JPH0336935B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a composite yarn comprising a core made of polyester long fibers and a sheath formed by winding short acrylic fibers and animal hair fibers around the core. More specifically, the present invention relates to a composite yarn using a polyester long fiber as a core, which is substantially made of a homopolymer of polyethylene terephthalate and can be dyed under normal pressure with a disperse dye as defined later. This composite yarn has good texture and mechanical properties that cannot be obtained with high-temperature, high-pressure dyeing, and has vivid coloring effects and water and moisture absorption functions. [Prior Art] Conventionally, natural fibers, chemical fibers, and synthetic fibers each have unique functions, but they also have various drawbacks, and the characteristics of natural fibers, chemical fibers, and synthetic fibers are also different. Attempts have been made to create composite yarns by mixing these fibers in various ways, thereby compensating for each other's deficiencies. For example, polyester fibers, especially polyethylene terephthalate fibers, are used in combination with natural fibers because of their excellent mechanical and thermal properties. By supplementing with fiber,
Composite yarns with superior performance have been made. [Problems to be Solved by the Invention] However, conventional polyethylene terephthalate fibers are difficult-to-dye fibers that cannot be dyed except under high temperature and high pressure conditions of 120 to 130°C. There was a limit to their compositing with fibers which significantly reduced their mechanical properties. For example, if a yarn that is a composite of acrylic fiber, animal hair fiber, and polyethylene terephthalate fiber is dyed under high temperature and pressure, the elasticity of the acrylic fiber and animal hair fiber will decrease, and the bulkiness that forms the texture of the yarn will decrease. is lost, resulting in thin threads with large sag. Furthermore, there was a drawback that the acrylic fibers and animal hair fibers were separated from each other due to the difference in shrinkage behavior between the acrylic fibers and the animal hair fibers. Furthermore, under high temperature and high pressure conditions, the acrylic fibers yellowed and white threads could not be obtained. In order to compensate for these drawbacks, the polyethylene terephthalate long fibers that make up the composite yarn are added to a dye bath containing a disperse dye with an accelerating dye substance called a carrier, such as O-phenylphenol, methylnaphthalene, chlorobenzene, or methyl salicylate, at temperatures around 100℃. After dyeing at a temperature of , acrylic fibers and animal hair 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 wastewater; and the light fastness of dyed products decreases because the carrier remains in the fibers and is difficult to remove. residual carrier may emit a pungent odor;
In addition, there is a risk of skin damage when dyed products are worn, and color reproducibility is difficult, requiring experienced techniques for color matching.Additionally, carrier dyeing may cause mechanical properties of polyethylene terephthalate fibers. Various problems occur, such as a change in strength or an increase in elongation. In addition, polyester long fibers with improved dyeability are known that are made by copolymerizing metal sulfonate group-containing compounds or polyether, but although these modified polyesters have improved dyeability, they In dyeing below ℃,
The dyeing concentration is not necessarily sufficient, and on top of that, polymerization and spinning are difficult, costs increase due to high raw material costs, or the excellent mechanical and thermal properties of polyethylene terephthalate are degraded, and other dye fastness properties are impaired. There were some drawbacks, such as poor performance in some cases. In the end, the chemical modification of polymers to make them easier to dye as described above mixes a third component that can act as a dyeing seat into the polymer, so it is inevitable that polyethylene terephthalate's original excellent heat resistance and mechanical properties will deteriorate. be. A common problem with these composite yarns is that they also occur in composite yarns, that is, core yarns, in which polyester long fibers form a core and acrylic fibers and animal hair fibers are wrapped around the core to form a sheath. In particular, if the polyester fiber in the core yarn, the acrylic fiber in the sheath, and the animal hair fiber in the core yarn are not dyed the same way, the appearance of the resulting composite yarn and textile products made using the composite yarn will be extremely poor. (make it look dirty). The present invention solves the problems of the prior art described above, and
The purpose of the present invention is to provide a core yarn that has good texture and mechanical properties that cannot be obtained by high-temperature and high-pressure dyeing, as well as having a vivid coloring effect and water-absorbing and moisture-absorbing functions. [Means for Solving the Problems] The above-mentioned object of the present invention is to provide a composite yarn comprising a core made of polyester long fibers and a sheath formed by winding short acrylic fibers and animal hair fibers around the core. The polyester long fibers are substantially made of a homopolymer of polyethylene terephthalate, have an initial modulus of 55 g/d or more at 30°C, and have a peak temperature (Tmax) of mechanical loss tangent (tan δ) at a measurement frequency of 110 Hz. is 105°C or less, has a tan δ peak value [(tan δ) max] of more than 0.135, has a crystallinity (Xc) of 30% or more,
The crystallite size (ACS) of the (010) plane is 35 Å or more, and the degree of crystal orientation (CO) of the (010) plane is 85%.
