JP2001355134A - Crimped yarn - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a crimped yarn having rapid dyeing property and capable of forming carpet enabling vivid and uniform dyeing in continuous dyeing and print dyeing. SOLUTION: This crimped yarn is characterized in that the yarn is a polyamide multifilament crimped yarn having 9-45 dtex single yarn fineness and 12% to 35% crimp elongation ratio after treatment with boiled water and the crystallinity of the single yarn surface layer part is >=1.05 times based on the lowest crystalline part of the inner layer part in measurement of crystallinity of single yarn cross section by laser Raman spectroscopy.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a crimped yarn, particularly a crimped yarn suitable for carpet. More specifically, the dyeability of the dye is fast, and in continuous dyeing and print dyeing,
The present invention relates to a crimped yarn that enables clear and uniform dyeing.

[0002]

2. Description of the Related Art In recent years, the functions required of carpets have been diversified, and there has been a demand for product development according to the purpose of use. As the dyeing method, conventional methods such as continuous dyeing, Wins dyeing, space dyeing, cheese dyeing, and print dyeing are used.

[0003] In particular, recently, a large number of products using print dyeing have been circulating. Specifically, print dyeing of tufted white yarn directly, or print dyeing to impart design and design properties to the tuft, which has once colored the base by continuous dyeing or wince dyeing, are performed. ing. In addition, a technique has been adopted in which a relatively light-colored dyed yarn is used, and further printing is performed on a tufted counterpart with a base color in order to enhance sharpness and enhance the value as a product. The feature of print dyeing is that various patterns, especially complicated patterns and bright patterns, can be easily made anywhere in the tufted area, and it is widespread in the field of luxury carpets, It is environmentally friendly because a large amount of staining solution does not need to be used.

[0004] However, the properties required of such print-dyed carpets are severe. First of all, it is necessary to give a beautiful pattern. In the field of high-grade carpets, in particular, a saxony carpet using a crimped yarn set as a twisted yarn as a cut pile yarn is mainstream, and it is necessary for the saxony carpet to express a pattern clearly and clearly. It is also required that the handle has excellent weather resistance and color fastness so that the pattern does not deteriorate over time. Accordingly, the demands for crimped yarns constituting carpets have become strict. In terms of the pattern cutting property for clearly expressing the pattern, especially in the case of the above-mentioned twisted set yarn, it is required that the tip of the pile does not easily open during the manufacturing process and during use, that is, a crimped yarn excellent in pencil point property. In addition, since the print dyeing method has a substantially shorter dyeing time than other dyeing methods, it is required that the dye be transferred and fixed to the inside of the fiber and dyed quickly. Furthermore, there is also a need to keep the dye from being unnecessarily diffused into adjacent piles, i.e. only where the dye is desired. In addition, if the dyeability is high, the point at which the dye is contained often leads to adsorption spots, which may cause streaks on the surface of the carpet, and it is necessary to balance these. Furthermore, it is also required that weather resistance and dyeing fastness be high.

[0005] In order to solve these problems, some proposals of crimped yarns for print dyeing have been made in the past.

For example, attempts have been made to reduce the crystallinity by lowering the draw ratio of the original yarn and to increase the number of amorphous portions where dyes can easily enter into a yarn structure. But in this case,
In the case of using a gold-containing dye having strict weather resistance and a high molecular weight, such as in a car mat application, there has been a problem that streaks due to dye spots are easily generated. In general, since the gold-containing dye has a large molecular weight, there is a problem in that a difference in the adsorptivity of the dye tends to occur in a fine portion of the fiber, so that a streak is easily generated on the surface of the carpet. Further, in this case, since the fixing of the fiber structure is insufficient, there has been a problem that the color fastness is poor.

[0007] For this reason, attempts have been made to increase dyeing properties by increasing the final amino terminal amount. However, in the dyeing method in a short time as described above, even if the equilibrium adsorption amount of the dye is increased, the actual dyeing property has almost no effect, and the dye adsorption amount varies. I could only say that it was easy to get stuck.

