JP7100801B2 - Spinned yarns containing flat acrylonitrile fibers with three-dimensional crimps and knitted fabrics or woven fabrics containing the spun yarns - Google Patents

Description

The present technique is to provide a spun yarn that has a voluminous feel and is excellent in heat retention when a knitted fabric or a woven fabric is produced.

Conventionally, acrylonitrile-based synthetic fibers have been used in the fields of clothing, piles, etc. due to their excellent color development and texture, and many developments aimed at improving functionality such as heat retention have been carried out so far. .. For example, in Patent Document 1, by forming an acrylic fiber in which two acrylonitrile-based polymers having different acrylonitrile content ratios are combined in a side-by-side manner, coil-like crimping is exhibited and an acrylic fiber having excellent bulkiness can be obtained. Is disclosed.

International Publication No. 2015/166956

However, in the case of the acrylic fiber disclosed in Patent Document 1, although the number of crimps and the crimp elongation rate show large values at first glance, it is actually due to mechanical crimping, and the cross section of the fiber. Since the shape is close to a circle and the moment of inertia of area on the short axis is high, it cannot be said that the coiled crimp is sufficiently expressed. In addition, since it has a cross-sectional shape close to a circle, the fiber bundles are easily organized, and the spun yarn using the fibers is bulky because the single fibers constituting the fiber bundles are densely converged after dyeing. So, there were still issues left.

The present invention has been made based on such a current situation, and an object thereof is to be able to sufficiently express coiled three-dimensional crimping, and to perform three-dimensional crimping even after dyeing as a spun yarn. It is an object of the present invention to provide a spun yarn capable of sufficiently exhibiting bulkiness, which is also a feature, and a woven fabric or knitted fabric containing the spun yarn.

As a result of diligent studies on the above-mentioned problems, the present inventors have found that the above-mentioned object can be achieved by using a spun yarn containing a flat acrylonitrile-based fiber having three-dimensional crimping. That is, the object of the present invention is achieved by the following means.

[1] A flat acrylonitrile fiber ( 1) containing two types of acrylonitrile-based polymer components having different acrylonitrile content ratios, the two types of acrylonitrile-based polymer having a side-by-side structure, and a flatness of 1.5 to 8. However, the spun yarn is characterized by containing 20% by weight or more (excluding those having recesses in the fiber cross section) .
[ 2 ] The acrylonitrile fiber is characterized in that the Cf value calculated by the following formula 1 based on the crimp number Cn and the crimp rate Ci obtained according to JIS L1015: 2010 after the unloaded boiling water treatment is 16 or more. The spun yarn according to claim 1.
(Equation 1)
Cf = Cn × (1-Ci / 100)
[ 3 ] The spun yarn according to claim 1 or 2 , wherein the moment of inertia of area per single yarn in the minor axis direction of the acrylonitrile fiber is 400 to 25,000 μm ⁴ .
[ 4 ] A woven fabric or knitted fabric containing the spun yarn according to any one of claims 1 to 3 .

According to the present invention, by making the cross section of the acrylonitrile-based fiber having three-dimensional crimp into a flat shape, the soft feeling of the fiber is increased and the three-dimensional crimp is more easily expressed. Further, since the bulk of the spun yarn increases after dyeing in the spun yarn containing the fiber, the spun yarn is contained in the spun yarn so that it does not easily settle even in repeated washing and is a woven fabric or knitted fabric having an excellent volume feeling. Can be provided.

Spinned yarn containing acrylonitrile-based fiber of Example 3 (before dyeing) Spinned yarn containing acrylonitrile-based fiber of Example 3 (after dyeing) Spinned yarn containing acrylonitrile fiber of Comparative Example 1 (after dyeing) Knitted fabric using the spun yarn (after dyeing) of Example 3 Knitted fabric using the spun yarn (after dyeing) of Comparative Example 1

The spun yarn of the present invention contains two types of acrylonitrile-based polymer components having different acrylonitrile contents, and contains 20% by weight or more of flat acrylonitrile-based fibers having a flatness of 1.5 to 8. It is preferably contained in an amount of 30% by weight or more, more preferably 50% by weight or more. Further, a spun yarn composed of 100% by weight of acrylonitrile-based fiber used in the present invention may be used. If the content of the acrylonitrile-based fiber is less than 20% by weight, it is difficult to obtain the bulky effect of the three-dimensional crimping, and the volume feeling when the woven fabric or knitted fabric is made is inferior.

