higher, and (tanδ)max is 0.13 or lower. As a result of examining the relationship between the structure of the amorphous region of the fiber made of polyethylene terephthalate homopolymer constituting the mixed knitted fabric and dyeability, we found that (tan δ) max >
It is preferable that Tmax is 0.135 and Tmax<105°C. As mentioned above, for bulky textured yarn, (tanδ)max≧0.08 and (tanδ)max≧(Tmax−105)×105)
It is preferable to satisfy the relationship ×10 ⁻² . In the case of conventional fibers made of polyethylene terephthalate homopolymers that are not dyeable under atmospheric pressure, there is no fiber that satisfies the above three conditions. In other words, conventional fibers made of polyethylene terephthalate homopolymers do not satisfy the above three conditions, and none exist that can be dyed under normal pressure. In order to further improve the dyeability of the fiber of the present invention, which is made of a homopolymer of polyethylene terephthalate that is not subjected to bulk processing and can be dyed under normal pressure, it is preferable that (tan δ) max is 0.14 or more. Further, for fibers processed to be bulky, (tan δ) max is preferably 0.11 or more. In the present invention, in order to obtain the mechanical properties of the polyethylene terephthalate fibers that can be dyed under normal pressure with the disperse dyes constituting the mixed knitted fabric, it is necessary to
It is preferable that the initial modulus at °C is 55 g/d or more. Here, the initial modulus at 30°C is expressed as the dynamic elastic modulus (E′ ₃₀ ) at 30°C. As (tan δ)max increases, E′ ₃₀ generally needs to increase in order to maintain shape retention. If E' ₃₀ is less than 55 g/d, the thermal stability of the fiber structure will be lowered, and the dimensional stability will also be poor, making the fiber soft. Regarding the fibers made of homopolymer of polyethylene terephthalate that can be dyed under normal pressure with disperse dyes and which constitute the blended knitted fabric of the present invention having these characteristics, we will further explain its structure and mechanical properties (strength, elongation, initial modulus, dynamic elastic modulus). ), and the relationship with stainability, the following points became clear. In the fiber made of a homopolymer of polyethylene terephthalate that can be dyed under normal pressure with a disperse dye and which constitutes the mixed knitted fabric of the present invention, the degree of crystallinity (Xc)
The size of microcrystals on the (010) plane (ACS) and the degree of crystal orientation on the (010) plane (CO) are both related to the mechanical properties of the fiber. Strength (3
g/d or more), and initial modulus (55 g/d
(above)), for fibers that have not been subjected to bulk processing, it is preferable that Xc be 30% or more, ACS be 35 Å or more, and CO be 85% or more. More preferably, Xc is 70% or more, ACS is 40Å or more,
CO is over 90%. Here, Xc, ACS, and CO are values measured by X-ray diffraction using the methods described below. Conventional unbulked polyethylene terephthalate fibers have an Xc of 50-70% and an ACS
is less than 30 Å and CO is 85-95%. Next, in the polyethylene terephthalate fiber that is not subjected to bulk processing and can be dyed under pressure, which constitutes the mixed knitted fabric of the present invention, the central refractive index (η _(p) ) of polarized light having an electric field vector in the fiber axis direction is smaller than 1.70, and If it is 1.65 or more, it has appropriate elongation (20 to 70%) and dyeability, and is preferable as a clothing fiber. The optimal range of (η _(p) ) is 1.65 to 1.68. In addition, the average birefringence (△η) is determined because the polyethylene terephthalate fibers, which can be dyed under normal pressure with disperse dyes and which are not subjected to bulk processing and which constitute the mixed knitted fabric of the present invention, have an initial modulus of 55 g/d or more at 30°C. 35×10 ^-3 or more is preferable, but on the other hand, from the viewpoint of structural stability against heat, it is desirably 50×10 ^-3 or more. In addition, from the viewpoint of dyeability and color fastness, it is preferably 120×10 ^-3 or less, more preferably 85×
10 ^-3 or less. When △η becomes less than 120×10 ^-3
Dynamic elastic modulus (E′) in the temperature range of 150-220℃
The rate of decrease in (expressed as E' ₂₂₀ /E' 150, where the values of E' at 150℃ and ₂₂₀ ℃ are E' ₁₅₀ and E' ₂₂₀ , respectively) becomes smaller, and E' ₂₂₀ /E' ₁₅₀ becomes larger than 0.75. . In other words, the structure becomes stable against heat. The color fastness is also improved. Further, when Δη is smaller than 85×10 ⁻³ , the dyeability under normal pressure is extremely excellent. A so-called fiber that satisfies the following relationship between the average refractive index (η _(p) ) at the fiber center and the refractive index η _(0.8) or η _(-0.8) at a distance of 0.8 times the radius from the fiber center. If the local average refractive index distribution is symmetrical with respect to the center of the fiber, it will have sufficient strength and have little staining, strong elongation, etc. Here, the local average refractive index distribution is said to be symmetrical with respect to the center of the fiber if the minimum value of the average refractive index η is (η _(p) −10×10 ⁻³ ) or more, and η _(0.8)
The difference between and η _(0.8) is 50×10 ^-3 or less, more preferably,
This refers to the case of 10×10 ^-3 or less. Note that the above η ₍₀₎ ,
The values of η _(0.8) , η _(-0.8) , △ _(0.8-0) , △η, etc. were measured using an interference microscope by the method described below. In addition, in the fibers made of homopolymer of polyethylene terephthalate that are not subjected to bulk processing and can be dyed at normal pressure with disperse dyes and which constitute the mixed knitted fabric of the present invention, the mechanical loss tangent (tan δ ₂₂₀ ) at 220°C is preferably as small as possible. The decrease in initial modulus due to increase becomes smaller. tanδ ₂₂₀
is 0.25 or less, the amount of decrease in the initial modulus becomes significantly small. In other words, it becomes a fiber with a structure that is stable against heat. The fibers made of a homopolymer of bulked polyethylene terephthalate that can be dyed under normal pressure with a disperse dye and which constitute the mixed knitted fabric of the present invention are processed by false twisting, jetting, or pressing the above-mentioned non-bulky fibers by a conventional method. It can be made by etc. As mentioned above, fibers made of homopolymer of polyethylene terephthalate that can be dyed under atmospheric pressure with bulked disperse dyes have an initial modulus of 55 g/d or more at 30°C and (tan δ) max.
