JP5465929B2 - Polyamide fiber, polyamide false twisted yarn and woven / knitted fabric - Google Patents

Description

  The present invention relates to a polyamide fiber and a polyamide false twisted yarn that are excellent in heat resistance against high-temperature hot water treatment and can be suitably used for various daily necessities, industrial materials, and clothing. The present invention relates to a woven or knitted fabric using these fibers and false twisted yarn.

Conventionally, monofilaments and multifilaments using nylon 6 or nylon 66 are often used as fibers using polyamide because they are advantageous in terms of cost.
These filaments have a certain degree of heat resistance and durability when used in a normal environment.

  However, when used for industrial materials where heat resistance is required, such as filters installed inside various devices, and when used for clothing used for dyeing treatment at high temperatures, these conventional polyamide fibers are: There is a problem that heat resistance is poor, and when high temperature treatment is applied, shrinkage occurs, strength decreases, and deterioration occurs.

  Patent Document 1 describes a fiber using nylon 11 as a polyamide. However, this fiber contains conductive carbon black in the polyamide resin, and is characterized by being excellent in the stability of the electric resistance value. In other words, in order to stabilize the electric resistance value, it is a fiber obtained by drawing and heat-treating in consideration of the arrangement of carbon black in the nylon 11 resin, and for this reason, strength and strength after high-temperature hydrothermal treatment. The retention rate was not sufficiently high, and the heat resistance and durability were poor.

  In recent years, reductions in petroleum resources and global warming have been seen as problems, and efforts have been made to deal with environmental problems on a global scale. Therefore, resin products such as fibers and films have been proposed that are made from plants that can be regenerated using resources that do not use petroleum as a raw material.

  Many fibers made of polylactic acid have been proposed as such environment-friendly fibers (see, for example, Patent Document 2). However, the fiber made of polylactic acid has a problem that it is not suitable for industrial materials because it has lower strength and wear resistance than polyamide fibers such as nylon 6 and nylon 66.

JP 2003-73923 A JP-A-12-27030

  The present invention is a polyamide fiber that solves the above problems, uses resources that do not use petroleum as a raw material, is environmentally friendly, has high strength retention after hot water treatment at high temperature, and is Polyamide fibers, false twisted yarns and woven fabrics using these fibers, which have a small water shrinkage ratio and are excellent in heat resistance and dimensional stability, and can be suitably used for various daily necessities, industrial materials, and clothing applications. Providing a knitted fabric is a technical issue.

The inventors of the present invention have arrived at the present invention as a result of studies to solve the above problems. That is, the gist of the present invention is the following (a) to (c).
(A) A multifilament having an elongation of 53.4-80% in which only nylon 11 containing a hindered phenol antioxidant and a phosphorus processing heat stabilizer is disposed, and the hindered phenol oxidation The total content of the inhibitor and the phosphorus processing heat stabilizer is 0.1 to 1.0% by mass, and the strength after hydrothermal treatment at 130 ° C. for 30 minutes is 3.0 cN / dtex or more, A summary of the polyamide multifilament is characterized in that the strength retention after hot water treatment at 130 ° C. for 30 minutes calculated by the following formula (1) is 80% or more and the hot water shrinkage is 10% or less. Is.
Strength retention after hot water treatment at 130 ° C. for 30 minutes (%) = (B / A) × 100 (1)
However, the strength before the hot water treatment is A, and the strength after the hot water treatment is B.
(A) A false twisted yarn comprising the polyamide multifilament described in (a), wherein the strength after hot water treatment at 130 ° C. for 30 minutes is 2.8 cN / dtex or more, and the following formula (2) A polyamide false twisted yarn characterized in that the calculated strength retention after hot water treatment at 130 ° C. for 30 minutes is 80% or more and the hot water shrinkage is 7% or less.
Strength retention after hot water treatment at 130 ° C. for 30 minutes (%) = (F / E) × 100 (2)
However, the strength before the hot water treatment is E, and the strength after the hot water treatment is F.
(C) A woven or knitted fabric using at least a part of the polyamide multifilament described in (a) or the polyamide false twisted yarn described in (a).

The polyamide fiber of the present invention and the polyamide false-twisted yarn of the present invention are filaments in which nylon 11 is arranged on at least the fiber surface in the cross-sectional shape of a single yarn, and have excellent strength and elongation characteristics, and hydrothermal treatment at high temperatures. The strength retention rate afterwards is high and the hot water shrinkage rate is small. For this reason, the polyamide fiber of the present invention and the polyamide false twisted yarn of the present invention can be subjected to dyeing treatments and various heat treatments at high temperatures, and products such as woven and knitted fabrics and nonwoven fabrics excellent in dyeability and workability can be obtained. Can be obtained.
The polyamide fiber and polyamide false-twisted yarn of the present invention contain a heat-resistant agent in nylon 11, so that the operability at the time of spinning is improved, and the above-described excellent yarn quality is easily obtained. It becomes possible.
Since the polyamide false twisted yarn of the present invention uses the polyamide fiber of the present invention, the polyamide false twisted yarn has the characteristics as described above, and the crimp elongation and crimp elastic modulus are in an appropriate range. A fabric having a like texture can be obtained, and can be suitably used for various apparel applications.
And the woven or knitted fabric using the polyamide fiber or the polyamide false twisted yarn of the present invention for at least a part thereof can be suitably used for apparel because of its excellent dyeability, and is excellent in hot water resistance and durability. From this point, it can be suitably used for various nets, fishing nets, industrial materials such as fishing lines, anchorage, paper canvas, filters, and the like.
Further, since nylon 11 is obtained by producing and synthesizing 11-aminoundecanoic acid based on castor oil extracted from castor seeds, the polyamide fiber of the present invention uses petroleum as a raw material. It is not a thing, but a fiber that takes the global environment into consideration.

