TW201816210A - Highly heat-shrinkable polyamide fibers, and filament-mixed yarn and woven or knit fabric each including same - Google Patents

Abstract

Provided is woven or knit fabric which gives senses of denseness, bulkiness, and softness. Highly heat-shrinkable polyamide fibers can be provided, the fibers having a glass transition temperature (Tg) of 85-95 DEG C, a degree of shrinkage with boiling water (B) of 30-50%, and a stress of heat shrinkage (H) of 0.20 cN/dtex or greater.

Description

   High heat-shrinkable polyamide fiber and mixed fiber yarn and knitted fabric using the same   

The present invention relates to a polyamide fiber having high heat shrinkability, and a mixed fiber yarn and knitted fabric using the same.

In recent years, the development of sewing items such as fabrics using special fibers that have not been found so far is actively progressing. Among them, there are many examples of using high-shrinkable fibers, such as mixed filaments composed of two different heat-shrinkable fibers; and after weaving a high-heat-shrinkable raw yarn, heat treatment with boiling water, steam, etc., There have been many examples of fabric development with fluffiness and swelling feeling, and improved hand feel and surface characteristics.

As a representative example of fibers with high shrinkage properties, such as high-shrinkage polyester fibers, but polyester fibers have higher Young's modulus characteristics than polyamide fibers. After shrinking, the hand feels hard, and there are problems with the comfort of the clothing. On the other hand, polyamide fibers have a low Young's modulus, can obtain a soft feel, and have excellent characteristics such as abrasion resistance. Therefore, they are suitable for clothing applications. However, in order to further impart performance, high shrinkage is targeted. Polyamide fibers have been extensively developed.

For example, the highly shrinkable polyamide fiber disclosed in Patent Document 1 is composed of crystalline polyamide and amorphous polyamide, and has a boiling water shrinkage of 35% or more. Further, the highly shrinkable polyamide fiber disclosed in Patent Document 2 is composed of crystalline polyamide and amorphous polyamide, and has a boiling water shrinkage of 15% or more. In addition, the highly shrinkable polyamide fiber disclosed in Patent Document 3 has a thermal shrinkage stress of 220 to 400 mg / d. The high-shrinkage polyamidamine fibers disclosed in Patent Document 4 have a thermal shrinkage stress of 0.15 cN / dtex or more.

    [Prior technical literature]         [Patent Literature]    

Patent Document 1: Japanese Patent Laid-Open No. 4-2814

Patent Document 2: Japanese Patent Laid-Open No. 3-64516

Patent Document 3: Japanese Patent Laid-Open No. 2000-73231

Patent Document 4: Japanese Patent Laid-Open No. 2007-100270

However, although the highly shrinkable polyamide fibers disclosed in Patent Documents 1 and 2 have high boiling water shrinkage, the shrinkage stress is small. Therefore, even if the polyamide fibers are woven or knitted, The heat treatment has not sufficiently shrunk, and a high-density fabric with a feeling of swelling cannot be obtained.

Although the high-shrinkage polyamide fibers disclosed in Patent Documents 3 and 4 have high thermal shrinkage stress, the glass transition temperature (Tg) is close to room temperature. When stored under tension, thermal shrinkage stress will decrease with time. Even if the knitted fabric woven and woven with this polyamide fiber is heat treated, the shrinkage stress is small, so it does not shrink sufficiently and cannot be obtained. High-density fabric with bloating.

Here, the present invention has been made to solve the above-mentioned problems, and an object thereof is to provide a high-shrinkage-resistant polyamide fiber having high shrinkage characteristics (H) and boiling water shrinkage (B) with high shrinkage properties; Some of them are fluffy mixed filaments using high heat-shrinkable polyamide fibers, and at least some of them are knitted fabrics with high heat-shrinkable polyamide fibers and / or mixed filaments, which have a feeling of swelling. , Soft high-density knitted fabric.

To achieve the above object, the highly heat-shrinkable polyamide fiber of the present invention has the following structure.