In Japanese Patent Publication No. Hei 6-37741, a multifilament having a cross section of a single thread having one or more hollow portions in a cross section excellent in a pencil point property is used as a blow dyed cut pile carpet. Proposals have been made to combine with specific twist set conditions. In this patent, although the bulkiness is certainly improved, the pencil point property is not good due to the existence of the hollow portion, and the pattern formed by spraying becomes unclear. In addition, since a known single yarn of the crimped yarn is used, there is a limit in the speed of dyeing.

Further, Japanese Patent No. 2,530,805 discloses that
A patent has been disclosed that uses a copolymer of nylon 6 and nylon 66, performs a crimping process at a high temperature, and then performs a saturated steam treatment to enable dyeing with a dark color.

[0010]

However, in this patent, since the treatment of the described characteristics is a treatment after crimping, the fiber structure is almost fixed in the process up to that point, and the lightness in dyeing is reduced. The improvement is marginal. In addition, since the chips are copolymerized, there is a problem that the polymerization of the chips is difficult and the spinning is difficult.

As described above, at present, there has not been proposed a crimped yarn for print dyeing that exhibits high dyeing properties while maintaining functions such as ordinary weather resistance and provides a clear pattern.

The present invention has been achieved as a result of studying the problem of the above-mentioned prior art as a problem. Therefore, an object of the present invention is to provide a crimped yarn having fast dyeing properties suitable for use in print dyeing and the like.

[0013]

Means for Solving the Problems In order to solve the above problems, the crimped yarn of the present invention mainly has the following constitution.
That is, it is a polyamide multifilament crimped yarn having a single yarn fineness of 9 dtex to 45 dtex and a crimp elongation after boiling water treatment of 12 to 35%. In the crystallinity measurement of the single yarn cross section by the following laser Raman spectroscopy, The crystallinity of the surface layer portion of the single yarn is 1.05, which is the lowest crystalline portion of the inner layer portion.
It is characterized by being twice or more.

However, the laser Raman spectroscopy in the present invention
The crystallinity measurement of the cross section of a single yarn by the
-The light is illuminated and the obtained Raman scattered light is 1640
cm ^-1Half of the nearby carbonyl mode (amide I mode)
The value width was used as an index of crystallinity.

[0015] In the mixed fiber crimped yarn of the present invention,
The following (1) to (4) are each preferred embodiments. (1) The single yarn cross-sectional shape is Y-shaped or star-shaped, and its degree of deformation is 1.8 to 4. (2) The crimped yarn contains 30 to 120 PPM of copper. (3) The total fineness is 600 to 2500 dtex. (4) The amount of amino terminal groups is 5 × 10 ⁻⁵ mol / g or less.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The crimped yarn of the present invention has a crimp elongation of 12 to 35%, preferably 15 to 25%, which indicates the rate of crimping when treated in boiling water as described below. It is necessary. When the crimp elongation rate after the boiling water treatment is in the above range, the expression of crimp is sufficient and a bulky carpet can be obtained. In addition, it is possible to maintain a pencil point property such that the tip of the pile does not open when used for twisted yarn setting. If the content is set to 35% or more, the texture becomes hard and the material becomes felt-like, and the process stability deteriorates due to severe heat treatment in production.

The crimp elongation rate after the boiling water treatment in the present invention is defined as a cheese-like shape at room temperature (20 to 3) after winding the crimped yarn.
5 ° C.) and the rate of crimping when treated in boiling water after standing for 20 hours or more in an atmosphere with a relative humidity of 50 to 75%, specifically, a value measured by the following method. .

That is, the crimped yarn to be measured is immersed in boiling water for 30 minutes in a no-load state, then dried to obtain an equilibrium moisture content, and an initial load of 2 mg / d is applied to the sample. After a lapse of seconds, a sample length of 50 cm (L ₁ ) is measured and marked, then a constant load of 100 mg / d is applied to the sample, and the elongation (L ₂ ) after a lapse of 30 seconds is measured. From the values of L ₁ and L ₂ , the crimp elongation of the treated yarn under no load is determined as {(L ₂ −L ₁ ) / L ₂ } × 100.