0.08 or more and (tanδ)max≧(Tmax−105)×
10 ^-2 is preferable. In addition, the bulky polyethylene terephthalate bulky fibers that can be dyed under normal pressure with disperse dyes and which constitute the mixed knitted fabric of the present invention have an initial modulus at 30°C.
To show above 55g/d, average birefringence (△η)
It is usually sufficient if it is 35×10 ^-3 or more, but this condition is not necessarily a necessary and sufficient condition to provide an initial modulus of 55 g/d or more. The initial modulus is
A sufficient condition for 55 g/d or more is that the value of △η is 45
×10 ^-3 or more, and (tan δ)max is 0.5 or less. In addition, Xc, ACS, and CO all have strong correlations with external deformation of fibers and thermal stability of the structure. Therefore, the bulky fiber has sufficient strength (3
g/d or more), initial modulus (55 g/d or more)
In order to have this, it is desirable that Xc be 30% or more, ACS be 38 Å or more, and CO be 80% or more. More preferably, Xc is 75% or more, ACS is 45Å or more,
CO is more than 85%. Bulky processed fibers such as conventional false-twisted yarns have an Xc of 20-30%, an ACS of about 30Å, and a CO
is approximately 85%. Furthermore, the average birefringence (△η) of the polyethylene terephthalate bulk processed fibers that can be dyed under pressure and which constitute the mixed knitted fabric of the present invention is 45×10 ^-3 or more as described above, but from the viewpoint of thermal stability, it is 50× More preferably 10 ^-3 or more, more preferably 50 × 10 ^-3 or more from the viewpoint of thermal stability, and 110 × from the viewpoint of dyeability and color fastness.
It is 10 ^-3 or less, more preferably 85×10 ^-3 or less. When △η becomes less than 110×10 ^-3 , E′ ₂₂₀ /E′ ₁₅₀ becomes
A value of 0.75 or more improves the thermal stability of the structure. Furthermore, those with Δη smaller than 85×10 ⁻³ have extremely excellent atmospheric dyeability. The Δη of conventional bulk processed fibers is 120×10 ^-3 or more, whereas the bulk processed polyethylene terephthalate fibers that constitute the blended knitted fabric of the present invention have a significantly smaller △η. This is one of the characteristics of the structure. A preferred method for producing fibers made of a homopolymer of polyethylene terephthalate that can be dyed under normal pressure with a disperse dye having the above-mentioned fine structure, constituting the mixed knitted fabric of the present invention, is described in Japanese Patent Application No.
As described in Specification No. 46407 (Japanese Unexamined Patent Publication No. 57-161120), fibers made of polyethylene terephthalate homopolymer spun at a spinning speed of 4000 m/min or more are heated at a temperature of 220°C to 300°C. It can be obtained by heat treatment using dry heat at a certain temperature. Alternatively, it can also be obtained by heat treatment using moist heat using superheated steam, saturated steam, or hot water within a temperature range of 180°C to 240°C. Note that the fibers obtained in this way and subjected to the above heat treatment are dyeable under normal pressure.