(1) A highly heat-shrinkable polyamide fiber, which has a glass transition temperature (Tg): 85 to 95 ° C, boiling water shrinkage (B): 25 to 50%, and heat shrinkage stress (H): 0.20 cN / dtex or more.

(2) The high heat-shrinkable polyamide fiber according to (1), wherein the total fineness is 5 to 80 dtex and the monofilament fineness is 0.9 to 3.0 dtex.

(3) A mixed-fiber yarn using at least a part of the high heat-shrinkable polyamide fiber described in (1) or (2).

(4) A knitted fabric using at least a part of the high heat-shrinkable polyamide fiber described in (1) or (2) and / or the mixed fiber yarn described in (3).

The highly heat-shrinkable polyamide fiber of the present invention has high heat shrinkage stress (H), boiling water shrinkage (B), and excellent shrinkage characteristics, and the glass transition temperature (Tg) is high, and there is no reduction in heat shrinkage stress over time. Therefore, with the highly heat-shrinkable polyamide fiber, at least a part of the mixed fiber using the highly heat-shrinkable polyamide fiber is fluffy, and at least a part of it is used with the high heat-shrinkable polyamide fiber and / or the mixed fiber yarn. Knitted fabric can be a high-density knitted fabric with a feeling of swelling and softness.

The highly heat-shrinkable polyamide fiber of the present invention is a fiber composed of crystalline polyamide and amorphous polyamide.

The crystalline polyfluorene is a crystalline polyamine having a melting point. The so-called polymer in which the hydrocarbon group is linked to the main chain via a fluorene bond is, for example, polydecamide, polyhexamethylenehexamidine, Polyhexamethylene hexamethylene diamine, polytetramethylene hexamethylene diamine, condensation polymerization type polyamidine of 1,4-cyclohexane dimethylamine and a linear aliphatic dicarboxylic acid, and the copolymerization of these Fit or mixture of these. Among them, from the viewpoint of easily presenting a homogeneous system and showing stability, it is preferable to use homopolyamine.

The crystalline polyamidoamine is preferably composed of diamines and dibasic acids. Specific examples of the diamines include butanediamine, hexamethylenediamine, nonanediamine, undecanediamine, and dodecyl methylene. Diamine, 2,2,4-trimethylhexanediamine, 2,4,4-trimethylhexanediamine, bis (4,4'-aminocyclohexyl) methane, m-xylylenediamine, etc. . Examples of dibasic acids include glutaric acid, pimelic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedione acid, dodecanedione acid, and hexadecanedioic acid. Keto acid, hexadecenedionic acid, pinane diketonic acid, diglycolic acid, 2,2,4-trimethyl adipate, phenylene dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid and the like. Any of the crystalline polyamides used in the highly heat-shrinkable polyamide fibers of the present invention may be used, but from the viewpoint of considering both manufacturing costs and fiber strength maintenance, polydecamide and polyhexamethylene are preferred. Dimethanamine.

The non-crystalline polyamide of the high heat-shrinkable polyamide fiber of the present invention is a polyamine which has not formed a crystal and has no melting point, and examples thereof include polycondensates of isophthalic acid / p-phthalic acid / hexanediamine, Polycondensate of isophthalic acid / terephthalic acid / hexamethylenediamine / bis (3-methyl-4-aminocyclohexyl) methane, isophthalic acid / 2,2,4-trimethylhexamethylenediamine / 2, Polycondensate of 4,4-trimethylhexamethylene diamine, polycondensate of terephthalic acid / 2,2,4-trimethylhexamethylenediamine / 2,4,4-trimethylhexamethylene diamine, isophthalic acid / Terephthalic acid / 2,2,4-trimethylhexamethylene diamine / 2,4,4-trimethylhexamethylene diamine polycondensate, isophthalic acid / bis (3-methyl-4-amino ring Hexyl) methane / ω-dodecylamine polycondensate, terephthalic acid / bis (3-methyl-4-aminocyclohexyl) methane / ω-dodecylamine polycondensate, and the like. The benzene ring of the terephthalic acid component and / or isophthalic acid component constituting the polycondensate also includes those substituted with an alkyl group or a halogen atom. In addition, these amorphous polyamines may be used alone or in combination of two or more. From the viewpoint of having a high glass transition temperature (Tg), the amorphous polyamide used in the highly heat-shrinkable polyamide fibers of the present invention is preferably a polycondensate of isophthalic acid / p-phthalic acid / hexamethylenediamine. .