The atmosphere conditions when the yarn is left before the boiling water treatment is the condition of the crimped yarn when used in the actual carpet manufacturing process, that is, the condition where the crimping property reaches an equilibrium state due to moisture absorption. It is selected from the viewpoint that it does not take too much time to reach the equilibrium state and that no dew condensation occurs.

The crimped yarn of the present invention needs to have a fineness of a single yarn constituting the multifilament of 9 to 45 dtex, more preferably 15 to 30 dtex.

If it is less than 9 dtex, the single yarn is thin, and it becomes difficult to give a difference in crystallinity in the fiber cross-sectional direction described later. Although the dyeing speed is increased due to an increase in the specific surface area, reflected and scattered light on the surface is conspicuous, and it is difficult to obtain a deep color. On the other hand, if it exceeds 45 dtex, the resulting carpet has a hard texture and is inferior in texture, and the convergence when formed into a multifilament is low. Would.

The greatest feature of the present invention is that the crystallinity of the crimped yarn exhibiting a specific crimp elongation is different in the cross-sectional direction of the single yarn, and the internal crystallinity is particularly low as compared with the surface layer of the fiber. Is to make the part exist.

Specifically, it is necessary that a portion having a certain degree of lower crystallinity than that of the surface layer exists inside a portion of the surface layer which exhibits crystallinity. The present inventors measure the crystallinity of the cross section of a single yarn by laser Raman spectroscopy, and if the cross-sectional structure shows a specific crystallinity structure, the crimped yarn is suitable for print dyeing. They have found that it is possible to achieve the present invention.

The measurement of the crystallinity in the cross section of a single yarn in the present invention is performed by irradiating a laser beam to a minute portion of the cross section of the single yarn and measuring Raman scattering light generated from the portion as described later. The crystallinity is quantitatively calculated from the half width of the vibration spectrum at a specific wavelength in the Raman spectrum and is evaluated as the crystallinity. In the present invention, the half value width of the carbonyl mode (amide I mode) at 1640 cm ⁻¹ was used as an index of crystallinity. The crystallinity is higher as the half width is smaller, and lower as the half width is larger. The measurement was performed at intervals of about 3 μ from the surface layer portion toward the center portion in the single yarn cross section. FIG. 1 shows a model diagram of a measurement location in a cross section of a single yarn.

In the present invention, when the parameter indicating the crystallinity determined by the above-mentioned measuring method is compared with the lowest point between the surface layer portion and the inner layer portion, the surface layer portion is 1.05 times or more, more preferably 1.1 times or more. It needs to be high. When the ratio is less than 1.05 times, the structural difference in the cross-sectional direction of the fiber is so small that a difference in dyeing property is hardly generated, so that the dyeing property of the fiber as a whole does not increase.

In the present invention, it suffices that a portion having low crystallinity as defined in the present invention is present in a part of the inside of the fiber from the surface layer of the fiber, and it is not necessary that all the inside have low crystallinity. Further, as described later, since the cross-sectional shape of the crimped yarn for carpet is usually non-circular, the inner layer portion having low crystallinity does not necessarily have to be arranged point-symmetrically in the fiber cross section.

In the structure of the crimped fiber in the cross section direction of a single yarn,
As described above, in order to have a portion having low crystallinity in the inner layer as compared with the surface layer portion, when a crystal layer that can be observed with a polarizing microscope is formed in the surface layer portion with a thickness of 1 μm or more and 10 μm or less, the difference between the inner and outer layers is reduced. It is preferable because it can be expressed. At first glance, it seems that the presence of a crystal layer in the surface layer portion impedes dye penetration, but the present inventors have found that the presence of this crystal layer accelerates the dyeing of a single yarn. Although the reason is not clear, it is considered that the crystallinity immediately inside the crystal layer is conversely low.