Further, bulk processed fibers can be obtained by conventional methods such as false twisting through a spindle, friction false twisting, bulking by pushing, rubbing, or jetting. All of these have the above-mentioned fine structure and can be dyed at normal pressure with disperse dyes. Note that the homopolymer of polyethylene terephthalate, which is the raw material for the fiber made of the homopolymer of polyethylene terephthalate that can be dyed under normal pressure with a disperse dye and which constitutes the mixed knitted fabric of the present invention, can be obtained by a known polymerization method. It may also contain additives commonly used in polyester fibers, such as matting agents, stabilizers, antistatic agents, and the like. Further, there is no particular restriction on the degree of polymerization as long as it is within the range for normal fiber formation. When spinning fibers made of a homopolymer of polyethylene terephthalate that can be dyed under atmospheric pressure with disperse dyes and which constitutes the blended knitted fabric of the present invention, the polymer viscosity, spinning temperature, atmospheric condition under the spinneret, cooling method, take-up speed, etc. By appropriately adjusting the amount, cooling solidification of the polymer stream spun from the spinneret and change in shape can be controlled, and fibers with good spinnability and desired properties can be obtained. In particular, it is important to control the cooling and solidification of spun fibers, and in order to obtain spinnability and desired properties, rapid cooling and solidification, particularly cooling and solidification by low-temperature cooling air perpendicular to the fibers from one direction, is not very desirable. FIG. 1 schematically shows an example of an apparatus for manufacturing a fiber made of a homopolymer of polyethylene terephthalate which can be dyed under normal pressure with a disperse dye and which constitutes the mixed knitted fabric of the present invention. The molten polyethylene terephthalate is spun by a spinneret (not shown) in a heated spinning head 2 and cooled into a fiber bundle 1 in the atmosphere. A tubular heating area 3 surrounding the spun fiber bundle 1 is provided below the spinneret, and a fluid absorption device 4 for cooling and suctioning the fiber bundle 1 is provided below it. The fiber bundle 1 that has passed through the tubular heating zone 3 and the fluid suction device 4 passes through the oil application device 5 and is then taken off by a take-off roller 6 . The spinning speed referred to in the present invention means the surface speed of the take-up roller 6. The taken-off fiber bundle is wound continuously or around a single take-up roller 6 and then pulled out by a pair of fiber bundle feeding rollers 7, and adjusted to an appropriate temperature within the temperature range of 220 to 300°C. The fiber bundle passes through a heated cylinder 8, is guided by a pair of fiber bundle feeding rollers 9, and is wound up by a winding roller 10. At this time, the fiber bundle feed roller 7
By adjusting the rotational speed of the fiber bundles 1 and 9, the fiber bundle 1 is elongated in the cylinder 8 to an appropriate elongation rate and subjected to heat treatment. Fibers made of polyethylene terephthalate homopolymer spun at a spinning speed of 4000 m/min or higher are heat-treated by the following method in addition to the above-mentioned heat treatment method. That is, the spinning speed is controlled by the take-up roller 6.
There is also a method of winding at a speed of 4000 m/min or more, gathering the fiber bundles into a tow, and then heat-treating the fiber bundles. Of course, the heat treatment method can be carried out by either a dry heat method or a moist heat method as described above. FIG. 2 is a schematic diagram showing an example of a method of subjecting a fiber bundle or tow of polyethylene terephthalate fibers produced under spinning conditions of a spinning speed of 4,000 m/min or more to heat-and-moisture treatment with superheated steam. In FIG. 2, numeral 11 indicates a fiber bundle or tow made of a homopolymer of polyethylene terephthalate that is yarn-proofed at a spinning speed of 4000 m/min or more. These are a pair of feed rollers 12
and reaches the guide roller 13. The fiber bundle and tow are guided by guide rollers 13 to a wet heat treatment device 15 . A slit 14 is provided at the entrance of the wet heat treatment apparatus 15, and a slit 14' is provided at the exit, so that the temperature inside the wet heat treatment apparatus 15 is not influenced by the outside atmosphere. In addition, the moist heat treatment apparatus 15 has a large number of slits 16 provided on the inner wall of the passage for the fibers to be treated so that superheated steam can be ejected from the upper and lower surfaces simultaneously. Additionally, heaters 17 are provided above and below inside the moist heat treatment apparatus 15 to reduce the temperature distribution of superheated steam. Meanwhile, the gauge pressure generated in boiler 24 is approximately 10
The saturated steam of Kg/cm ² enters the heating device 21 through the valve 23 and is heated by the heater 22 to become superheated steam at a temperature of 180 to 240°C. The superheated steam is sent to the moist heat treatment device 15 by the valve 20,
The heater 17 adjusts the temperature so that the temperature does not drop and the temperature distribution does not become large.
6, the fibers 11 to be treated are subjected to moist heat heat treatment. The fiber bundle or tow 11 that has been subjected to the moist heat treatment passes through the guide roller 18 through the slit 14',
It is taken off by a take-off roller 19. Fibers made of polyethylene terephthalate homopolymer spun at a spinning speed of 4000 m/min or higher and heat-treated at 220 to 300°C with dry heat or 180 to 240°C with wet heat are dispersed and have the above-mentioned microstructure. It can be dyed under normal pressure with a dye. By making this into a mixed knitted fabric by a known method, a mixed knitted fabric containing the pressure-dyeable polyester fiber of the present invention can be produced. A method for measuring the structural properties of the polyethylene terephthalate fibers constituting the knitted fabric of the present invention will be described below. <Mechanical loss tangent (tanδ) and dynamic elastic modulus (E′)
> Using a Rheovibron DDV-c type dynamic viscoelasticity measuring device manufactured by Toyo Baldwin, sample amount 0.1 to 1 mg, measurement frequency 110 Hz,
At each temperature in dry air with a heating rate of 10℃/min.