In the highly heat-shrinkable polyamide fiber of the present invention, the weight ratio of the crystalline polyamide to the amorphous polyamide is crystalline polyamide / amorphous polyamide = 90/10 to 50/50. If the weight ratio of amorphous polyamide is less than 10% by weight, the shrinkage characteristics of heat shrinkage stress (H) and boiling water shrinkage (B) become small. When making mixed fiber filaments, even if heat treatment is performed, the filament length is unlikely to occur. Poor, unable to obtain sufficient bulkiness, and when fabrics are manufactured, even if heat treatment is performed, they will not sufficiently shrink, and high-density fabrics with a swelled and soft feel cannot be obtained. When the weight ratio of the amorphous polyamide is more than 50% by weight, the yarn drawability is insufficient and the yarn cannot be customized. Therefore, it is preferably crystalline polyamidoamine / amorphous polyamidoamine = 80/20 ~ 60/40, and more preferably 70/30 ~ 60/40.

Here, the "weight ratio" refers to the measurement of the proton NMR of the highly heat-shrinkable polyamine fiber, from the peak area (A) of the signal (usually around 3 ppm) derived from the carboxy α-position hydrogen that forms the amine bond and the aromatic origin. The peak area (B) of the signal of a group hydrocarbon (usually around 7 ppm), and the repetition ratio of the crystalline polyfluorene to the amorphous polyamine (A = the number of crystalline polyamine repeats × 2 + Number of repeats of fluorene x 2 and B = number of repeats of amorphous polyamine x 4). Mass analysis was performed on the same high-heat-shrinkable polyamide fiber, and the mass of the polyamide repeat unit was measured. The weight ratio was calculated from the product of the obtained repeat ratio and the repeat unit mass of each polyamide.

In addition, to the high heat-shrinkable polyamide fiber, if necessary, pigments, heat stabilizers, antioxidants, weathering agents, flame retardants, plasticizers, release agents, lubricants, foaming agents, Antistatic agents, moldability improvers, reinforcing agents, etc.

The highly heat-shrinkable polyfluorene fiber is a miscible system in which crystalline polyamine and amorphous polyamine are mutually compatible. The miscibility system and immiscibility system are judged based on the TEM observation results of 3000 times. If a phase separation structure of islands with a dispersed phase with a diameter of 10 nm or more is observed, it is judged as an "immiscibility system". If no diameter is observed, When the sea-island phase separation structure with a dispersed phase of 10 nm or more is judged as a "miscible system". In a miscible system, by forming an amorphous polyamine tangled with a crystalline polyamide during the formation of a fibrous structure, a high strain band is formed in the amorphous portion of the crystalline polyamide, and the desired Boiling water shrinkage (B) and thermal shrinkage stress (H).