In the present invention, the crystal layer at the surface portion of the cross section of a single yarn can be confirmed by a known method. By observing a single yarn cut to a thickness of several μm using a polarizing microscope, the crystal layer can be confirmed as a white reflecting portion. In some cases, it can be confirmed as a log-cross spherulite. The appearance of a crystal layer that can be observed with the above-mentioned polarizing microscope on the entire surface of the single yarn cross section does not improve the dyeing properties, but needs to be present only in the surface layer. In addition, when the spherulites existing in the form of spots inside the fiber are present in such a number that does not affect the average crystallinity of the spot, even if they are present in the fiber inner layer, the effect of the present invention is not affected. Do not give.

In the crimped yarn of the present invention, it is necessary that the polymer constituting the crimped yarn is polyamide in order to achieve both the above-mentioned high crimping performance and high dyeability. The polyamide in the present invention includes polycapramide and polyhexamethylene adipamide. Polycapramide is particularly preferred in that dyeing properties are faster. Further, a polyamide copolymer containing 5% by weight or less of a copolymer component so as not to impair the effects of the present invention may be used. Specific copolymerization components include ε-caproamide, tetramethylene adipamide, hexamethylene sebacamide, hexamethylene isophthalamide, tetramethylene terephthalamide,
Xylylene phthalamide and the like. Furthermore, a copolymer component is added to improve the spinning property and the quality of the final product,
In addition, a polyamide to which a pigment is added for the purpose of expressing a light color serving as a base on a carpet may be used.
The pigment may be either an organic substance or an inorganic substance, but generally, carbon black, red iron or phthalocyanine pigments are used at a concentration corresponding to the desired color. Further, as described in US Pat. No. 5,108,684, a sulfonated copolymer containing an alkali metal salt may be used to improve the contamination.

If necessary, matting agents such as titanium oxide, antistatic agents, weathering agents, heat-resistant agents, antioxidants and the like may be used in the polymer.

The cross-sectional shape of the single yarn of the crimped yarn of the present invention can be applied to various cross-sectional shapes without any particular limitation. Round section,
Examples include a triangular cross section, a flat cross section, a Y-shaped cross section, a polygonal cross section, a star cross section, and a hollow cross section. Above all, a Y-shaped cross section or a star-shaped cross section is preferable as a carpet because high bulkiness can be exhibited. In particular, in the case of a twisted yarn set product, a Y-shaped or star-shaped cross section having no hollow portion can be said to be a more preferable cross-sectional shape from the viewpoint that a high pencil point property can be imparted.

The Y-shaped or star-shaped cross-sectional shape referred to in the present invention is a known cross-sectional shape. Three or more protrusions of substantially the same shape project radially from the center of the fiber cross section.
In this case, the degree of deformation is more preferably 1.8 to 4. By setting the degree of deformation within this range, the pencil point property is good and the bulky property is high.
It is possible to obtain a well-balanced carpet that is not only sharp in print dyeing but also excellent in bulkiness and texture.

The crimped yarn of the present invention contains 30 to 120 PPM, more preferably 50 to 90 PPM of copper as a weathering agent in the yarn.
It is preferable to contain it in the amount of M.

The method of incorporating copper is not particularly limited, but it is preferable to blend or knead a copper compound having good dispersibility before spinning. Any of organic and inorganic compounds may be used as a stable and usable copper compound during spinning. Preferred examples include benzimidazole, copper iodide, copper acetate and the like. The above amount is preferably contained as a copper component. By setting the amount to 30 PPM or more and 120 PPM, it becomes possible to express higher weather resistance and more color fastness without affecting the spinnability.

The fineness of the crimped yarn in the present invention is from 600 to 600.
2500 dtex, more preferably 800-2000 d
tex is preferred. With a fineness in this range, a bulky property and a voluminous feel can be obtained, and a preferable pattern as a carpet can be easily produced. Further, breakage of a single thread or dropout of a vial at the time of tufting can be prevented, resulting in excellent process stability. Furthermore, in applications where a firmer waist is required or in applications where higher durability is required, the crimped yarn multifilament of the present invention may be subjected to a conventional method.
A ply or a three-ply twist may be used, but with the fineness described above, a carpet excellent in texture and pencil point properties can be obtained. The number of twists of the ply twists can be set according to the desired flexibility and waist without any particular limitation,
Normally, both the number of twists and the number of twists are preferably 150 to 230 t / m, and the condition of 170 to 210 t / m is more preferably employed. If it exceeds 230 t / m, the pile becomes easy to turn on the side on the carpet surface, and the pattern becomes poor.