Hereinafter, the present invention will be described in detail.
First, the polyamide fiber of the present invention comprises a filament in which nylon 11 is disposed on at least the fiber surface in the cross-sectional shape of a single yarn.

  As a cross-sectional shape in which nylon 11 is arranged at least on the fiber surface, a single component type using only nylon 11 is preferable, but a composite type combining other thermoplastic resin and nylon 11 is preferable. There may be. In the case of the composite type, in order to obtain such a cross-sectional shape, a core-sheath type shape in which nylon 11 is arranged in the sheath portion and a multilayer shape in which nylon 11 is arranged in the outermost layer are used. preferable.

  In addition, both the single component type and the composite type may have not only a round cross section but also a polygonal irregular cross section such as a triangle or a square, and may have a hollow portion.

  In the case of a composite type, the proportion of nylon 11 is preferably 50% by mass or more, and more preferably 60% by mass or more. If the ratio of nylon 11 is too small, it will be difficult to satisfy the strength retention rate and hot water shrinkage rate after high temperature hot water treatment as described later.

  Further, the polyamide fiber of the present invention may be a monofilament composed of only one single yarn or a multifilament composed of a plurality of single yarns as long as the cross-sectional shape of the single yarn satisfies the above-mentioned shape. May be. Furthermore, it may be either a short fiber obtained by cutting a monofilament or a multifilament short, or a long fiber used without being cut.

  In the case of multifilament, it is preferable that the single yarn fineness is 0.1 to 50 dtex and the total fineness is 20 to 3000 dtex. In the case of a monofilament, it is preferably 10 to 500 dtex.

  Nylon 11 used in the present invention is obtained by polycondensation of 11-aminoundecanoic acid. And since 11-amino undecanoic acid is produced | generated based on the castor oil extracted from the seed of the castor (castor bean), it consists of a plant-derived component.

  Nylon 11 may be copolymerized with other polyamide-forming monomers such as ε-caprolactam and hexamethylene diammonium adipate, and blends with other polyamides such as nylon 6 and nylon 66. You may have done.

  As described above, when the polyamide fiber of the present invention is made into a composite type, other thermoplastic resins used with nylon 11 can be polyamide, polyester, polyolefin, etc. Polyamide is preferably used from the viewpoint of preventing the above, and nylon 6, nylon 66, nylon 12, nylon 46 and the like are particularly preferable.

  And the polyamide fiber of the present invention has a strength after hot water treatment at 130 ° C. for 30 minutes of 3.0 cN / dtex or more, and after hot water treatment at 130 ° C. for 30 minutes calculated by the following formula (1). The strength retention is 80% or more.

In the hot water treatment at 130 ° C. for 30 minutes in the present invention, a tubular knitted fabric is prepared using the polyamide fiber of the present invention, and immersed in a warm bath in the state of this tubular knitted fabric, and heated at 130 ° C. for 30 minutes. Water treatment. The treatment method is not particularly limited as long as it is a method of immersing a tubular knitted fabric in a warm bath and performing hot water treatment at 130 ° C. for 30 minutes, but as an example, using a mini color dyeing machine manufactured by Texam Giken, An example is a method in which the tubular knitted fabric is put into a metal pot containing water, treated at 130 ° C. for 30 minutes, taken out, and dried.
The strength of the polyamide fiber is measured at a gripping interval of 20 cm and a pulling speed of 20 cm / min using a constant speed extension type tester in accordance with the method described in the standard test of tensile strength and elongation of JIS L1013. . When measuring the strength of the polyamide fiber after the hot water treatment, the hot-water-treated tubular knitted fabric is knitted, the polyamide fiber is taken out, and measured according to the method described above.

The strength after hydrothermal treatment at 130 ° C. for 30 minutes is preferably 3.5 cN / dtex or more, more preferably 3.8 cN / dtex or more.
When the strength after hot water treatment at 130 ° C. for 30 minutes is less than 3.0 cN / dtex, the hot water resistance is poor, and the dyeing treatment and various heat treatments cannot be performed at a high temperature.

And, the strength retention after the hot water treatment at 130 ° C. for 30 minutes calculated by the following formula (1) needs to be 80% or more, among which 82% or more is preferable. Is preferably 85% or more.
Strength retention after hot water treatment at 130 ° C. for 30 minutes (%) = (B / A) × 100 (1)
However, the strength before the hot water treatment is A, and the strength after the hot water treatment is B.

  When the strength retention is less than 80%, when high-temperature dyeing or high-temperature processing is performed, the strength is lowered and the heat resistance is poor.

Furthermore, the polyamide fiber of the present invention has a hot water shrinkage of 10% or less, and preferably 8% or less. The hot water shrinkage rate in the present invention is measured and calculated by immersing in hot water at 130 ° C. for 30 minutes in accordance with JIS L 1013 hot water shrinkage rate skein shrinkage rate (Method A). The treatment method is not particularly limited as long as it is a method in which skein is immersed in a warm bath and subjected to hot water treatment at 130 ° C. for 30 minutes, but as an example, a mini color dyeing machine manufactured by Teksam Giken is used. An example is a method in which a sample wrapped in gauze so as not to prevent shrinkage and tangling is put into a metal pot containing water, treated at 130 ° C. for 30 minutes, taken out, and air-dried.
When the hot water shrinkage rate exceeds 10%, shrinkage generated during high-temperature dyeing or high-temperature processing is large, and products such as woven and knitted fabrics and nonwoven fabrics obtained are inferior in quality and poor in dimensional stability.

  The strength of the polyamide fiber of the present invention (before hydrothermal treatment) is preferably 3.0 cN / dtex or more and an elongation of 20 to 140%. The strength is preferably 4.0 cN / dtex or more, and the elongation is preferably 25 to 80%. When the strength is less than 3.0 cN / dtex, fluff and yarn breakage are liable to occur during knitting and post-processing, and process passability tends to deteriorate.