Measure tanδ and E′. From tanδ-temperature curve
The same peak height [(tan δ) max] as the peak temperature (Tmax) °C of tan δ can be obtained. Figure 3 shows a polyethylene terephthalate fiber A that can be dyed under normal pressure with a disperse dye used in the mixed knitted fabric of the present invention, a bulky yarn B obtained by false twisting the polyethylene terephthalate, a conventional polyethylene terephthalate fiber C, and a conventional polyethylene terephthalate false twisted yarn. A typical example of D is schematically shown. FIG. 4 schematically shows a typical example of the E'-temperature curve. Note that the indications of A, B, C, and D in the figure are the same as in FIG. 3. <Average refractive index (η, η⊥) and average birefringence (△η)> By the interference fringe method using a transmission quantitative interference microscope (for example, interference microscope Interfaco manufactured by Carl Zeiss Jena, German Democratic Republic) The average refractive index distribution observed from the side of the fiber can be measured. This method applies to fibers with a circular cross section. The refractive index of a fiber is characterized by the refractive index η for polarized light with an electric field vector parallel to the fiber axis, and the refractive index η⊥ for polarized light with an electric field vector perpendicular to the fiber axis. All measurements explained here are performed using green light (wavelength λ = 549 nm)
use. When the slide glass and cover glass are optically uniform, a mounting medium is injected that has a curvature (N) that provides a shift in interference fringes within a range of 0.2 to 2 wavelengths and is inert to the fibers. Immerse the sample fiber in mounting medium. The fiber is placed with its axis perpendicular to the optical axis of the interference microscope and the interference fringes. This pattern of interference fringes was photographed and approximately 1,500
Enlarge and analyze. In Figure 5, the curvature index of the fiber encapsulant is N, and the refractive index between points S〓−S〓 on the outer periphery of the fiber is η (or η⊥).
The thickness between S〓−S〓 is t, the wavelength of the light beam used is λ, and the distance between parallel interference fringes in the background (corresponds to 1λ)
is D, and the deviation of the interference fringes due to the fiber is d, then the optical path difference Γ is Γ=(d/D)λ=[η or η⊥)−
N]t. Therefore, η (or η⊥)=Γ/d+N holds true. If the cross-sectional shape of the fiber is circular, the thickness t is given by 2√ ² − ² using the coordinate x and the radius R. When the radius of the fiber is R, the distribution of the refractive index η (or η⊥) of the fiber at each position can be determined from the optical path difference at each position from the center 0 to the outer periphery R of the fiber. When x is the distance from the center of the fiber to each position, X=x/R=0, that is, the refractive index at the center of the fiber is called the average refractive index (η ₍₀₎ or η⊥ _(p) . It becomes 1 at the point, and it takes a value between 0 and 1 at other parts. For example, the refractive index at the point where X=0.8 is expressed as η _(0.8) (or η⊥ _(0.8) ). Also, the average refractive index η _{( 0)} and η⊥ _(0), the average refractive index (△η) is expressed as △η=η ₍₀₎ −η⊥ ₍₀₎ .
In FIG. 5, reference numeral 31 indicates fibers, 32 indicates interference fringes due to the mounting medium, and 33 indicates interference fringes due to fibers. FIG. 6 shows the distribution of η of each fiber, and the indications of A, B, C, and D are the same as in FIG. 3. In Figure 6, the horizontal axis indicates the distance from the center
x/R, and the η value is displayed on the vertical axis. X=0 is the center of the fiber, and X=1 and X=-1 are points on the outer periphery of the fiber. In the case of a non-circular cross section, the thickness t is not given as a function of only R and x, so a separately measured value is used. As a method for measuring t, it is calculated by the following formula from the measured values of Γ obtained using different types of mounting medium. t=(Γ ₁ −Γ ₂ )/(N ₂ −N ₁ ) where N ₁ and N ₂ are the refractive index of the mounting medium 1 and 2, Γ ₁ ,
Γ ₂ is the retardation measured in mounting medium 1 and 2. <Size of microcrystals (ACS)> Measure the X-ray diffraction intensity in the equator direction using the symmetric reflection method, and calculate the ACS from the diffraction angle dependence curve of the X-ray diffraction intensity.
is calculated. X-ray diffraction intensity was measured using an X-ray generator (RU-200PL) manufactured by Rigaku Corporation and a goniometer (SG-9R).