In the present invention, it is even more preferable that the amount of amino terminal groups of the polyamide polymer used is 5 × 10 ⁻⁵ mol / g or less. In general, the higher the amount of amino terminal groups, the higher the equilibrium adsorption amount. However, in the case of print dyeing, it is more important that the dyeing speed is faster than the equilibrium adsorption amount. The wearing speed hardly changes. Rather, taking into account various product forms and processes, such as the case of dyeing once in a normal bath and then printing on it, or pre-dying the plain part with in-bath dyeing, the amino terminal group If the amount is too large, the dye molecules vary in dyeing, and spots and streaks are likely to appear. From this point, it is not preferable that the amount of the amino terminal group is present more than necessary, and it is preferable that the amount is 5 × 10 ⁻⁵ mol / g or less, more preferably 4.5 × 10 ⁻⁵ mol / g or less.

By using the crimped yarn of the present invention, it is possible to provide a carpet that has a clear pattern in print dyeing, that is, has excellent pattern cutting properties. Particularly, in a saxony-style carpet set with twisted yarn, the effect is large, but of course, it is applicable even if the crimped yarn of the present invention is used as a part of a pile constituting a carpet. is there.

Hereinafter, an example of a production method for obtaining a crimped yarn of the present invention which has fast dyeing properties and excellent fastness will be described.
To produce the crimped yarn of the present invention, melt spinning, spinning oil,
A generally known method comprising stretching, crimping and each step is employed.

As the melt spinning apparatus used in the present invention, both an extruder type spinning machine and a pressure type spinning machine can be used, but the former is preferable in terms of product uniformity and yield in the spinning process. In particular, when a soaked polymer is used, an extruder type spinning machine is advantageous.

In producing the soaked yarn, the soaked chip can be obtained in advance or by blending a predetermined amount of a pigment with a polymer in a spinning machine. A preferred method is a known master chip method. . In this case, the pigment concentration in the master chip may be designed based on the pigment concentration in the yarn and the blend ratio.

In order to give a difference in crystallinity in the cross section direction of the single yarn and to provide a portion having low crystallinity in the inside of the present invention, it is necessary to use a fiber having a specific single yarn fineness in which the fiber shape is fixed. It is necessary to enhance the cooling of the device more than the cooling by air, and the cooling can be achieved by interposing a liquid such as water. In this case, the liquid to be interposed is preferably brought into contact with the yarn at 40 ° C. or lower. For example, a method of using a water-containing oil agent containing water in the oil agent to be applied immediately after formation of the yarn, or spraying water at the time of cooling can be adopted. At this time, by combining the yarn temperature when water is interposed and the cooling rate correlated to the amount and liquid temperature of the liquid,
It is possible to control the presence or absence of a crystal layer and to control the thickness of the crystal layer. Therefore, the conditions for interposing the liquid may be determined as appropriate in accordance with the conditions such as the amount of polymer discharged and the take-up speed during manufacturing. When using wet lubrication,
It is preferable to apply the composition at a location as close to the spinning as possible without affecting the spinnability.

The yarn thus produced retains its cross-sectional structure even after stretching and crimping, which will be described later, and can be a yarn having a surface crystal layer.

When the crystallinity of this yarn was measured in the direction of the cross section of a single yarn, the inside of the crystal layer had a structure with lower crystallinity than the surface layer.
A portion having a low crystallinity of 5 times or more exists inside.

The polymer in the form of a thread is subjected to stretching and heat setting as required. At the time of stretching, a steam processing device or the like may be used in combination for the purpose of fixing the stretching point.

When the polymer to be used is polyamide, it is necessary to have a certain degree of orientation and crystallization in order to impart a desired crimp in a later step. It is preferable to perform stretching. If the magnification is lower than 2 times, the fixing of the fiber structure is not sufficient, and not only the crimping performed in the subsequent step is weak, but also the weather resistance is poor.