This is achieved by a composite yarn characterized by the above characteristics. The polyester fiber of the present invention consisting essentially of a homopolymer of polyethylene terephthalate is a novel fiber that can be dyed with a disperse dye, and
It can be manufactured by the method described below. "Can be dyed under normal pressure with disperse dyes" means disperse dye CI Disperse Blue 56 (CI Disperse Blue 56).
Disperse Blue56: For example, Resolin Blue FBL
[Product name of Bayer AG, Federal Republic of Germany])
100 in a dye bath with a dye usage of 3% owf, a bath ratio of 50 times, a pH of 6 (adjusted with acetic acid), and a dispersant (for example, 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 were 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. In order for a polyester fiber made of a homopolymer of polyethylene terephthalate to maintain its mechanical performance as a clothing fiber, it is required to have an initial modulus of 55 g/d or more at 30°C. The characteristic value expressing the structure of the amorphous region is the mechanical loss tangent (tanδ) at a measurement frequency of 110Hz.
The peak temperature (Tmax) of and the peak value of tan δ [(tan δ) max] are appropriate. Tmax is usually located 50℃ higher than the glass transition temperature, and (tanδ)
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 polyethylene terephthalate fiber is
130℃ or higher, (tanδ)max is 0.13 or lower. As a result of examining the relationship between the structure of the amorphous region of long fibers made of polyethylene terephthalate homopolymer constituting the composite yarn according to the present invention and dyeability, it was found that (tan δ)
It is necessary that max>0.135 and Tmax≦105°C. 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 homopolymers of polyethylene terephthalate do not satisfy the above three conditions, and none exist that can be dyed under normal pressure with disperse dyes. It is more preferable that the value of (tan δ) max is 0.14 or more. In the present invention, in order to obtain the mechanical properties of polyethylene terephthalate fibers that can be dyed at normal pressure with disperse dyes, the initial modulus at 30° C. is 55 g/d or more as described above. Here, the initial modulus at 30°C means 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. The structure and mechanical properties (strength, elongation, initial modulus, dynamic As a result of examining the relationship between the elastic modulus (elastic modulus) and stainability, the following points were clarified. In the fiber made of a polyethylene terephthalate homopolymer that can be dyed under normal pressure with a disperse dye constituting the composite yarn of the present invention, the degree of crystallinity (Xc), the size of microcrystals on the (010) plane (ACS), and ( 010) The degree of crystal orientation (CO) of the plane is related to the mechanical properties of the fiber, and the polyethylene terephthalate fiber has sufficient strength (3
g/d or more), and initial modulus (55 g/d
(more than 30%), Xc must be more than 30%, ACS
must be 35 Å or more, and CO must be 85% or more. More preferably, Xc is 70% or more and ACS is
40 Å or more, CO is 90% or more. Here Xc,
ACS and CO are values measured by X-ray diffraction using the methods described below. Conventional polyethylene terephthalate fibers have an Xc of 50-70%, an ACS of less than 30 Å, and a CO of 85-95%. Next, in the pressure-dyeable polyethylene terephthalate fiber constituting the composite yarn of the present invention, the central refractive index (n ₍₀₎ ) of polarized light having an electric field vector in the fiber axis direction is in the range of 1.65 to 1.68. Furthermore, the average birefringence (Δn) is 55 g/d at 30°C, which can be dyed at normal pressure with the disperse dye constituting the present invention.