A scintillation counter is used as the counter, a pulse height analyzer is used as the counting section, and the measurement is performed using Cu-Kα rays (wavelength λ = 1.5418 Å) made monochromatic with a nickel filter. The fiber sample was placed in an aluminum sample holder so that the fiber axis was perpendicular to the X-ray diffraction plane. At this time, the thickness of the sample is approximately
Set it so that it is 0.5mm. The X-ray generator was operated at 30KV and 80mA, and the scanning speed was 1°/
Record the diffraction intensity from 35° to 7° in 2θ at a time constant of 1 second with a divergent slit of 1/2°, a receiving slit of 0.3 mm, and a scattering slit of 1/2°. The full scale of the recorder is set so that the resulting diffraction intensity curve falls within the scale. Polyethylene terephthalate fibers generally have three major reflections in the range of equatorial diffraction angles 2θ=7° to 26°. (100), (010), from the low angle side
(1TO) surface. To find ACS, for example LE
"Polymer X-ray Diffraction" by Alexander, Kagaku Doujin Publishing, Chapter 7 Using Scherrer's equation. A straight line connects the diffraction intensity curves between 2θ = 7° and 2θ = 35° to form the baseline. Drop a perpendicular line from the top of the diffraction peak to the baseline, and draw the midpoint between the peak and the baseline on this perpendicular line. A horizontal line through the midpoint is drawn between the diffraction intensity curves and the diffraction peaks. If the principal reflections are well separated, they will intersect two shoulders of the peak of the curve, but if they are poorly separated, they will intersect only one shoulder. Measure the width of this peak. If it intersects only one shoulder, measure the distance between the intersecting point and the midpoint and double it. If it crosses two shoulders, measure the distance between both shoulders. These measured values are converted into radians and used as the line width. Furthermore, this line width is corrected using the following equation. β=√ ² − ² Here, B is the measured value of the line width, and b is the broadening constant, which is the line width (half width) in radians of the peak of reflection from the (111) plane of a silicon single crystal. The size of microcrystals (ACS) is ACS (Å) =
It is given by K·λ/βcosθ. Here, K is 1, λ is the wavelength of the X-ray (1.5418 Å), β is the line width after correction, and θ is the Bragg angle, which is 1/2 of the diffraction angle 2θ. <Crystallinity (Xc)> X obtained in the same way as measuring the size of microcrystals
From the line diffraction intensity curve, connect the 2θ=7° and 2θ=35° diffraction intensity curves with a straight line to form the baseline. As shown in Figure 7, the valley around 2θ = 20° is set as the apex, connected with a straight line along the base of the low-angle side and the high-angle side, and separated into crystalline part a and amorphous part b. Find the crystallinity Xc. Xc = Scattering intensity of crystal part / Total scattering intensity x 100 (%) <Crystal orientation (CO)> Rigaku Corporation X-ray generator (RU-200PL), fiber sample measuring device (FS-3), goniometer (SG-9), a scintillation counter is used for the counter, a pulse height analyzer is used for the counting part, and Cu-Xα rays (wavelength λ =
1.5418 Å) to measure the X-ray diffraction intensity curve in the azimuthal direction. Polyethylene terephthalate fibers generally have three main types of reflection on the equator line, and (010) plane reflection is used to measure the degree of crystal orientation (CO).
The diffraction angle 2θ of the (010) plane is determined from the diffraction intensity curve in the equatorial direction. The above-mentioned X-ray generator is 30KV,
Operate at 20mA. Attach the sample fibers to the fiber sample measuring device so that they are parallel to each other. Adjust the thickness of the sample to approximately 0.5 mm. Set the goniometer at the 2θ value determined from the diffraction intensity curve in the equatorial direction. Using the symmetrical transmission method, the azimuthal direction is scanned from −30 to +30° and the diffraction intensity in the azimuthal direction is recorded. Furthermore, the diffraction intensity in the azimuth directions of −180° and +180° is recorded. At this time, the scanning speed was 4°/min, the chart speed was 10 mm/min, the time constant was 1 second, the collimator was 2 mmφ, and the receiving slit had a vertical width of 19 mm and a horizontal width of 3.5 mm. To determine CO from the obtained diffraction intensity curve in the azimuthal direction, first take the average value of the diffraction intensities obtained at ±180°, and use the horizontal line passing through this value as the baseline. Drop a perpendicular line from the top of the peak to the baseline and find the midpoint of its height. A horizontal line passing through the midpoint is drawn, the distance between the two intersections of this line and the diffraction intensity curve is measured, and this value is converted into an angle (°) and the value is defined as the orientation angle H (°). The degree of crystal orientation is given by CO (%) = [(180°-H)/180°] x 100. <Dye exhaustion rate> Disperse dye Resolin Blue FBL (product name of Bayer AG, Federal Republic of Germany, CIDisperse Blue56) at 3% owf, bath ratio 50 times, PH6 (adjusted with acetic acid), dispersant Disper TL (product of Meisei Chemical Industry Co., Ltd.) name) 1g/
Place the sample fiber in a dye bath with the composition of 100