The glass transition temperature (Tg) of the highly heat-shrinkable polyamide fiber of the present invention is 85 to 95 ° C. The glass transition temperature (Tg) of the high thermal shrinkage stress polyamide fiber of the present invention is a reactivity index of crystalline polyamide and amorphous polyamide, which depends on the non-crystalline properties of crystalline polyamide when the fiber is formed. Formation of a high strain band generated by the crystal portion. By setting the glass transition temperature (Tg) within this range, even if the polyamide fiber is stored in a state where no tension is applied, the required thermal shrinkage stress (H2) over time can be exhibited. If the glass transition temperature (Tg) is less than 85 ° C, the high strain band generated in the amorphous portion of the crystalline polyamide is relaxed. Therefore, if the polyamide fiber is stored in a state where no tension is applied, it cannot be used. Obtain the required heat shrinkage stress (H2) over time. If the glass transition temperature (Tg) exceeds 95 ° C, the reaction between the amorphous polyamine and the crystalline polyamine is excessive, resulting in a small crystal size. Therefore, although the initial heat shrinkage stress (H) is high, The ammonium fibers are stored under no tension, and the required heat shrinkage stress (H2) over time cannot be obtained. The glass transition temperature (Tg) of the high heat-shrinkable polyamide fiber is preferably 87 to 93 ° C. The heat shrinkage stress (H2) of the high heat shrinkable polyamide fiber over time is preferably 0.20 cN / dtex or more, more preferably 0.25 cN / dtex or more, and particularly preferably 0.30 cN / dtex or more. In addition, if the heat shrinkage stress is too high, the power of shrinkage is too high when fabrics are made, causing the holes at the interlaced points of the fabric to be excessively blocked, resulting in weakening of friction and easy occurrence of fluff and fluff. The tendency of fabric quality to decrease. Therefore, the upper limit of the heat shrinkage stress (H2) over time of the highly heat-shrinkable polyamide fiber is preferably 0.50 cN / dtex.

The boiling water shrinkage (B) of the highly heat-shrinkable polyamide fiber of the present invention is 25 to 50%. By setting it within this range, when making mixed fiber yarns, when performing heat treatment using boiling water, steam, etc., a difference in yarn length will occur due to the shrinkage difference with fibers with different shrinkage characteristics, and a fluffy mixed fiber can be obtained. Filaments. In addition, when fabrics are manufactured, high-density fabrics with sufficient shrinkage and swelling feeling can be obtained when heat treatment is performed using boiling water, steam, or the like. If the boiling water shrinkage (B) is less than 25%, the silk length difference will not easily occur even when heat treatment is performed during the production of mixed fiber yarns, resulting in failure to obtain sufficient bulkiness, and even when heat treatment is performed when fabrics are produced, It does not shrink sufficiently, and it is impossible to obtain a high-density fabric with a swelled and soft feeling. If the boiling water shrinkage (B) exceeds 50%, when fabrics are manufactured, when the fabric is subjected to heat treatment, the dimensional change is too large, the fabric density is too dense, the feel becomes hard, and the swelling and softness are poor. In addition, at the fabric interlacing point, The pores are clogged to cause spots and shrinkage spots, so the quality of the obtained fabric is poor. The boiling water shrinkage (B) of the high heat-shrinkable polyamide fiber is preferably 30 to 45%. Here, the "boiling water shrinkage (B)" refers to forming a fiber sample into a loop of 50 cm, applying an initial load of 1/30 (g) of the fineness, obtaining the length A, and then immersing it in boiling water for 30 minutes without applying it. After that, it was naturally dried, and the initial load of 1/30 (g) of the fineness was applied again to obtain the length B, and the boiling water shrinkage (B) was calculated according to the following formula.