Further, the flat acrylonitrile-based fiber used in the present invention has a two-component structure as described above, and the fiber itself exhibits a coil-shaped three-dimensional crimp due to the difference in the heat shrinkage rate of the acrylonitrile-based polymer. Can be made to. Therefore, it is superior in bulkiness and durability to mechanically applied normal crimping, and the spun yarn containing the fiber and the woven fabric or knitted fabric containing the spun yarn have an excellent volume feeling, and are repeated. By washing, it can be made hard to settle.

Further, as the above-mentioned two-component structure, a side-by-side structure in which two acrylonitrile-based polymer components are bonded to each other or a random structure in which the number of layers differs depending on each single fiber can be mentioned. By adopting such a two-component structure, it is possible to develop three-dimensional crimping in the fiber due to the difference in the heat shrinkage rate of the constituent components. Further, as the laminated structure, it is preferable that the fibers are laminated so as to be parallel to the long axis direction of the fiber cross section because three-dimensional crimping is likely to occur. Of the two types of laminated structures described above, the side-by-side structure is preferable because it is easier to develop three-dimensional crimping.

Further, the flat acrylonitrile fiber used in the present invention has a flat cross-sectional shape, and the lower limit of the flatness calculated by dividing the long axis length of the fiber cross section by the short axis length is 1.5. The above is preferable, and 1.7 or more is more preferable. The upper limit is preferably 8 or less, more preferably 5 or less, and even more preferably less than 4. With this shape, the moment of inertia of area in the minor axis direction of the fiber is lowered, so that the softness of the fiber is improved and crimping due to the difference in heat shrinkage of the polymer components constituting the fiber is exhibited. It becomes easier to do. As a result, the spun yarn containing the fiber can be made excellent in bulkiness, and the woven fabric or knitted fabric containing the spun yarn has an excellent voluminous feel and is less likely to settle even in repeated washing. It can be made excellent in durability.

The flat acrylonitrile fiber used in the present invention preferably has the above-mentioned Cf value of preferably 16 or more, more preferably 18 or more, still more preferably 20 or more. The Cf value referred to here represents the number of crimps per inch of the fiber when the fiber is stretched at a specific ratio, and if this Cf value is high, even after the fiber is stretched. , It can be said that sufficient crimping remains in the fiber. When this Cf value is 16 or more, sufficient crimping remains even after processing into a woven fabric or knitted fabric or after repeated washing, and improvement in volume and durability can be expected. On the other hand, if it is less than 16, the number of crimps of the fiber may be reduced due to processing into a woven fabric or knitted fabric, repeated washing, etc., and a satisfactory volume feeling as a woven fabric or knitted fabric may not be obtained. ..

Further, in the flat acrylonitrile fiber adopted in the present invention, the lower limit of the moment of inertia of area per single yarn in the minor axis direction of the fiber cross section is preferably 400 μm ⁴ or more, more preferably 700 μm ⁴ or more. It is more preferably 1000 μm ⁴ or more. The upper limit of the moment of inertia of area is preferably 25,000 μm ⁴ or less, more preferably 20000 μm ⁴ or less, and even more preferably 15,000 μm ⁴ or less. When the moment of inertia of area is in the range of 400 to 25,000 μm ⁴ , in addition to obtaining a soft touch, it becomes easier to develop three-dimensional crimping, so that the spun yarn containing the fiber becomes bulky. It becomes easy to obtain a woven fabric or a knitted fabric that is satisfactory in terms of volume and softness.

Further, the acrylonitrile-based polymer constituting the flat acrylonitrile-based fiber used in the present invention may be a copolymer of acrylonitrile and another vinyl-based monomer, and the acrylonitrile content ratio is preferable as the monomer composition. Is preferably 40% by weight or more, more preferably 70% by weight or more, still more preferably 80% by weight or more. If the acrylonitrile content is less than 40% by weight, sufficient fiber strength may not be obtained when the fiber is made. Further, it is preferable that the acrylonitrile content ratio of the highly shrinkable component among the two acrylonitrile-based polymer components is less than 90% by weight because excellent three-dimensional crimping can be easily obtained.