After dyeing at ℃ for 120 minutes, collect the dye solution, calculate the amount of dye in the remaining solution from the absorbance, subtract this from the amount of dye used for dyeing, and calculate the dye exhaustion rate (%). was calculated. The sample fibers for dyeing were scoured in an aqueous solution of 2 g of the scouring agent Scoreroll FC (product name of Kao Atlas Co., Ltd.) at 60°C for 20 minutes, dried and conditioned (under conditions of 20°C and 65% RH). (left for 48 hours) was used. <Dyeing fastness> A sample dyed in the same manner as in the case of dye exhaustion rate evaluation was treated with 1 g of sodium hydrosulfite/
, bath ratio 50 with an aqueous solution of 1 g of sodium hydroxide
The samples were evaluated after reduction washing at 80°C for 20 minutes. Color fastness is determined by light fastness (JIS L-
1044), abrasion fastness (based on JIS L-0849), and sublimation fastness (based on JIS L-0854). <Tensile strength and elongation> The initial length was 5 cm using Tensilon UTM-20 model tensile testing machine manufactured by Toyo Baldwin (However, for fibers with crimps such as bulky fibers, the stretched 5 cm) and a tensile speed of 20 mm/min. <Boiling Water Shrinkage Rate> The length of the sample under a load of 0.1 g/d is _L0 , and after the load is removed and treated in boiling water for 30 minutes, the length measured again under the same load is L. The boiling water shrinkage rate is expressed by the following formula. Boiling water shrinkage rate (%)=L ₀ −L/L×100 The present invention will be explained in more detail with reference to Examples below. Example 1 A polyethylene terephthalate homopolymer having an intrinsic viscosity [η] (hereinafter referred to as [η]) of 0.65 at 35°C was prepared in a 2/1 mixed solvent of phenol/tetrachloroethane using the apparatus shown in FIG. The spinning temperature was 303℃, the pore diameter was 0.35mmφ, and the number of holes was 36.
The fiber bundle is spun from a spinneret, cooled and solidified by a flow of air at 22°C that is supplied from the entire periphery of the fiber bundle in parallel to the running direction of the fiber bundle, and then a finishing agent is applied.
The yarn was wound at a speed of 4000 m/min to obtain a yarn of 75 d/36. Next, this thread was made to pass through the heating cylinder for heat treatment shown in Fig. 1 without contacting it, and the temperature inside the heating cylinder was adjusted to 250°C, and the elongation rate was 1.3%.
Heat treatment was performed for 0.9 seconds. At the same time, for comparison, after spinning at a spinning speed of 1300 m/min, the yarn was stretched 3.3 times at 30°C.
The 75d/36f fibers were also heat treated in the same way. The physical properties of each fiber are summarized in Table 1.

【table】

[Table] Polyester yarn 75d/ obtained by the above manufacturing method
36f or comparison yarn and polyurethane yarn 40d bare yarn were knitted under the following conditions on a double circular knitting machine in a Jiyaguard device, and dyed and finished to create swimwear fabrics. Knitting conditions: Toyota KJ36 type Jiyaguard knitting machine Gauge: 28 pieces/inch Hook diameter: 30 inches Number of stitches:
36 rotation speed: 12RPM Thread used: Polyester 75d/
36f Polyurethane 40d Knitting method: Cylinder needles were selected by Jiyaguard needles, dial needles were arranged in two types alternately and selected alternately. With 6 yarn feeders as one complete yarn feeder, yarn feeder Nos. 1, 2, 4, and 5 are used to knit polyester yarn with regular two-color jaguard.
For yarn feeders No. 3 and 6, polyurethane yarn was knitted on the dial side. The basis weight of the gray fabric was 193 g/m ² for the product of the present invention and 195 g/m ² for the comparative product. This knitted fabric was dyed and finished using conventional dyeing and finishing processes. The staining and reduction washing conditions are shown below. Dye, auxiliary agent Sumikalon Yellow S-7GL (manufactured by Sumitomo Chemical)
1.2%owf Sumikalon Blue E-R (manufactured by Sumitomo Chemical) 2.1
%owf Disper T/L (manufactured by Meisei Kagaku) 1g/ (Note) For carrier dyeing Tetrosin K (manufactured by Yamakawa Pharmaceutical) 10%owf Dyeing bath ratio 1:20 Normal pressure dyeing: 40-100℃/30 minutes temperature increase 100℃, 40 minutes Dyeing carrier staining: Same as normal pressure staining High pressure staining: 40-130℃/40 minutes temperature increase 130℃ 40 minutes dye reduction washing bath ratio 1:20

[Table] Table 3 summarizes the color development, isochromaticity, and fastness of the products of the present invention and comparative products. As is clear from this table, the knitted fabric of the present invention exhibits dyeability even when dyed under normal pressure (100°C) at the same level as conventional dyed products at 130°C, and also exhibits excellent color fastness and color consistency between polyester yarn and polyurethane yarn. You can see that this is a product that lasts. In addition, polyurethane yarn is unwound from 100℃ dyed products and 130℃ dyed products,
Toyo Baldwin Manufactured by Nshiron UTM--
Initial length 5cm, tensile speed 50 using 20 type tensile testing machine
The elongation stress was measured in cm/min, and is shown in FIG. 8 with stress on the vertical axis and elongation rate on the horizontal axis. As can be seen from this figure, since the knitted fabric of the present invention can be dyed at 100°C, a decrease in the elasticity of the polyurethane yarn during dyeing was prevented, resulting in a knitted fabric with high elasticity.