Boiling water shrinkage (B) (%) = [(A-B) / A] × 100

The thermal shrinkage stress (H) of the highly heat-shrinkable polyamide fiber of the present invention is 0.20 cN / dtex or more. Here, the "heat shrinkage stress (H)" refers to a KE-2 type heat shrinkage stress measuring machine manufactured by Kanebo Engineering, which is used to connect the fiber threads to be measured into a loop of 16 cm in circumference and apply the thread fineness (denier). The initial load of 1 / 30g was measured when the temperature was changed at a temperature increase rate of 100 ° C / min. The peak value (maximum value) of the obtained thermal stress curve was measured and set as the thermal shrinkage stress (cN / dtex). By setting the thermal shrinkage stress (H) of the highly heat-shrinkable polyamide fiber within this range, when manufacturing mixed fiber yarns, heat treatment with boiling water, steam, etc. is used to restrict fibers with different shrinkage characteristics. Shrink and shrink, you can get more fluffy mixed fiber. When fabrics are manufactured, when heat treatment is performed by using boiling water, steam, or the like, fibers with different shrinkage characteristics shrink and shrink sufficiently to obtain a high-density fabric with a more swelled and soft feel. When the heat shrinkage stress (H) is less than 0.20cN / dtex, the heat shrinkage stress (H) is still insufficient even when heat treatment is performed during the production of mixed filaments, it is difficult to show a difference in wire length, and sufficient bulkiness cannot be obtained. Also, when fabrics are manufactured, even if heat treatment is performed, they will not shrink uniformly and shrink spots will occur, making it impossible to obtain a density fabric with a feeling of swelling. The thermal shrinkage stress (H) of the high heat-shrinkable polyamide fiber is preferably 0.25 cN / dtex or more, and more preferably 0.30 cN / dtex or more. In addition, if the heat shrinkage stress is too high, when the fabric is made, the shrinking power is too high, and the holes at the fabric interlacing points are excessively blocked, so the friction becomes weak, and fluff and fluff are easy to occur. The tendency of fabric quality to decrease. Therefore, the upper limit of the heat shrinkage stress (H) of the highly heat-shrinkable polyamide fiber is preferably 0.50 cN / dtex.

The main point of the highly heat-shrinkable polyamide fiber of the present invention is that the shrinkage in boiling water (B) and the heat shrinkage stress (H) exhibit shrinkage characteristics within the above-mentioned ranges. That is, it is important to satisfy both: when the heat treatment is performed using boiling water, steam, or the like, a boiling shrinkage (B) indicating a dimensional change and a thermal shrinkage stress (H) indicating a shrinking power (force). When the boiling water shrinkage (B) and the heat shrinkage stress (H) are set within the above ranges, heat treatment is performed by using boiling water, steam, and the like when producing a mixed fiber yarn containing at least a part of high heat shrinkable polyamide fiber. You can show the difference in filament length with fibers with different shrinkage characteristics. By making the shrinkage and shrinkage of fibers with different shrinkage characteristics further, you can obtain more fluffy mixed fiber yarns. In addition, when fabrics are manufactured, by performing heat treatment with boiling water, steam, or the like, the fibers with different shrinkage characteristics are subjected to silk shrinkage and are sufficiently contracted to obtain a high-density fabric with a more swelled and soft feel.

The total fineness of the highly heat-shrinkable polyamide fiber of the present invention is preferably 5 to 80 dtex. In particular, from the viewpoint of the strength and lightness of the fabric when used as sports apparel, down jackets, outer linings and backing base fabrics, 8-50 dtex and 8-40 dtex are particularly preferred. The monofilament fineness of the high heat-shrinkable polyamide fiber is preferably 0.9 to 3.0 dtex. In particular, from the viewpoint of fabric strength and softness when used as sports apparel, down jackets, outer linings and underlays for inner linings, 0.9 to 2.0 dtex and 0.9 to 1.3 dtex are particularly preferred. By setting the monofilament fineness within this range, even if a seam product or a high-density knitted fabric that is heat-treated with mixed fiber yarns such as boiling water and steam is used, a comfortable and comfortable wearing feeling can be achieved when wearing.

The high elongation of the highly heat-shrinkable polyamide fiber of the present invention is only required to be the normal elongation used in clothing applications. From a high-end processing point of view, a better elongation of 25-50% and a strength of 2.5 cN / dtex or more.

The fineness unevenness (U%) in the long side direction of the highly heat-shrinkable polyamide fiber of the present invention is preferably 1.2% or less from the viewpoint of uneven weft density when using a fabric for clothing. More preferably, it is less than 1.0%. Extra good is below 0.8%.

The cross-sectional shape of the high heat-shrinkable polyamide fiber of the present invention is not particularly limited, and it can be set to any shape according to the application, and is preferably circular, triangular, flat, Y-shaped, or star-shaped.

The manufacturing method of the highly heat-shrinkable polyamide fiber of this invention is demonstrated.