  The polyamide fiber of the present invention is a filament in which nylon 11 is arranged on at least the fiber surface in the cross-sectional shape of a single yarn, and is produced by a spinning and drawing conditions manufacturing method as described later, thereby producing the above-described strong drawing. It is possible to obtain a polyamide fiber having a high degree of strength, a strength retention rate and a hot water shrinkage rate.

  And as for the polyamide fiber of this invention, it is preferable to use the nylon 11 in which the heat-resistant agent contains, and it is preferable that content of the heat-resistant agent in a filament is 0.1-1.0 mass%. By including a heat-resistant agent in the nylon 11, the spinning temperature can be lowered, the viscosity of the nylon 11 can be suppressed, and the amount of monomer deposited during spinning can be reduced. . Thus, there is no yarn breakage in the spinning process, and spinning can be performed with good operability, and undrawn yarn having excellent quality and performance can be supplied in the subsequent drawing process. Furthermore, the heat resistance of polyamide fiber can be improved by containing a heat-resistant agent.

  And as a heat-resistant agent, it is preferable to use a hindered phenolic antioxidant. As the hindered phenol-based antioxidant, IRGANOX (manufactured by Ciba Japan) is preferably used.

  Furthermore, it is preferable to use a phosphorus processing heat stabilizer in combination as a heat-resistant agent. As the phosphorus processing heat stabilizer, IRGAFOS (manufactured by Ciba Japan) is preferably used.

  The content of these heat-resistant agents in the filament (total amount when used in plural types) is preferably 0.2 to 0.8 mass%, more preferably 0.2 to 0.6 mass%. Is preferred. When the content of the heat-resistant agent in the filament is less than 0.1% by mass, the effect of improving the spinning operability as described above becomes poor. On the other hand, when the content of the heat-resistant agent exceeds 1.0% by mass, the effect is not only saturated, but also causes thread breakage during spinning.

  The nylon 11 in the present invention contains various additives such as a plasticizer, a flame retardant, a matting agent, an inorganic filler, a reinforcing agent, a colorant, and a pigment as long as the effects are not impaired. May be.

  Next, the polyamide false twisted yarn of the present invention will be described. The polyamide false twisted yarn of the present invention is obtained by applying false twist to the polyamide fiber of the present invention as described above. That is, a false twisted yarn comprising a multifilament in which nylon 11 is arranged on at least the fiber surface in the cross-sectional shape of a single yarn, and the strength after hot water treatment at 130 ° C. for 30 minutes is 2.8 cN / dtex or more The strength retention after the hot water treatment at 130 ° C. for 30 minutes calculated by the following formula (2) is 80% or more.

  In addition, the hot water treatment for 30 minutes at 130 ° C. in the present invention is to create a tubular knitted fabric using the polyamide false twisted yarn of the present invention, soak in a warm bath in the state of this tubular knitted fabric, 130 ° C., The hot water treatment is performed for 30 minutes. Then, the strength of the polyamide false twisted yarn is measured at a holding interval of 25 cm and a pulling speed of 30 cm / min using a constant-speed extension type testing machine in accordance with the method described in JIS L1013 tensile strength and elongation standard time test. To do. When measuring the strength of the polyamide false twisted yarn after the hot water treatment, the polyamide false twisted yarn is taken out by knitting the hot-water treated tubular knitted fabric, and measured according to the method described above.

The strength after hydrothermal treatment at 130 ° C. for 30 minutes is 2.8 cN / dtex or higher, preferably 3.0 cN / dtex or higher, and more preferably 3.5 cN / dtex or higher.
When the strength after the hot water treatment at 130 ° C. for 30 minutes is less than 2.8 cN / dtex, the hot water resistance is poor and the dyeing treatment and various heat treatments cannot be performed at a high temperature.

And, the strength retention after the hot water treatment at 130 ° C. for 30 minutes calculated by the following formula (2) is required to be 80% or more, among which 85% or more is preferable. Is preferably 90% or more.
Strength retention after hot water treatment at 130 ° C. for 30 minutes (%) = (F / E) × 100 (2)
However, the strength before the hot water treatment is E, and the strength after the hot water treatment is F.

  When the strength retention is less than 80%, when high-temperature dyeing or high-temperature processing is performed, the strength is lowered and the heat resistance is poor.

Furthermore, the polyamide false twisted yarn of the present invention has a hot water shrinkage of 7% or less, and preferably 5% or less. The hot water shrinkage rate in the present invention is measured and calculated by immersing in hot water at 130 ° C. for 30 minutes in accordance with JIS L 1013 hot water shrinkage rate skein shrinkage rate (Method A).
When the hot water shrinkage rate exceeds 7%, shrinkage generated during high-temperature dyeing or high-temperature processing is large, and products such as woven or knitted fabric and nonwoven fabric obtained are inferior in quality and poor in dimensional stability.

  The strength of the polyamide false twisted yarn (before hydrothermal treatment) of the present invention is preferably 3.0 cN / dtex or more and an elongation of 20 to 60%. The strength is preferably 3.2 cN / dtex or more, and the elongation is preferably 25 to 50%. When the strength is less than 3.0 cN / dtex, fluff and yarn breakage are liable to occur during knitting and post-processing, and process passability tends to deteriorate.

  By using the polyamide fiber of the present invention, the polyamide false twisted yarn of the present invention can be made into a polyamide fiber having the above strength, strength retention and hot water shrinkage.

  Further, the polyamide false twisted yarn of the present invention is preferably made of nylon 11 containing a heat-resistant agent as in the case of the polyamide fiber of the present invention, and the content of the heat-resistant agent in the filament is 0.1 to 1. It is preferably 0% by mass.