[Table] Example 2 A polyethylene terephthalate homopolymer with [η] of 0.63 was produced using the spinning apparatus shown in Figure 1.
The fibers are spun at a spinning temperature of 302°C using a spinneret with a hole diameter of 0.35mmφ and 24 holes, and are cooled and solidified by a flow of air at 20°C that is supplied from all around the fibers in parallel to the running direction of the fibers. An oil agent was applied and the fiber bundle was wound at a speed of 4300 m/min to obtain a fiber bundle of 50D/24f. This fiber bundle was heat-treated with superheated steam at 195° C. for 0.7 seconds under a 0.5% elongation using a moist heat treatment apparatus shown in FIG. At the same time, for comparison, a 50d/24f fiber that had been spun at a spinning speed of 1350 m/min and then drawn 3.25 times at 30°C was heat-treated in the same manner. The physical property values of each fiber are summarized in Table 4.

【table】

【table】

[Table] Polyester 50d/24f obtained by the above manufacturing method
Using the yarn or comparison yarn and polyurethane yarn 40d bare yarn, it was knitted using a tricotto machine under the following conditions, and dyed and finished to create a warp-knitted 2-way swimsuit. Knitting conditions: Warping and knitting were performed using a normal warp knitting process. Polyurethane yarn was stretched to 600 yarns using a 21" beam using a warping machine for elastic yarn manufactured by Riva (West Germany), and was stretched to double the length. Polyester yarn was stretched to 21" using a warping machine manufactured by Karl Mayer (West Germany). 600 beams,
It was wound at a winding tension of 0.1 g/d. Manufactured by Karl Mayer (West Germany) Gauge 28/inch Beam number 6 Yarn feeding amount Polyester 160cm/Lack Polyurethane 80cm/Lack Number of courses on knitting machine 80 courses/in Structure: Half yarn used Front Polyester Back Polyurethane Fabric weight 330g /m Width 120cm Number of courses 114 courses/Inch well number 75 wells/
Inch dyeing conditions: Dyeing and reduction washing are performed in the normal dyeing and finishing process using a 2-way tricot, and the finishing set is 170 mm.
It was carried out at ℃ for 30 seconds. Dye auxiliary agent Siketone Polyester Blue 7GSF (Mitsui Toatsu Chemicals) 0.6%owf Siketone Navy Blue BGSF (Mitsui Toatsu Chemicals) 2.3%owf Tesper TL (Meisei Chemicals) 1g/ (For carrier dyeing: Tetrosin K ( (Manufactured by Yamakawa Pharmaceutical) 10% owf) Dyeing conditions Bath ratio 1:20 Normal pressure dyeing Room temperature 40℃ to approx. 100℃/30 minutes Carrier staining Approx. Minutes 130℃ x 40 minutes Stain reduction washing (carrier staining) High pressure staining (normal pressure staining) Hydrosulfite soda 2g/ 1g/
Carbonated soda 2g/ 1g/
Sunmoor RC-100 (manufactured by NICCA CHEMICAL)
2g / 1g / 80° x 30 minutes 65° x 20 minutes Bath ratio 1:30 After dyeing, color fastness, color development, isochromism, and constant elongation recovery were evaluated. Table 5 shows the physical property values of the inventive product and the comparative product. As shown in Table 5, 2 has excellent constant elongation recovery, color fastness, color development, and same color property.
I got a weighted swimsuit.

【table】

【table】 [Brief explanation of drawings]

FIG. 1 is a schematic diagram showing an example of the spinning and heat treatment process of polyethylene terephthalate fibers constituting the blended knitted fabric of the present invention, FIG. 2 is a schematic diagram of a heat treatment apparatus using superheated steam used in an example of the present invention, and FIG.
The figure is a graph schematically representing the mechanical loss tangent (tan δ) vs. temperature curve, and Figure 4 shows the dynamic elastic modulus (E').
- A graph schematically representing a temperature curve, FIG. 5, is an example of an interference fringe pattern used to measure the radial refractive index (η ₍₀₎ or η⊥) distribution in the cross section of the fiber. In the figure, a is a cross-sectional view of the fiber, and b is a diagram of an interference fringe pattern. FIG. 6 is a schematic diagram showing an example of the refractive index (η) distribution in the radial direction of the fiber;
Figure 7 shows the X of polyethylene terephthalate fiber.