As the two acrylonitrile-based polymer components having different acrylonitrile content ratios adopted in the present invention, the acrylonitrile content ratio is preferably 1.0% by weight or more, and more preferably 1.5% by weight or more. .. As a result, three-dimensional crimping due to the difference in heat shrinkage due to the difference in the acrylonitrile content ratio is sufficiently developed, so that the spun yarn can be made bulky. Therefore, the woven fabric or knitted fabric containing the spun yarn can be made excellent in volume. On the other hand, if the difference in the acrylonitrile content ratio is less than 1.0% by weight, the difference in heat shrinkage between the two acrylonitrile-based polymers becomes small, the desired crimping cannot be obtained, and the spun yarn is poorly bulky. The woven or knitted fabric may be less voluminous.

The other vinyl-based monomer that can be copolymerized with acrylonitrile is not particularly limited, but is limited to acrylic acid, methacrylic acid, or esters thereof; acrylamide, methacrylamide or N-alkyl substituents thereof; acetic acid. Vinyl esters such as vinyl; vinyl halide or vinylidene such as vinyl chloride, vinyl bromide, vinylidene chloride; unsaturated sulfonic acid such as vinyl sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid, p-styrene sulfonic acid or These salts and the like can be mentioned. As long as the above-mentioned composition is satisfied, a plurality of types of the above-mentioned acrylonitrile-based polymer may be used as constituents.

The lower limit of the fineness of the flat acrylonitrile fiber is preferably 0.5 dtex or more, more preferably 1.0 dtex or more, and further preferably 2.0 dtex or more. The upper limit of the fineness is preferably 20 dtex or less, more preferably 15 dtex or less, and further preferably 8 dtex or less. If the fineness is less than 0.5 dtex, it may be difficult to obtain the desired bulkiness because the fibers are too fine. Further, when it exceeds 20 dtex, since the fiber is too thick, the moment of inertia of area of the fiber tends to be high, and the softness may be deteriorated, or the expression of crimping may be lowered and the bulkiness may be insufficient. There is.

The method for synthesizing the acrylonitrile-based polymer constituting the flat acrylonitrile-based fiber described above is not particularly limited, and a suspension polymerization method, an emulsion polymerization method, a solution polymerization method, or the like, which are well-known polymerization means, are used. can do.

Further, the method for producing the flat acrylonitrile-based fiber of the present invention using the obtained polymer is not particularly limited, but an example in the case of producing using the wet spinning method is generally well used. Two acrylonitrile-based polymers having different acrylonitrile content ratios produced by known aqueous suspension polymerization are dissolved in a solvent to prepare a stock solution (high acrylonitrile-containing polymer stock solution (A), low acrylonitrile-containing polymer stock solution). (B).

Here, examples of the solvent for dissolving the acrylonitrile-based polymer include organic solvents such as dimethylformamide, dimethylacetamide, dimethylsulfoxide and acetone, and inorganic solvents such as nitrate, zinc chloride aqueous solution and sodium thiocyanate aqueous solution. ..

The prepared A and B stock solutions were mixed with A / B in weight ratio of A / B = 20/80 to 80/20 by using, for example, a composite spinning apparatus as disclosed in Tokusho 39-24301. A side-by-side type fiber can be produced by guiding the fiber to a composite spinneret, extruding it into a coagulation bath, and then performing washing with water, stretching, densification and drying, wet heat treatment, oil treatment, crimping treatment, and the like. It is also possible to make a random type by spinning a spinning stock solution that is randomly multi-layered with a mixer or the like, and by changing the nozzle hole type to be used or changing the spinning speed. , It becomes possible to obtain a fiber having a desired flat shape. At that time, an arbitrary Cf value can be obtained by changing the weight ratio of A and B and the wet heat treatment temperature.

The spun yarn of the present invention may contain other fibers in addition to the above-mentioned flat acrylonitrile-based fibers. The other fibers are not particularly limited, but are limited to acrylonitrile fibers other than the above-mentioned flat acrylonitrile fibers, natural fibers such as cotton, wool and cashmere, regenerated fibers such as rayon and cupra, cellulose acetate fibers and promix. Semi-synthetic fibers such as, nylon, polyester, synthetic fibers such as urethane, and the like can be mentioned, and a plurality of these may be used.

The other fibers are not particularly limited in terms of cross-sectional shape, but may be round or non-round, and examples of the non-round type include flat, triangular, Y-shaped, and cross-shaped cross sections.