To have an initial modulus of greater than or equal to 35×10 ^-3
The above is preferable, but on the other hand, from the viewpoint of structural stability against heat, it is desirable to be 50×10 ^-3 or more. In addition, from the viewpoint of dyeability and color fastness, preferably 120×
It is 10 ^-3 or less, more preferably 85×10 ^-3 or less. When Δn is less than ¹²⁰
The values of E′ at ℃ and 220℃ are E′ ₁₅₀ and E′ _220, respectively.
(expressed as E′ ₂₂₀ /E′ ₁₅₀ ) becomes smaller,
E′ ₂₂₀ /E′ ₁₅₀ is greater than 0.75. In other words, the structure becomes stable against heat. The color fastness is also improved. Furthermore, those with Δn smaller than 85×10 ^-3 have extremely excellent normal pressure dyeability. A so-called fiber that satisfies the following relationship between the average refractive index (n ₍₀₎ ) at the center of the fiber and the refractive index n _(0.8) or n _(-0.8) at a distance of 0.8 times the radius from the center of the fiber. When the local average refractive index distribution is symmetrical with respect to the center of the fiber, it has sufficient strength and has few staining spots, strong elongation spots, 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 n is (n ₍₀₎ −10×10 ⁻³ ) or more, and
This refers to the case where the difference between n _(-0.8) and n _(0.8) is 50×10 ^-3 or less, more preferably 10×10 ^-3 or less. Furthermore, the above
The values of n ₍₀₎ , n _(0.8) , n _(-0.8) , Δ _(0.8-0) ), Δ, etc. were measured using an interference microscope by the method described below. In addition, in the fiber made of a polyethylene terephthalate homopolymer that can be dyed under normal pressure with a disperse dye constituting the composite yarn of the present invention, the mechanical loss tangent (tan δ ₂₂₀ ) at 220°C is preferably as small as possible, and the initial modulus decreases as the temperature rises. decrease will be smaller. When tan δ 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. A preferred method for manufacturing a fiber 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 composite yarn of the present invention is disclosed in the patent application filed in 1983 by the present applicant.
4000 as described in specification 46407
A fiber made of polyethylene terephthalate homopolymer spun at a spinning speed of m/min or higher.
It can be obtained by heat treatment using dry heat at a temperature within the range of 220°C to 300°C. 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. The fiber thus obtained and subjected to the above heat treatment is made dyeable under normal pressure. 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, constituting the composite yarn of the present invention, can be obtained by a known polymerization method. Additionally, additives used in regular polyester fibers, such as matting agents, stabilizers,
It may also contain an antistatic agent. 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 normal pressure with a disperse dye constituting the composite yarn of the present invention, the polymer viscosity, the spinning temperature, the state of the atmosphere under the spinneret, the cooling method, the take-up speed, etc. By appropriately adjusting , it is possible to control the cooling solidification and change in shape of the polymer stream spun from the spinneret, and fibers with good spinnability and desired properties can be obtained. In particular, control of cooling and solidification of spun fibers is important, and in order to obtain spinnability and desired properties, rapid cooling and solidification, particularly low-temperature cooling and solidification perpendicular to the fiber 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 that can be dyed under atmospheric pressure with a disperse dye constituting the composite yarn 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 suction 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" used in the present invention means the surface speed of the take-up roller 6. The taken-off fiber bundle is continuously or once taken off by the taking-off roller 6.