  Furthermore, the polyamide false twisted yarn of the present invention preferably has a crimp elongation of 40 to 65%, and more preferably 45 to 60%. The crimp elastic modulus is preferably 20 to 40%, and more preferably 22 to 38%.

  In general, polyamide fibers and false twisted yarns using polyamide fibers have a slimy feeling due to the unique properties of polyamide, and are poor in lightness and softness.

  The polyamide false twisted yarn of the present invention can have a polyester-like texture by satisfying the above-described crimp elongation rate and crimp elastic modulus. That is, it has swelling characteristics and expansion / contraction characteristics like a yarn (2-heater false twisted yarn) obtained by heat-treating polyethylene terephthalate after false twisting. Furthermore, the excellent high color developability which was not obtained with polyethylene terephthalate is obtained, and can be suitably used as a clothing material for outer clothing.

The crimp elongation rate and crimp elastic modulus in the present invention are measured as follows according to the method described in DIN 53840 Part 1.
1. Sample Preparation Using a measuring machine having a frame circumference of 1.125 m, a tension of 0.1 cN / dtex is applied and the false twisted yarn is wound into a bowl shape. At this time, it is wound up so that the fineness becomes 2500 dtex. Remove the sample from the frame and leave it in an environment of 20 ° C. and 65% humidity for 24 hours without applying a load.
In order to wind up so that the fineness of the yarn becomes 2500 dtex, the number of windings is varied depending on the fineness of the false twisted yarn used (for example, in the case of 74 dtex to 78 dtex, 16 folds are made. Also, 112.5 dtex to 117.5 dtex). In the case of 11 times, see DIN 53840 Part 1 Tabie 1).
Further, the false twisted yarn used as a sample is allowed to stand in an environment of 20 ° C. and 65% humidity for at least 24 hours and then wound into a bowl shape.
2. Crimp development Load 0.001 cN / dtex before placing in oven. Heat at 120 ° C for 10 minutes with the load applied.
Remove the load and leave it in an environment of 20 ° C and 65% humidity for at least 24 hours.
3. Determination of straight line length
(1) Multiply the first load (2.5 g) and the second load (497.5 g) and measure the length (G) of the heel after 10 seconds.
(2) Next, the second load is removed, and the length (Z) of the heel after 10 minutes is measured while the first load is applied.
(3) Next, with the first load applied, the third load (22.5 g) is applied, and the length (F) of the heel after 10 seconds is measured.
4). Calculation of Crimp Elongation Rate and Crimp Elastic Modulus The crimp elongation rate and crimp elastic modulus are calculated by the following equations.
Crimp elongation (%) = [(G−Z) / G] × 100
Crimp elastic modulus (%) = [(G−F) / G] × 100

  If the crimp elongation is less than 40% or the crimp elastic modulus is less than 20%, a polyester-like yarn having the above-described swelling characteristics and stretch characteristics cannot be obtained. On the other hand, when the crimp elongation rate exceeds 65% or the crimp elastic modulus exceeds 40%, the stretchability is strong, the swelling is strong, and the nylon 66 or nylon 6-like thread is formed. It is not suitable for use as a material.

  In order to obtain a false twisted yarn having a crimp elongation rate and a crimp elastic modulus as described above, false twist coefficient 29000 to 34000 [false twist coefficient: T√D, where D is fineness (dtex), and T is false twist. Number (t / m)], and false twisting is preferably performed under the conditions of false twisting temperature of 150 to 170 ° C.

Next, the woven or knitted fabric of the present invention will be described.
The woven or knitted fabric of the present invention is knitted and woven using at least a part of the above-described polyamide fiber of the present invention. The woven or knitted fabric using the polyamide fiber of the present invention for either one or both of warp and weft, Examples thereof include a woven fabric using the polyamide fiber of the present invention as part of the weft, a knitted fabric using the polyamide fiber of the present invention as the whole or part of the knitting yarn, and the like.

  In the woven or knitted fabric of the present invention, in order to achieve the effect of the excellent properties of the polyamide fiber of the present invention, 40% by mass or more, further 50% by mass or more in the woven / knitted fabric is composed of the polyamide fiber of the present invention. It is preferable. In the case of a woven or knitted fabric in which the composition ratio of the polyamide fiber of the present invention is less than 40% by mass and a large amount of other petroleum-derived raw materials are used, the ratio of plant-derived raw materials in the woven or knitted fabric is low. It cannot be called a woven or knitted fabric with consideration.

  The woven or knitted fabric of the present invention is knitted and woven using at least a part of the above-described polyamide false twisted yarn of the present invention, and the polyamide false twisted processing of the present invention is applied to either one or both of warp and weft. Examples include woven fabrics using yarns, woven fabrics using polyamide false twisted yarns of the present invention as part of warps and wefts, and knitted fabrics using polyamide false twisted yarns of the present invention as all or part of knitting yarns. .

  In the woven or knitted fabric of the present invention, in order to achieve the effect of the excellent properties of the polyamide false twisted yarn of the present invention, 40% by mass or more, and further 50% by mass or more in the woven or knitted fabric is the polyamide false twisted process of the present invention. It is preferably composed of yarn. In addition, in the case of a woven or knitted fabric in which the proportion of the polyamide false twisted yarn of the present invention is less than 40% by mass and uses many other petroleum-derived raw materials, the ratio of plant-derived raw materials in the woven / knitted fabric is low, It cannot be said that weaving and knitting in consideration of the global environment.

  Since the woven or knitted fabric of the present invention is made using the polyamide fiber or polyamide false twisted yarn of the present invention, it can be dyed at a high temperature, and is excellent in dyeability. It can be suitably used for clothing applications. Moreover, from the point which is excellent in hot water resistance, durability, etc., it can be used conveniently for various nets, fishing nets, anchorages, papermaking canvases, filters and the like.