Next, the drawn yarn is crimped. The crimp can be applied by a known heating fluid processing process, and various crimp applying methods such as a jet nozzle type, a jet stuffer type, and a gear system can be adopted, but a high crimp can be easily applied. Therefore, the jet nozzle method and the jet stuffer method are more preferable.
A crimp nozzle described in JP-B-58-28380 is used. Further, for the purpose of fixing the crimp, Japanese Patent Application Laid-Open No.
There is no limitation on combining a cooling device as described in Japanese Patent No. 321058 or a rotary filter. In the crimping, the drawn yarn may be continuously crimped without being wound as it is, or the undrawn yarn or the one that has been wound in the drawn yarn stage may be released, and subjected to a crimping step. Is also good.

When a crimped yarn is produced, the yarn introduced into the crimping nozzle may be entangled in advance for the purpose of controlling the processability and the crimping characteristics.
In order to impart a high crimp, it is preferable that the yarn to be supplied to the crimp nozzle is hardly entangled,
From the point of the crimp level and the processability, and furthermore, the pattern of the final mixed crimped yarn, the degree of entanglement of the original yarn may be set.

The yarn speed introduced into the crimping nozzle is usually 50
The range is preferably from 0 to 3500 m / min. When the yarn speed is in this range, efficient production is possible, and the crimp after passing through the nozzle is easily fixed, and stable running is easy.

The resulting crimped yarn may be entangled (original yarn entanglement) before winding, if necessary, in order to pass the process at the time of tufting. The yarn entanglement is
It can be provided by using a known entangled nozzle using compressed air. The air pressure may be appropriately set so as to have a predetermined number of entanglements according to the fineness and tension of the yarn.

A carpet using the crimped yarn of the present invention as a pile yarn is a carpet exhibiting high dyeing properties. In other words, when used for print dyeing or the like, the transfer of the dye into the interior of the single yarn occurs quickly, does not move to the periphery, and a carpet with a clear pattern is obtained.

In general, the basis weight is 700 to 1500 g /
When m ² and the pile height are in the range of 3.0 to 10.0 mm, a carpet can be clearly expressed, and the tuft is easy, and the texture and the volume are excellent.

The above-mentioned carpet using the crimped yarn of the present invention can be mixed with other yarns for the purpose of suppressing static electricity as long as the texture, pattern and color tone are not impaired. It is possible. Particularly preferably, a conductive fiber having a low specific resistance can be mixed. The above-described carpet using the crimped yarn of the present invention exhibits excellent performance particularly in the case of a Saxony type carpet provided with a twisted yarn set.

[0053]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail with reference to embodiments. In addition, all the physical properties described in the present invention were measured by the following methods. (1) Relative viscosity of sulfuric acid: A sample was dissolved in 98% sulfuric acid at a concentration of 1% by weight, and measured at 25 ° C. using an Ostwald viscometer. (2) Total fineness: measured according to JIS L1090. (3) Deformation degree of Y-type yarn or star-shaped cross-section yarn: The ratio of the diameter of the circumscribed circle to the diameter of the inscribed circle in the cross-section of the Y-type yarn or star-shaped yarn is calculated as the degree of deformation. The average value of measurements of five single yarns is used.

(4) Measurement of crystallinity by laser Raman spectroscopy: It was measured using Ramaonor T-64000 (Jobin Yvon) and using an argon laser. In the obtained Raman scattered light, the half width of the carbonyl mode (amide I mode) around 1640 cm −1 was used as an index of crystallinity. The smaller the half width, the higher the crystallinity. As shown in FIG. 1, the measurement was performed from the surface layer to the center in the cross section of the single yarn,
It was measured every other time. (5) Observation of cross-section crystal layer: One single yarn is taken out of the multifilament, hardened with paraffin, and then cut into a thickness of about 5 μm with a microtome. Next, the section was observed with a polarizing microscope.