After the fiber bundle is wound, it is pulled out by a pair of fiber bundle feed rollers 7, passes through a heating cylinder 8 whose temperature is adjusted to an appropriate temperature within the temperature range of 220 to 300°C, and is guided by a pair of fiber bundle feed rollers 9. He, take-up roller 1
It is wound up by 0. At this time, by adjusting the rotational speeds of the fiber bundle feed rollers 7 and 9, the fiber bundle 1 is elongated to an appropriate elongation rate in the heating cylinder 8 and subjected to heat treatment. The fibers made of polyethylene terephthalate homopolymer spun at a spinning speed of 4,000 m/min or higher and heat-treated at 220 to 300°C with dry heat have the above-mentioned microstructure and can be dyed with disperse dyes under normal pressure. It is what it is. By mixing this with short acrylic fibers and animal hair fibers using a spinning machine or the like in a known manner, a composite yarn containing the polyester long fibers that can be dyed under normal pressure according to the present invention can be produced. That is, the composite yarn of the present invention is produced by first using the polyethylene terephthalate long fibers that can be dyed under normal pressure as a core, acrylic short fibers and animal hair fibers as a sheath, and spinning the core yarn of the sheath core in the spinning process of the spinning process. However, it is not necessarily limited to these methods. In short, any composite yarn may be used as long as it has a core made of polyethylene terephthalate long fibers that are substantially made of a polyethylene terephthalate homopolymer and can be dyed under normal pressure with a disperse dye, and a sheath made of acrylic short fibers and animal hair fibers. The resulting composite yarn of the present invention has mechanical properties reinforced by polyethylene terephthalate long fibers that can be dyed under pressure, and the texture and appearance of the yarn are reinforced by acrylic fibers. , the water-absorbing, moisture-absorbing and heat-resistant surfaces are covered with animal hair fibers. Therefore, the composite yarn has higher heat resistance, water absorption, and moisture absorption performance than conventional yarns made of 100% acrylic fibers, and has extremely good coloring properties compared to yarns made of 100% polyester fibers, is soft, and It has a bulky texture. Furthermore, since the composite yarn can dye acrylic fibers, animal hair fibers, and polyethylene terephthalate fibers in the same color by atmospheric pressure dyeing, the mechanical properties of the acrylic fibers are less likely to deteriorate due to heat, and a soft texture can be maintained. It also prevents animal hair from becoming brittle due to heat, and maintains the unique voluminous texture of animal hair even after dyeing. When the composite yarn is dyed in the thread state and woven/knitted, and when it is woven/knitted in the raw silk state before dyeing, the number of weaving defects and knitting defects is greatly reduced, and the resulting The resulting woven and knitted fabrics are extremely soft and have the firmness and firmness that are essential for clothing. Furthermore, since it contains polyethylene terephthalate fibers, it has good heat setting properties with steam, has few defects such as shrinkage and elongation after washing, and has extremely excellent dimensional stability. The "acrylic fiber" used in the present invention refers to a fiber made of a linear polymer containing at least 50% by weight of acrylonitrile and capable of being dyed with a cationic dye under normal pressure. In addition, “animal hair fiber”
refers to natural animal fibers such as wool, angora, cashmere, mohair, alpaca, etc., excluding silk fibers. In addition, the content of polyethylene terephthalate fiber constituting the composite yarn of the present invention is 5 to 80% by weight.
Weight percent is preferred. If the content of polyethylene terephthalate fiber is less than 5% by weight, the heat resistance and dimensional stability of the resulting composite yarn will decrease, and if it exceeds 80% by weight, the unique texture of acrylic fibers and animal hair fibers will deteriorate.
In other words, flexibility and volume are lost. Further, the mixing ratio of acrylic fiber to animal hair fiber is preferably 20 to 95% by weight. If the acrylic fiber content is less than 20%, the soft texture and color development of acrylic will decrease, and if the animal hair fiber content is less than 5%, the effects of heat resistance and water absorption/moisture absorption performance will not be apparent. A method for measuring the structural properties of the polyethylene terephthalate fibers constituting the composite yarn 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 measurement 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 [(tanδ)max] as the peak temperature (Tmax)°C of tanδ is obtained. FIG. 2 schematically shows typical examples of tan δ-temperature curves of polyethylene terephthalate fiber A that can be dyed under normal pressure with the disperse dye of the present invention and conventional polyethylene terephthalate fiber B. FIG. 3 schematically shows a typical E'-temperature curve for a similar fiber. Note that the indications of A and B in the figure are the same as in FIG. 2. <Average refractive index (n, n⊥) and average birefringence (Δn)> Fibers are measured by the interference fringe method using a transmission quantitative interference microscope (for example, an interference microscope Interfaco manufactured by Carl Zeiss Jena, Germany). The distribution of the average refractive index observed from the side 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 n for polarized light with an electric field vector parallel to the fiber axis and the refractive index n⊥ 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. Injecting between an optically uniform slide glass and a cover glass a mounting medium that has a refractive index (N) that provides a shift in interference fringes within a range of 0.2 to 2 wavelengths and is inert to the fibers; The sample fiber is immersed in the 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 4, the refractive index of the fiber encapsulant is N, and the refractive index between points S' and S'' on the outer periphery of the fiber is n (or n⊥).