It is a graph showing an example of a line diffraction intensity curve. Here, a is a crystalline region and b is an amorphous region. FIG. 8 is a graph showing the elongation-stress measurement results of polyurethane yarns unwound from the knitted fabric according to the present invention and the comparative knitted fabric. In Figures 3, 4, and 6, A is a polyethylene terephthalate fiber that can be dyed under normal pressure with the disperse dye used in the mixed knitted fabric of the present invention, and B is a fiber C that is obtained by false twisting the polyethylene terephthalate fiber, which is a conventional fiber. D indicates the value of the polyethylene terephthalate fiber, and D indicates the value of the conventional false twisted polyethylene terephthalate fiber. 1 is a fiber bundle, 2 is a spinning head, 3 is a tubular heating area, 4 is a fluid suction device, 5 is an oil application device, 6 is a take-up roller, 7 is a fiber bundle feed roller, 8 is a heating cylinder for heat treatment, 9 is a fiber A bundle feeding roller, 10 a fiber bundle winding roller, 11 a fiber bundle, tow, 1
2 is a feed roller, 13 is a guide roller,
14 and 14' are slits for preventing excessive leakage of superheated steam in the moist heat treatment device 15 and suppressing temperature fluctuations, 15 is a moist heat treatment device, 16 is a slit for spouting superheated steam in the moist heat treatment device, 17
is a heating heater, 18 is a guide roller, 19
31 is a take-up roller, 31 is a fiber, 32 is an interference pattern due to the mounting medium, 33 is an interference pattern due to the fiber, 34,3
5 and 36 respectively indicate polyurethane yarns unwound from the greige fabric of the present invention and the dyed fabric of the comparative example at 130°C.

Claims (1)

[Scope of Claims] 1. In a knitted fabric made of a mixture of polyurethane fiber and polyester fiber, the polyester fiber has an initial modulus of 55 g/d or more at 30°C and a mechanical loss tangent (tan δ) at a measurement frequency of 110 Hz. Bulky, non-pressurized fibers with a peak temperature (Tmax) of 105°C or less and a tanδ peak value [(tanδ)max) of more than 0.135 and/or an initial modulus at 30°C of 55g/
Bulky machining that satisfies the formula (tanδ)max≧(Tmax−105)×10 ^-2 between Tmax (℃) and (tanδ)max, and has a value of (tanδ)max of 0.08 or more. 1. A knitted fabric made of a mixture of polyurethane fiber and polyester fiber, characterized in that the fabric is made of a polyurethane fiber and can be dyed under normal pressure with a disperse dye. 2. Polyester fibers are fibers that are spun at a spinning speed of 4,000 m/min or higher and then heat-treated by dry heat at a temperature of 220°C to 300°C, and/or 4,000 m/min.
Claims 1. The fibers are obtained by spinning at a spinning speed of 1 minute or more, followed by heat treatment by dry heat at a temperature of 220°C to 300°C, and then bulking by a conventional method. A knitted fabric made of a mixture of polyurethane fiber and polyester fiber according to item 1. 3 Polyester fibers are fibers that are heat-spun at a spinning speed of 4,000 m/min or higher and then heat-treated with moist heat at a temperature of 180°C to 240°C and/or 4,000 m/min.
Claim 1, characterized in that the fiber is obtained by being spun at a spinning speed of 1 minute or more, then subjected to heat treatment using moist heat at a temperature of 180°C to 240°C, and then subjected to bulk processing by a conventional method. A knitted fabric made of a mixture of polyurethane fiber and polyester fiber as described in 1. 4 Polyester fiber that has not been bulked
Claim 1, characterized in that it has a (tan δ) max value of 0.14 or more, and an average birefringence (△n) of 50×10 ^-3 or more and 120×10 ^{-3 or} less. A knitted fabric made of a mixture of polyurethane fiber and polyester fiber. 5 Polyester fibers that have not been bulked
Tmax is below 100℃ and crystallinity (Xc) is 30
% or more, the size of (010) crystallites (ACS) is
Crystal orientation (CO) of 35 Å or more and (010) plane
85% or more of the mixed knitted fabric of polyurethane fiber and polyester fiber according to claim 1. 6 △ of polyester fiber that has been subjected to bulk processing
A knitted fabric made of a mixture of polyurethane fiber and polyester fiber according to claim 1, wherein n is 110×10 ^-3 or less and 45×10 ^-3 or more. 7 Polyester fibers that have undergone bulk processing
The peak temperature (Tmax) of tanδ is 115℃ or less,
Furthermore, the crystallinity (Xc) is 35% or more, the (010) crystallite size (ACS) is 38 Å or more, and the (010) crystal orientation (CO) is 80% or more. A knitted fabric made of a mixture of polyurethane fiber and polyester fiber according to claim 1. 8 △ of polyester fiber that has undergone bulk processing
n is 45×10 ^-3 or more, Tmax is 105°C or less, and (tanδ)max is 0.11 or more, and
Claims characterized by: A knitted fabric made of a mixture of polyurethane fiber and postester fiber according to item 1.