(6) Dyeability Acid dye: Kayano in 1 liter hot water bath kept at 98 ° C.
l Add 0.5 g of Navy blue, add 1.6 g / L of sodium dihydrogen phosphate and 0.4 g / L of disodium hydrogen phosphate as assistants, and adjust the pH to 6-7. Cracked crimped yarn with length
Sample 30cm (about 0.3g) and immerse in the above hot water bath for 5 minutes. It is taken out after 5 minutes, washed twice with normal temperature water and normal temperature, and then naturally dried. Using the obtained sample, a section is cut out by the following method and a cross section of a single yarn is observed. (1) Set the thread in the embedding frame. Apply 5 to 10T / 10cm twists to bundle the threads and apply an appropriate tension to the threads. (1 / 10g /
(about d) (2) Pour paraffin at 120 ° C to 130 ° C into the embedding frame.
Allow to cool and solidify for about 10 minutes. (3) Attach the solidified block to the microtome sample stage.
Cut to a thickness of 10 to 10 (μ). (4) The cut sample is placed on a slide glass coated with egg white, and then placed in a dryer at 105 ° C. for 10 minutes. (5) Slide the slide glass removed from the dryer
For 1 minute, then drop one drop of liquid paraffin and place on a cover glass. (6) Observe the cross section with a microscope and evaluate the degree of penetration of the dye from the surface in three steps. 5 points are the state where the dye has penetrated to the center of the fiber, 1
The dots indicate a state in which no fiber has penetrated into the fiber, and 2 to 4
The dots indicate the middle. Three or more points pass.

(7) Pencil point properties The crimped yarn is subjected to 190 t / m of bottom twist and top twist, and
Perform spell basset at ℃. A carpet was prepared using the set yarn, and the opening of the pile tip was relatively visually evaluated. The opening of the tip was evaluated in five steps. Five points are the highest points and three or more points pass. The evaluation was the average value of 10 persons. (8) Amount of amino terminal group A sample of 2 g is collected and dissolved in a mixed solution of phenol and ethanol. It is determined by neutralization titration with N / 50 normal hydrochloric acid.

Example 1 An extruder type was prepared by adding 200 ppm of copper iodide to a regular type nylon 6 chip having a sulfuric acid relative viscosity of 2.8 and an amino terminal group amount of 4.3 × 10 ⁻⁵ mol / g. At a spinning temperature of 265 ° C. At this time, the base used was the base of the Y-shaped discharge hole, and the base having 80 holes was used. The discharged polymer was cooled by cold air flowing at a speed of 40 m / min in a direction perpendicular to the yarn, and then an oil agent was applied by an oil agent roll installed 3.5 m below the die. The oil agent at this time is disclosed in
A water-based emulsion oil having an emulsion concentration of 15% by weight and containing a leveling agent for an ester component and a nonionic activator component for a polyhydric alcohol described in JP-A-226074 was used. The temperature of the oil agent was 25 ° C., and the oil component was attached so that the amount of the oil component after winding was 1.2% by weight with respect to the yarn.

Subsequently, the film was stretched and heat-set without winding, and then subjected to crimping with a Taslan (registered trademark) type crimping nozzle described in JP-B-58-28380 and wound up. Stretching ratio is 3.0, stretching speed is 3000m / mi
Finally, a crimped multifilament having a degree of deformation of a single yarn cross section of 3.0, a fineness of 1170 dtex, 54 filaments and a crimp elongation of 22% after boiling water treatment was obtained.

When the cross section of the single yarn of the obtained crimped yarn was observed with a polarizing microscope as described above, a crystal layer of 4 μm was observed on the surface layer. FIG. 2 shows the results of crystallinity measurement of the obtained single yarn by laser Raman spectroscopy. The half value width of the highest crystallinity portion of the surface layer is 13.0 cm ⁻¹ , and 10 μm from the surface layer.
The half width at the lowest crystallinity point was 16 cm ^-1 . The crystallinity of the surface layer is lower than that of the inner part,
It is observed to be 1.23 times lower.

This crimped yarn is used as a multifilament 3
The piece was cut at a length of 0 cm, immersed in a dyeing bath for 5 minutes in the manner described above, and dyeability was evaluated. Table 1 shows the results.