The thickness between S' and 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=[n (or n⊥)
−N]t. Therefore n (or
n⊥)=Γ/t+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 n (or n⊥) of the fiber at each position can be determined from the optical path difference at each position from the center O 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=O, that is, the refractive index at the center of the fiber is called the average refractive index (n ₍₀₎ or n⊥ ₍₀₎ ). x is 1 on the outer periphery and takes a value between 0 and 1 in other parts, but for example, the refractive index at the point x=0.8 is expressed as n _(0.8) (or n⊥ _(0.8) ). Furthermore, from the average refractive index n ₍₀₎ and n⊥ _(0), the average birefringence (Δn) is expressed as Δn=n ₍₀₎ −n⊥ ₍₀₎ .
In FIG. 4, reference numeral 31 indicates fibers, 32 indicates interference fringes due to the mounting medium, and 33 indicates interference fringes due to fibers. FIG. 5 shows the distribution of n for each fiber, and the indications of A and B are the same as in FIG. 2. Fifth
In the figure, the horizontal axis shows the distance from the center, X=x/R, and the vertical axis shows the n value. 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 ) Here, 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 X-ray diffraction intensity from the diffraction angle dependence curve using the ACS.
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 chart speed of 10 mm/min, a time constant of 1 second, a tie 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°. From the low angle side (100), (010), (1
10) It is a surface. To obtain the ACS, for example, the Scherrer equation in "Polymer X-ray Diffraction" by LE Alexander, Kagaku Dojin Publishing, Chapter 7 is used. A straight line connects the diffraction intensity curves between 2θ=7° and 2θ=35° to form a 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 radical representation 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 crystallite size (ACS) is given by ACS(Å)=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 diffraction intensity curves of 2θ = 7° and 2θ = 35° with a straight line and use it as a baseline. As shown in Figure 6, the valley around 2θ = 20° is set as the apex, connected by straight lines along the base of the low angle side and the high angle side, and separated into crystalline part a and amorphous part b, and the area method is performed according to the following formula. 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 section, and Cu-Kα 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 aforementioned X-ray generator
Operates at 330kV, 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 azimuth 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 is 4°/min, the charting speed is 10mm/min,
Time constant 1 second, collimator 2mmφ,
The receiving slit is 19mm long and 3.5mm wide. 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, CLDisperse 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 for 120 minutes at ) was calculated. The sample fibers for dyeing were refined in an aqueous solution containing 2 g of the refining 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/Elongation> Measurement was performed using a Tensilon UTM-20 model tensile testing machine manufactured by Toyo Baldwin Co., Ltd. at an initial length of 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 [Examples] 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 0.64 at 35°C was prepared in a 2/1 mixed solvent of phenol/tetrachloroethane using the apparatus shown in FIG. The spinning temperature was 298℃, the pore diameter was 0.35mmφ, and the number of holes was 24.
The fiber bundle is spun from a spinneret, cooled and solidified by a flow of air at 20°C 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 4400 m/min to obtain a yarn of 75 d/24 f. Next, the thread was passed 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 0.2%.
Heat treated for 0.95 seconds. The physical properties of this fiber and as a comparative example before heat treatment are summarized in Table 1. From the results in Table 1, fibers made of polyethylene terephthalate homopolymer spun at a spinning speed of 4400 m/min or higher and heat-treated at 250°C for 0.95 seconds under 0.2% elongation can be dyed with disperse dyes under normal pressure. Furthermore, it is found that the color fastness is excellent, and the mechanical properties and thermal stability are also sufficiently satisfactory.

【table】

[Table] Next, when hanging a 0.4 g/mm roving made of a blend of acrylic staple fibers 2d x 76 to 126 mm and wool fibers (blending ratio, acrylic fiber: wool fiber: 70:30 weight percent) on a spinning machine, , from before the front roller of the spinning machine, the above-mentioned pressure-dyeable polyethylene terephthalate long fibers are placed in the center of the roving in the draft state.