  In the woven or knitted fabric of the present invention, the woven structure is flat, twill, satin or the like, and the knitted structure is not particularly limited, such as a tengu or milling cutter, and sizing and twisting may be performed. However, when the elongation is higher than nylon 6 or nylon 66, the tension during sizing, twisting, warp preparation, etc. is preferably adjusted to 0.2 cN / dtex or less. 0.15 cN / dtex or less is more preferable.

In addition, since the polyamide fiber of the present invention has a lower hot water shrinkage rate than ordinary nylon 6 and nylon 66, the density at the time of designing the woven or knitted fabric may be adjusted as appropriate in consideration of the hot water shrinkage rate. When a fabric cover factor (CF) is illustrated, 1000-2500 are preferable and 1500-2300 are more preferable. The cover factor is a coefficient representing the density of the fabric structure determined by the thickness of the yarns constituting the fabric and the fabric density, and is represented by the following formula.
CF = X · √D + Y · √D
CF: Cover factor
X: Woven density of woven fabric (line / 2.54cm)
Y: Weft density of woven fabric (line / 2.54cm)
D: Apparent fineness (dtex)

If the CF of the woven fabric is less than 1000, the gap of the woven fabric becomes large, so it is difficult to obtain a stretched and waisted woven fabric. If the CF of the woven fabric exceeds 2500, weaving is difficult and the resulting woven fabric has a hard texture. It tends to be.
In addition, since the specific gravity of nylon 11 used in the present invention is lighter than that of normal nylon 6 or nylon 66, nylon 11 or nylon 6 fiber is used together with the polyamide fiber or false twisted yarn of the present invention when performing the knitting or weaving. When used, when these fibers have the same fineness as the fibers of the present invention, the fibers of the present invention have a larger diameter. Therefore, it is preferable to design an optimum woven or knitted fabric in consideration of these matters.

  The knitted or knitted fabric obtained above is scoured, preset, dyed and final set according to a conventional method, but the nylon 11 used in the present invention has a melting point near 185 ° C., and the texture is high when the temperature is high. Since curing may occur, the temperature of the presetting or final setting is preferably 160 ° C. to 180 ° C., and it is preferable not to raise the temperature excessively even when finishing such as calendering.

  Further, when dyeing, nylon 11 is less likely to be dyed at temperatures near 100 ° C. than nylon 6 or nylon 66, and therefore it is preferable to dye at 120 to 130 ° C. . The polyamide fiber and polyamide false-twisted yarn of the present invention have a strength retention after hot water treatment of 130 ° C. for 30 minutes of 80% or more, so there is little reduction in strength even at the dyeing temperature, and good color development. And strength retention can be achieved.

Next, the manufacturing method of the polyamide fiber (single-type multifilament) of the present invention will be described using an example.
Melt spinning at a spinning temperature of 230 to 270 ° C. using nylon 11 containing 0.1 to 1.0% by mass of a heat-resistant agent such as a hindered phenol antioxidant and having a relative viscosity of 1.6 to 2.4 To do. The spun yarn is cooled and solidified, and then taken up by a first roller having a surface temperature of 30 to 80 ° C. at a speed of 3000 m / min or more. The yarn taken up by the first roller is drawn by a second roller having a surface temperature of 100 to 180 ° C., so that it is drawn at a draw ratio of 1.1 to 2.8 times between the rollers, and a winding speed of 3400 to 5000 m / min. Wind up with.

The method for producing the polyamide false twisted yarn of the present invention will be described using an example.
Using the polyamide fiber of the present invention obtained as described above, spindle rotation speed: 250,000-450,000 rpm, false twist number: 2000-5000 T / M, draw ratio: 1.0-1.7 times, heater temperature 140-180 ° C. Perform false twisting.
At this time, the obtained false twisted yarn may be appropriately adjusted so that the crimp elongation rate is 40 to 65% and the crimp elastic modulus is 20 to 40%, but the false twist number, the draw ratio, and the heater temperature are increased. If it sets, the said crimp elongation rate and a crimp elastic modulus can be made high.
As an example of specific processing conditions, when a multifilament made of only nylon 11 having 90 dtex / 34f and an elongation of 60% is false-twisted using a pin-type false twister, the spindle rotation speed is 325,000 rpm, and the false twist number is 3500 T. The polyamide false twisted yarn of the present invention can be obtained by false twisting at / M, a draw ratio of 1.2 times and a heater temperature of 160 ° C.
In the present invention, when the portion other than the fiber surface of the polyamide fiber is nylon 6, nylon 66, or polyester, crimping may be weakened if the heater temperature during false twisting is low. It is also preferable to increase the heater temperature within the range where it is not fused, or to increase the number of false twists and the draw ratio.