Example 2 In Example 1, in cooling after spinning the polymer from the die, water was sprayed onto the yarn by spraying at a point 1 m from the die by spraying, and cooling was performed. After applying the same hydrous oil agent as in 1, stretching, crimping and winding were performed under the same conditions. The stretching ratio was 3.0, the stretching speed was 2500 m / min, and finally the degree of deformation of the single yarn cross section was 2.5 and the fineness was 1170 dtex.
A crimped multifilament having 54 filaments and a crimp elongation (after) of 18% of the crimped yarn after the boiling water treatment was obtained.

When the cross section of the single yarn of the obtained crimped yarn was observed with a polarizing microscope as described above, a crystal layer was observed on the surface as in Example 1. Table 1 shows the results of the crystallinity measurement by laser Raman spectroscopy of the obtained single yarn and the results of the dyeability after dyeing for 5 minutes.

Example 3 In Example 1, the number of filaments was set to 90, and the single yarn fineness was reduced. Cooling immediately below the base occurred faster than in Example 1, and the degree of deformation was 3.5.
And larger than Example 1. Then, water-containing lubrication was applied and crimping was performed in the same manner as in Example 1. The results of the used crimped yarn are shown in Table 1 [Comparative Example 1] In Example 1, spinning cooling was performed only by air cooling with cold air.

[Comparative Example 2] In Example 1, the heat treatment in the crimping step was weakened to obtain a yarn having a low crimp level.

As shown in Table 1, in Examples 1 to 3, the crimp level of the present invention and the crystallinity of the inner layer satisfy both 1.05 times or more of the crystallinity of the surface layer in the laser Raman spectroscopic analysis. , Fast dyeing properties, and good carpet removal.

In Comparative Example 1, there was no portion having low crystallinity in the inner layer of the cross section of the single yarn, and the crimped yarn had poor dyeing properties.

In Comparative Example 2, the setability was poor due to the low crimp elongation rate, and the tip of the pile was open when cut into piles, which resulted in poor handleability.

[0068]

[Table 1]

[0069]

According to the crimped yarn of the present invention, it is possible to form a carpet having a fast dyeing property suitable for print dyeing and a sharp pattern. The carpet obtained by using the crimped yarn of the present invention exhibits excellent performance particularly in the case of a print-dyed carpet.

[Brief description of the drawings]

FIG. 1 is a model diagram of one embodiment of a measurement point of crystallinity in a cross section of a single yarn.

FIG. 2 is a graph showing the results of measuring the crystallinity of the single yarn obtained in Example 1 by laser Raman spectroscopy.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4L035 BB36 DD02 EE20 GG03 4L036 MA06 MA20 MA33 PA12 PA41 RA04 UA12 UA16

Claims (5)

[Claims] 1. A polyamide multifilament crimped yarn having a single yarn fineness of 9 to 45 dtex and a crimp elongation after boiling water treatment of 12 to 35%, and the crystallinity of the cross section of the single yarn determined by laser Raman spectroscopy described below. A crimped yarn characterized in that, in the measurement, the crystallinity of the surface layer portion of the single yarn is 1.05 times or more the lowest crystalline portion of the inner layer portion. Measurement of the crystallinity of the cross section of a single yarn by laser Raman spectroscopy: A laser beam was applied to the cross section of the single yarn, and the Raman scattered light obtained was 1640 cm ^-1.
The half width of the nearby carbonyl mode (amide I mode) is used as an index of crystallinity. The measurement is performed from the surface layer to the center in the cross section of the single yarn, and is measured at intervals of about 3 μm, and the crystallinity in the cross section direction is compared. 2. A single yarn having a Y-shaped or star-shaped cross section,
The crimped yarn according to claim 1, wherein the degree of deformation is 1.8 to 4. 3. The crimped yarn according to claim 1, wherein the crimped yarn contains 30 to 120 PPM of copper. 4. The crimped yarn according to claim 1, wherein the total fineness is 600 to 2500 dtex. 5. The crimped yarn according to claim 1, wherein the amount of the amino terminal group is 5 × 10 ⁻⁵ mol / g or less.