Supply 75d/24f, twist coefficient is 95, spinning count 1/30
(meter count) and a spinning speed of 16 m/min to obtain a composite yarn in which polyethylene terephthalate fiber constitutes the core and acrylic fiber and wool fiber constitute the sheath. (The spinning draft rate at this time is 31 times, and the yarn feeding tension of polyethylene terephthalate long fiber 75d/24f is 22 times
It was set to g. ) The obtained core yarn of the present invention, which is made of polyethylene terephthalate fibers, acrylic staple fibers, and wool fibers and is dyeable under normal pressure, was rolled up into a cheese shape in a stainless steel dyeing tube at a tension of 10 g, and dyed with the following dyeing recipe using a cheese dyeing machine. Stained for 60 minutes at °C. (Bath ratio 1:50, PH5) Refining agent... Score roll FC-250 <manufactured by Kao Atlas Co., Ltd.> 2 g/input, refined for 10 minutes at 70°C Cationic dye... Diacrylic type <manufactured by Mitsubishi Kasei>
2% owf input disperse dye...Dyanics type <Mitsubishi Kasei> 3
%owf input loosening agent...Ospin TAN <Tokai Oil Co., Ltd.> 1.5%
owf input dispersant...Noigen HC <manufactured by Dai-ichi Kogyo Association> 1.5g/
Input The obtained composite yarn (core yarn) has little yarn deformation due to dyeing, high strength and high elongation, and also has the waist and soft feel essential for clothing yarn, as well as water absorption and hygroscopicity. The yarn was made entirely of acrylic fibers, wool fibers, and polyethylene terephthalate fibers dyed in the same color.

[Brief explanation of drawings]

FIG. 1 is a schematic diagram showing an example of spinning and heat treatment steps for polyethylene terephthalate fibers constituting the composite yarn of the present invention. In the figure, 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, and 8 is a heating tube for heat treatment. , 9 is a fiber bundle feeding roller, and 10 is a fiber bundle winding roller. FIG. 2 is a graph schematically showing a mechanical loss tangent (tan δ)-temperature curve. FIG. 3 is a graph schematically showing a dynamic elastic modulus (E')-temperature curve. Figure 4 is an example of an interference fringe pattern used to measure the radial refractive index (n or n⊥) distribution in the cross section of a fiber. In Figure 4, a is a cross-sectional view of the fiber, and b is an interference fringe pattern. This is a diagram.
In the figure, 31 is a fiber, 32 is an interference pattern caused by the mounting medium, and 33 is an interference pattern caused by the fiber. FIG. 5 is a schematic diagram showing an example of the refractive index (n) distribution in the radial direction of the fiber. FIG. 6 is a graph showing an example of an X-ray diffraction intensity curve of polyethylene terephthalate fiber, in which a indicates a crystalline region and b indicates an amorphous region. In addition, Figures 2 and 3
In FIG. 5, A shows the value of polyethylene terephthalate fiber which can be dyed under normal pressure with the disperse dye used for producing the composite yarn of the present invention, and B shows the value of the conventional polyethylene terephthalate fiber.

Claims (1)

[Scope of Claims] 1 A composite yarn comprising a core made of polyester long fibers and a sheath formed by winding acrylic short fibers and animal hair fibers around the core, wherein the polyester long fibers are substantially composed of polyethylene. Made of terephthalate homopolymer, with an initial modulus of 55 g/d or more at 30°C, and a measurement frequency of 110 Hz.
The peak temperature (Tmax) of the mechanical loss tangent (tanδ) at As described above, the composite yarn is characterized in that the size (ACS) of microcrystals on the (010) plane is 35 Å or more, and the degree of crystal orientation (CO) on the (010) plane is 85% or more. 2. The fiber is obtained by spinning polyester long fibers at a spinning speed of 4000 m/min or more and then heat-treating the fibers by dry heat at a temperature of 220°C to 300°C. Composite yarn. 3. The fiber according to claim 1, which is a fiber obtained by spinning polyester long fibers at a spinning speed of 4000 m/min or more and then heat-treating the fibers by moist heat at a temperature of 180°C to 240°C. Composite yarn. 4 Polyester long fibers (tan δ) of 0.14 or more
max value, and the average birefringence (Δn) is 50×
10 ^-3 or more and 120×10 ^-3 or less composite yarn according to claim 1.