The count of the spun yarn of the present invention is not particularly limited and may be appropriately selected depending on the intended use, but the cotton count is preferably in the range of 5 to 120. Further, if it is a woven or knitted fabric for clothing, it is more preferable to have a count of 10 to 100.

Since the spun yarn of the present invention described above is excellent in bulkiness and softness, it can be suitably used for woven fabrics, knitted fabrics and the like.

For example, when the spun yarn of the present invention is used for a woven fabric, it can be used as a warp and / or a weft of the woven fabric, and the woven fabric can be woven by a normal weaving process. Further, when the spun yarn of the present invention is used for knitting, it can be knitted by a normal circular knitting or warp knitting process.

The types of looms and knitting machines used at that time are not particularly limited. In addition, the texture and density of the woven and knitted fabric are selected according to the required texture and volume.

The obtained woven fabric or knitted fabric is appropriately dyed and finished by a general dyeing process and conditions according to the material to be used, and the final finish is a woven or knitted fabric. Further, if necessary, it can be dyed with raw cotton dyed or spun yarn before the weaving and knitting process.

Further, the spun yarn of the present invention can be used for a part of the woven fabric or the knitted fabric, or can be used for the whole woven fabric or the knitted fabric, and can be determined according to the use and purpose thereof.

The woven and knitted fabric using the spun yarn of the present invention can be preferably used in various fields such as clothing and materials, and is not particularly limited, but for example, underwear, underwear, shirts, jumpers, sweaters, and pants. , Training wear, tights, belly band, muffler, hat, gloves, socks, ear pads, filters, curtains, etc. In particular, it can be suitably used for applications requiring heat retention such as inner shirts and inner tights for sportswear, sweaters, and winter clothing, and inner materials for winter sports such as mountain climbing, skiing, and skating.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to the following Examples. The parts and percentages in the examples are shown on a mass basis unless otherwise specified. The heat retention rate and the evaluation of the bulkiness of the spun yarn before and after dyeing described in the examples are measured by the following methods.

(1) Number of crimps Cn
Measured and calculated according to JIS L1015.

(2) Crisp rate Ci
Measured and calculated according to JIS L1015.

(3) Based on the Cn and Ci measured and calculated by the Cf value JIS L1015, it is calculated by the following formula 3.
(Equation 3)
Cf = Cn × (1-Ci / 100)

(4) Flatness 150 to 200 single fibers are taken out from the sample fibers and arranged to form a fiber bundle. The cross section of the fiber bundle was cut and a cross section photograph was taken using an optical microscope. The minor axis (A) and the major axis (B) of 50 fibers were measured from the cross-sectional photograph, and calculated by the flatness ( B ) / ( A ).

(5) Moment of inertia of area When the fiber cross section is circular, the moment of inertia of area of the fiber was calculated by πD ^4/64 (where D is the diameter of the circle). In the case of a fiber having a rectangular cross section, the moment of inertia of area was calculated by a ³ b / 12 (where a is the length of the short side and b is the length of the long side). In the case of a fiber having an elliptical or oval cross section, if the flatness is in the range of 1.5 to 8, a rectangular shape having a major axis as the length of the long side and a minor axis as the length of the short side. Since the difference is small enough to be close to the moment of inertia of area, the above equation for the case where the cross section is rectangular was used as a substitute for the calculation.

(6) Preparation of spun yarn and knitted fabric 70% of sample fiber (fiber length 64 mm variable cut) and 30% of ordinary acrylic fiber (K8-3.3TV64 manufactured by Nippon Exlan Industry Co., Ltd.) as other fibers. A 36-count (cotton-count and 21.3-count) spun yarn was produced. A dyeing solution in which 200% of the cationic dye Nichilon Black G (manufactured by Nissei Kasei Co., Ltd.) is added to the spun yarn at a ratio of 2.5% to the weight of the spun yarn. After dyeing, the yarn was soaped, washed with water, and dried to obtain a spun yarn after dyeing. In addition, a tenjiku knitted fabric (10 gauge) was prepared using the obtained spun yarn after dyeing.