Next, the present invention will be specifically described with reference to examples.
The strength, strength retention rate, hot water shrinkage rate, crimp elongation rate, and crimp elastic modulus of polyamide fiber and polyamide false twisted yarn before and after hydrothermal treatment were measured by the same methods as above, and dyeability and dimensional stability Evaluation of property and texture was performed as follows.
In addition, since evaluation and a measurement of dyeability, dimensional stability, and feeling are performed in the state of a cloth, about the obtained polyamide fiber and polyamide false twisted yarn (Examples 1-9, Comparative Examples 1- In (2), these were evaluated and measured after forming a woven fabric having the following woven structure.
Woven structure: Polyamide fiber or polyamide false twisted yarn obtained for both warp and weft was used to obtain a plain woven fabric having a warp density of 150 / 2.54 cm and a weft density of 90 / 2.54 cm.
[Dyeability]
Each step of dyeing the resulting woven fabric (woven fabric using the fibers of Examples 1 to 9 and Comparative Examples 1 and 2) and knitted fabric (knitted fabric of Example 10 and Comparative Example 3) was performed under the conditions shown below. Then, the reflectance of the woven or knitted fabric after dyeing was measured with an MS-2020 spectrophotometer manufactured by Macbeth Co., Ltd., and an L * value, which was a value obtained by calculating a density index from the CIE Lab color difference formula, was calculated. Furthermore, visual evaluation by 10 panelists was performed and evaluated in the following three stages.
○ ... 8 or more panelists judged to have good colorability △ ... 5 to 7 panelists judged to have good dyeability × ... 4 or less panelists judged to have good dyeability When evaluating the dyeability of the polyamide fiber and the polyamide false twisted yarn (in Examples 1 to 9 and Comparative Examples 1 and 2), scouring and presetting were performed after making the plain fabric of the above-mentioned woven structure. The dyeing was performed at 130 ° C. for 30 minutes, and after soaping, fixing and final setting, the evaluation was performed.
・ Scouring Scouring Agent: Sunmall FL (Nikka Chemical Co., Ltd.) 1g / l
Temperature x time: 80 ° C x 20 minutes Preset temperature x time: 160 ° C x 1 minute Dyeing dye: Mitsui Nylon Black GL (Mitsui BASF) 5% om.f.
Leveling agent: Levelan NKD (manufactured by Maruhishi Oil Chemical Co., Ltd.) 2% om.f.
Acetic acid (48% product): 0.2 ml / l
Temperature x time: described in the examples or comparative examples Bath ratio: 1:50
・ Soaping Soaping agent: Sunmall FL (manufactured by Nikka Chemical) 1g / l
Temperature × Time: 80 ° C. × 20 minutes ・ Fix Fixing agent: Sun Life E-37 (manufactured by Nikka Chemical Co., Ltd.) 1% o.m.f.
Temperature x time: 80 ° C x 20 minutes-Final set Temperature x time: 160 ° C x 1 minute [Dimensional stability]
Using the woven fabric (fabrics using the fibers of Examples 1 to 9 and Comparative Examples 1 and 2) and the knitted fabric (Example 10 and the knitted fabric of Comparative Example 3) after dyeing in the above evaluation of the dyeability, A sample having a width direction of 3 cm and a length direction of 30 cm is prepared as a sample used for measurement in the longitudinal direction, and a sample having a width direction of 30 cm and a length direction of 3 cm is prepared as a sample used for measurement in the weft direction. And after leaving each sample to stand for 24 hours in a room adjusted to a standard state (20 ° C., 65% RH), it corresponds to the longitudinal direction of the sample (for example, when measuring the warp direction of the fabric, it corresponds to warp) ) Count the number of yarns, then suspend the sample in the longitudinal direction and load as [number of yarns counted previously] x [total fineness of the yarn (dtex)] x [1/30] gf To load. After being left for 1 minute, a mark with a mark length of 25 cm is attached to the approximate center of the sample, and this is designated as PAS.
Next, remove the load from the sample, immerse it in a water bath for 1 minute, leave it on the filter paper for 5 seconds, lightly drain it, apply the above load again, leave it for 1 minute, Measure and set this as PAW.
And the dimensional change rate (%) was computed from the following formula.
Dimensional change rate (%) = (| PAS−PAW | / PAS) × 100
In addition, about the textile fabric, the dimensional change rate of the warp direction and the weft direction was calculated, and it was set as the average value of both. For the knitted fabric, a value calculated only in the weft direction was used.
[Feel]
The texture of the woven fabric (the woven fabric using the fibers of Examples 1 to 9 and Comparative Examples 1 and 2) and the knitted fabric (the knitted fabric of Example 10 and Comparative Example 3) after being dyed in the evaluation of the dyeability. Based on a sensory test by 10 panelists, the evaluation was made in the following three stages.
○ ・ ・ ・ 8 or more panelists judged that almost no feeling of sliminess was felt △ ・ ・ ・ 5 to 7 panelists judged that almost no feeling of sliminess was felt × ・ ・ ・ Almost no feeling of sliminess was felt 4 or fewer panelists

Example 1
Using a nylon 11 chip having a relative viscosity (measured at a concentration of 1 g / dl and a temperature of 25 ° C. using 96% sulfuric acid as a catalyst) of 2.01, Irganox 1010 (hindered phenol-based antioxidant: manufactured by Ciba Japan Co., Ltd.) 05% by mass, Irgafos168 (Phosphorus-based processing heat stabilizer: Ciba Japan Co., Ltd.) 0.1% by mass was added, the moisture content was adjusted to 0.05% by mass, and then supplied to an extruder type melt extruder. It was melted at a spinning temperature of 250 ° C. and discharged from a spinneret having 34 spinning holes having a hole diameter of 0.3 mm. The melt-spun yarn was cooled by blowing a cooling air of 15 ° C. to give an oil, and then taken up by a first roller (take-off roller: surface temperature 50 ° C.) of 3000 m / min. Subsequently, the yarn taken up by the first roller is taken up by a second roller (heating roller) having a surface temperature of 130 ° C. so that the yarn is drawn at a draw ratio of 1.5 times and taken up at a take-up speed of 4400 m / min. , 78 dtex / 34 filament polyamide 11 was obtained.

Example 2
Using a nylon 11 chip having a relative viscosity (measured at a concentration of 1 g / dl and a temperature of 25 ° C. using 96% sulfuric acid as a catalyst) of 2.01, Irganox 1010 (hindered phenol-based antioxidant: manufactured by Ciba Japan Co., Ltd.) 05% by mass, Irgafos168 (Phosphorus-based processing heat stabilizer: Ciba Japan Co., Ltd.) 0.1% by mass was added, the moisture content was adjusted to 0.05% by mass, and then supplied to an extruder type melt extruder. It was melted at a spinning temperature of 250 ° C. and discharged from a spinneret having 34 spinning holes having a hole diameter of 0.3 mm. The melt-spun yarn was cooled by blowing a cooling air of 15 ° C. to give an oil, and then taken up by a first roller (take-off roller: surface temperature 50 ° C.) of 3000 m / min. Subsequently, the yarn taken up by the first roller is taken up by a second roller (heating roller) having a surface temperature of 130 ° C. so that the yarn is drawn at a draw ratio of 1.5 times and taken up at a take-up speed of 4400 m / min. A polyamide fiber consisting of nylon 11 having 90 dtex / 34 filaments was obtained.