(6) Insulation evaluation (Thermorabo II dry contact method)
The knitted fabric prepared by the above method is cut into 2 x 2 cm pieces. Using a KES-F7 Thermolab II tester (under windward of 30 cm / sec) manufactured by Kato Tech Co., Ltd., set the test piece on a hot plate set at a constant temperature (room temperature + 10 ° C). Then, the amount of heat (a) dissipated through the test piece is determined. Separately, the amount of heat (b) dissipated without setting the test piece was obtained, and the heat retention rate (%) was calculated according to the following formula.
Insulation rate (%) = (1-a / b) x 100

(7) Observation of spun yarn Using a microscope manufactured by Keyence Co., Ltd. (model number: VHX-2000, lens: VH-Z100R), the magnification of the lens was set to 100 times, and the shape observation of the spun yarn after dyeing described above and the shape observation of the spun yarn were performed. The knitted fabric produced by using the spun yarn was observed.

(Production Examples 1 to 4) Preparation of Acrylonitrile Fiber Acrylonitrile polymer A was prepared by suspend polymerization of 88 parts by weight of acrylonitrile and 12 parts by weight of vinyl acetate as high heat shrinkage components. Further, 90 parts by weight of acrylonitrile and 10 parts by weight of methyl acrylate were suspended and polymerized as low heat shrinkage components to prepare an acrylonitrile-based polymer B.

10 parts each of the acrylonitrile-based polymers A and B are dissolved in 90 parts of a 50% sodium rodaneate aqueous solution, and Ap and Bp are shown in Table 1 using, for example, the composite spinning apparatus disclosed in Japanese Patent Publication No. 39-24301. Guided to a composite spinneret with the composition ratio described in 1 above, extruded into a 10% rodane soda aqueous solution which is a coagulation bath, then stretched 10 times with boiling water, dried with hot air at 115 ° C., and further heat-treated in pressurized steam at 120 ° C. Acrylonitrile-based fibers were obtained. Needless to say, the single-component fiber can be produced by using a conventionally known method for producing acrylonitrile. By utilizing the difference in the type or pore size of the mixer and spinneret used at this time, acrylonitrile-based fibers a to d having adjusted fineness and cross-sectional shape were produced. Detailed data of each fiber is shown in Table 1.

(Examples 1 to 3, Comparative Example 1)
Acrylonitrile-based fibers a to d were used as sample fibers to prepare spun yarns by the above-mentioned method. Table 2 shows the types of acrylonitrile-based fibers constituting the spun yarn and the results of heat retention evaluation of the knitted fabric produced using the spun yarn. In addition, microscope images of the produced spun yarn and knitted fabric are shown as FIGS. 1 to 5.

The flat acrylonitrile fiber of the present invention was contained, and as can be seen from the spun yarn before dyeing (FIG. 1) and the spun yarn after dyeing (FIG. 2), the flat acrylonitrile fiber of the present invention was contained. Since the spun yarn develops three-dimensional crimping in the dyeing process, the spun yarn after dyeing becomes very bulky. On the other hand, the spun yarn of Comparative Example 1 having a round fiber cross section was poor in bulk as can be seen from FIG. Therefore, the knitted fabric (FIG. 4) produced by using the spun yarn containing the flat acrylonitrile fiber of the present invention is knitted as compared with the knitted fabric (FIG. 5) produced by using the spun yarn of Comparative Example 1. The structure is such that the gaps in the ground mesh are filled. As a result, the one using the spun yarns of Examples 1 to 3 has an improved heat-retaining effect as compared with the one using the spun yarn of Comparative Example 1 which is a conventional product, and further, the structure of the knitted fabric collapses. It is considered that it is difficult and has excellent washing durability.

Claims (4)

Flat acrylonitrile fiber (however, fiber ) containing two types of acrylonitrile-based polymer components having different acrylonitrile content ratios, the two types of acrylonitrile-based polymer having a side-by-side structure, and a flatness of 1.5 to 8. A spun yarn characterized by containing 20% by weight or more (excluding those having recesses in the cross section) . The claim is that the acrylonitrile fiber has a Cf value of 16 or more calculated by the following formula 1 based on the crimp number Cn and the crimp ratio Ci obtained according to JIS L1015: 2010 after the no-load boiling water treatment. The spun yarn according to 1.
(Equation 1)
Cf = Cn × (1-Ci / 100) The spun yarn according to claim 1 or 2 , wherein the moment of inertia of area per single yarn in the minor axis direction of the acrylonitrile fiber is 400 to 25,000 μm ⁴ . A woven fabric or knitted fabric containing the spun yarn according to any one of claims 1 to 3 .

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