Example 3
Using a nylon 11 chip having a relative viscosity (measured at a concentration of 1 g / dl and a temperature of 25 ° C. using 96% sulfuric acid as a catalyst) of 2.01, Irganox 1010 (hindered phenol-based antioxidant: manufactured by Ciba Japan Co., Ltd.) 1% by mass, Irgafos168 (phosphorous processing heat stabilizer: manufactured by Ciba Japan) was added by 0.2% by mass, the moisture content was adjusted to 0.05% by mass, and then supplied to an extruder type melt extruder. It was melted at a spinning temperature of 250 ° C. and discharged from a spinneret having 48 spinning holes having a hole diameter of 0.2 mm. The melt-spun yarn was cooled by blowing a cooling air of 15 ° C. to give an oil agent, and then taken up by a first roller (take-off roller: surface temperature 50 ° C.) at 3300 m / min. Subsequently, the yarn taken up by the first roller is taken up by a second roller (heating roller) having a surface temperature of 150 ° C. to be drawn between the rollers at a draw ratio of 1.3 times, and taken up at a take-up speed of 4200 m / min. , 78 dtex / 48 filament polyamide 11 was obtained.

Example 4
Using a nylon 11 chip having a relative viscosity (measured at a concentration of 1 g / dl and a temperature of 25 ° C. using 96% sulfuric acid as a catalyst) of 2.01, Irganox 1010 (hindered phenol-based antioxidant: manufactured by Ciba Japan Co., Ltd.) 2% by mass, Irgafos168 (phosphorous processing heat stabilizer: manufactured by Ciba Japan Co., Ltd.) was added in an amount of 0.4% by mass, the moisture content was adjusted to 0.05% by mass, and then supplied to an extruder type melt extruder. It was melted at a spinning temperature of 250 ° C. and discharged from a spinneret having 48 spinning holes having a hole diameter of 0.15 mm. The melt-spun yarn was cooled by blowing a cooling air at 15 ° C. to give an oil agent, and then taken up by a first roller (take-off roller: surface temperature 50 ° C.) at 3500 m / min. Subsequently, the yarn taken up by the first roller is taken up by a second roller (heating roller) having a surface temperature of 150 ° C. so as to be drawn between the rollers at a draw ratio of 1.2 times, and taken up at a take-up speed of 4100 m / min. A polyamide fiber made only of nylon 11 having a 56 dtex / 48 filament was obtained.

Comparative Example 1
Using a nylon 6 chip with a relative viscosity (96% sulfuric acid as a catalyst, concentration of 1 g / dl, temperature of 25 ° C.) of 2.41, without adding Irganox1010 and Irgafos168, adjusting the moisture content to 0.05 mass% Then, it was supplied to an extruder type melt extruder, melted at a spinning temperature of 255 ° C., and discharged from a spinneret having 34 spinning holes having a hole diameter of 0.3 mm. The melt-spun yarn was cooled by blowing a cooling air of 15 ° C. to give an oil agent, and then taken up by a first roller (take-off roller: surface temperature 50 ° C.) at 3200 m / min. Subsequently, the yarn taken up by the first roller is taken up by a second roller (heating roller) having a surface temperature of 140 ° C. to be drawn between the rollers at a draw ratio of 1.3 times, and taken up at a take-up speed of 4200 m / min. , 78 dtex / 34 filament polyamide 6 was obtained.

Example 5
Using the polyamide fiber obtained in Example 1 as a feed yarn, using a pin-type false twister, the spindle rotation speed was 325,000 rpm, false twist number Z-3570 T / M, the draw ratio was 1.06 times, and the heater temperature was 160 ° C. Twisting was performed to obtain a polyamide false twisted yarn.

Example 6
Using the polyamide fiber obtained in Example 2 as a supply yarn, using a pin-type false twister, the spindle rotation speed was 325,000 rpm, the false twist number was Z-3570 T / M, the draw ratio was 1.20 times, and the heater temperature was 160 ° C. Twisting was performed to obtain a polyamide false twisted yarn.

Example 7
Using a nylon 11 chip having a relative viscosity (measured at a concentration of 1 g / dl and a temperature of 25 ° C. using 96% sulfuric acid as a catalyst) of 2.01, Irganox 1010 (hindered phenol-based antioxidant: manufactured by Ciba Japan Co., Ltd.) 05% by mass, Irgafos168 (Phosphorus-based processing heat stabilizer: Ciba Japan Co., Ltd.) 0.1% by mass was added, the moisture content was adjusted to 0.05% by mass, and then supplied to an extruder type melt extruder. It was melted at a spinning temperature of 250 ° C. and discharged from a spinneret having 34 spinning holes having a hole diameter of 0.3 mm.
The melt-spun yarn was cooled by blowing a cooling air of 15 ° C. to give an oil agent, and then taken up by a first roller (take-off roller: surface temperature 50 ° C.) at 3100 m / min. Subsequently, the yarn taken up by the first roller is drawn by a second roller (heating roller) having a surface temperature of 130 ° C. so that the yarn is drawn at a draw ratio of 1.02 and taken up at a take-up speed of 3200 m / min. A polyamide fiber made only of nylon 11 having 110 dtex / 24 filament was obtained.
Using the above-mentioned polyamide fiber as a supply yarn, using a pin type false twisting machine, false twisting is performed at a spindle rotation speed of 325,000 rpm, false twisting number Z-3570 T / M, a draw ratio of 1.45 times, and a heater temperature of 160 ° C. A false twisted yarn was obtained.

Example 8
A polyamide false twisted yarn was prepared in the same manner as in Example 7 except that the same polyamide fiber as in Example 7 was used as the supply yarn, false twisting was performed at a draw ratio of 1.40 times and a heater temperature of 170 ° C. Obtained.

Example 9
Using the polyamide fiber obtained in Example 2 as a supply yarn, using a disk-type false twister, the yarn speed is 500 M / MIN, the disc (5 mm thickness) configuration Z1-10-1, the draw ratio is 1.20 times, D / False twisting was performed at Y1.82 and heater temperature (short heater / long heater) 250/250 ° C. to obtain a polyamide false twisted yarn.

Comparative Example 2
Using the polyamide fiber obtained in Comparative Example 1 as a feed yarn, using a pin-type false twister, the spindle rotation speed was 325,000 rpm, the false twist number was Z-3570 T / M, the draw ratio was 1.06, and the heater temperature was 180 ° C. Twisting was performed to obtain a polyamide false twisted yarn.

Example 10
Using the polyamide false twisted yarn obtained in Example 5, a 33-inch, 28-gauge circular knitting machine was used, and a mock-lodia structure with a wale density of 58 / 2.54 cm and a course density of 46 / 2.54 cm. A knitted fabric was prepared.
After scouring and pre-setting in the above-described dyeability evaluation, dyeing was performed at 130 ° C. for 30 minutes. Thereafter, soaping, fixing, and final setting were performed to obtain a knitted fabric having a wale density of 63 pieces / 2.54 cm and a course density of 50 pieces / 2.54 cm.

Comparative Example 3
A knitted fabric (a mock-lodia knitted fabric with a wale density of 58 pieces / 2.54 cm and a course density of 46 pieces / 2.54 cm) except that the polyamide false twisted yarn obtained in Comparative Example 2 was used. ) And processed in each step in the dyeability evaluation to obtain a knitted fabric having a wale density of 65 pieces / 2.54 cm and a course density of 53 pieces / 2.54 cm.

  Tables 1 and 2 show the characteristic values and evaluation results of the polyamide fibers of Examples 1 to 4 and Comparative Example 1, Examples 5 to 9 and the polyamide false twisted yarn of Comparative Example 2, Example 10 and Comparative Example 3. Show.

As is clear from Tables 1 and 2, the polyamide fibers of Examples 1 to 4 and the polyamide false-twisted yarns of Examples 5 to 9 are excellent in high elongation characteristics, and after hot water treatment at 130 ° C. for 30 minutes. The strength retention was 80% or more, and the hot water shrinkage was small. Furthermore, the polyamide false twisted yarns of Examples 5 to 9 had a crimp elongation percentage and a crimp elastic modulus in appropriate ranges. For this reason, the woven fabric obtained from these fibers and false twisted yarn and the knitted fabric of Example 10 were excellent in dyeability, dimensional stability, and texture evaluation, and could be dyed at high temperatures. .
On the other hand, since the polyamide fiber of Comparative Example 1 was made of nylon 6, the strength retention after hot water treatment at 130 ° C. for 30 minutes was as low as less than 80%, and the hot water shrinkage rate also exceeded 12%. It was. Since the polyamide false twisted yarn of Comparative Example 2 was obtained by using the polyamide fiber of Comparative Example 1, the strength retention after hot water treatment at 130 ° C. for 30 minutes was as low as less than 80%, and the hot water shrinkage rate Was over 7%. Further, the crimp elongation rate and the crimp elastic modulus were also outside the scope of the present invention. For this reason, the woven fabric obtained from this fiber and false twisted yarn and the knitted fabric of Comparative Example 3 have good dyeability evaluation, but have a large dimensional change rate and cannot be dyed at high temperature. Moreover, it was also inferior to evaluation of a texture.

Claims (7)

A multifilament having an elongation of 53.4-80% in which only nylon 11 containing a hindered phenolic antioxidant and a phosphorus processing heat stabilizer is disposed,
The total content of the hindered phenolic antioxidant and the phosphorus processing heat stabilizer is 0.1 to 1.0% by mass,
The strength after the hot water treatment at 130 ° C. for 30 minutes is 3.0 cN / dtex or more, the strength retention after the hot water treatment at 130 ° C. for 30 minutes calculated by the following formula (1) is 80% or more, A polyamide multifilament having a hot water shrinkage of 10% or less.
Strength retention after hot water treatment at 130 ° C. for 30 minutes (%) = (B / A) × 100 (1)
However, the strength before the hot water treatment is A, and the strength after the hot water treatment is B. L * value is 15.9 to 16.7, The polyamide multifilament of Claim 1 characterized by the above-mentioned. A false twisted yarn comprising the polyamide multifilament according to claim 1 or 2, wherein the strength after hot water treatment at 130 ° C for 30 minutes is 2.8 cN / dtex or more, and is calculated by the following formula (2): A polyamide false twisted yarn characterized by having a strength retention of 80% or more and a hot water shrinkage rate of 7% or less after the hot water treatment at 130 ° C. for 30 minutes.
Strength retention after hot water treatment at 130 ° C. for 30 minutes (%) = (F / E) × 100 (2)
However, the strength before the hot water treatment is E, and the strength after the hot water treatment is F.   L * value is 12.3-13.2, The polyamide false twisted yarn of Claim 3 characterized by the above-mentioned.   The polyamide false twisted yarn according to claim 3 or 4, which has a crimp elongation of 40 to 65% and a crimp elastic modulus of 20 to 40%. A woven or knitted fabric comprising the polyamide multifilament according to claim 1 or 2 as at least a part thereof. A woven or knitted fabric comprising the polyamide false twisted yarn according to any one of claims 3 to 5 as at least a part thereof.