When the crystalline polyamide and the amorphous polyamide are mixed and melted, for example, a melt-kneading method using a pressurized metal, a uniaxial extruder, or a biaxial extruder can be used. The melt-kneading method is preferably, for example, a pressurized metal method or an extruder method. In order to obtain a high heat shrinkage stress (H) from a crystalline polyamine and an amorphous polyamine in a mutually soluble system, a uniaxial extruder is preferably used. When a pressurized metal is used, since it does not mix uniformly, a phase separation structure of an island is formed, and a high heat shrinkage stress (H) cannot be obtained. In addition, if a biaxial extruder is used, the crystalline polyamine and the amorphous polyamine react excessively, and the high strain band formed in the amorphous portion of the crystalline polyamine is reduced, making it impossible to obtain High heat shrinkage stress (H). A mixed polymer of crystalline polyamide and amorphous polyamide that has flowed into the spinneret is ejected from a known spinning nozzle. In addition, the melting temperature and the spinning temperature (so-called thermal insulation temperature around the polymer piping or spinneret) are preferably the melting point of polyamidamine + 20 ° C to the melting point + 60 ° C.

Regarding the method for manufacturing the highly heat-shrinkable polyamide fiber of the present invention, regardless of, for example, a method of continuously performing a spinning-drawing step (direct spinning drawing method), a method of winding up undrawn yarn first, and then performing drawing ( Two-step method), or a method (high-speed spinning method) in which the spinning speed is set to a high speed of 3000 m / min or more and the extension step is substantially omitted (high-speed spinning method) can be produced, but from the viewpoint of high-efficiency production and manufacturing cost It is preferably a single-step method of the direct spinning stretching method and the high-speed spinning method.

The production of melt spinning by a direct spinning stretching method is exemplified.

The polyamide yarn discharged from the spinning nozzle is cooled, solidified, and supplied with oil in the same manner as ordinary melt spinning. The first godet is used to draw at 500 to 4000 m / min. After the extension between the roller and the second godet roller is performed at 1.0 to 4.0 times, the bobbin is wound up at a speed of more than 2000 m / min, preferably 3000 to 4500 m / min.

At this time, by properly designing the peripheral speed ratio (elongation ratio) and the winding speed (winder speed) between the first godet roller and the second godet roller, the target polyurethane yarn can be obtained. degree.

In addition, by setting the first godet roller as a heating roller and performing thermal stretching, the fluidity of the polymer is improved, a high strain band is generated in the amorphous portion of the crystalline polyamide, and the heat shrinkage stress (H ). The heat elongation temperature is preferably 130 to 160 ° C, and more preferably 140 to 160 ° C.

Furthermore, by setting the second godet roller as a heating roller and performing heat setting, the heat shrinkage stress of the yarn can be appropriately designed. The heat setting temperature is preferably 130 to 180 ° C, and more preferably 150 to 170 ° C.

In addition, the steps up to the winding are all performed using a known associating device, and associating may also be performed. If necessary, you can increase the number of contacts by performing multiple contacts. Moreover, you may add an oil agent just before winding.

At least a part of the mixed fiber yarn of the present invention uses the high heat shrinkable polyamide fiber of the present invention. By blending highly heat-shrinkable polyamide fibers with fibers with different shrinkage characteristics, it is possible to make use of boiling water, steam, and the like when the heat shrinkage characteristics are poor to show a difference in filament length, and fluffy mixed fiber yarns can be obtained. The "differentially shrinkable fibers" herein means fibers having different boiling water shrinkage (B) when heat treatment is performed using boiling water, steam, or the like. It is not limited to chemical fibers and natural fibers. Examples of chemical fibers include polyamine fibers and polyethylene terephthalate, such as polydecylamine and polyhexamethylenehexamidine. A representative polyester-based fiber or a polyolefin-based fiber such as polypropylene. Polyamine-based fibers and polyester-based fibers are preferred for clothing applications. Sportswear, down jackets, outer linings and inner linings are better for polyamid fibers.

Furthermore, the high heat-shrinkable polyamide fiber of the present invention has a low boiling water shrinkage ratio (B) with fibers having different shrinkage characteristics, and is preferably 10 to 30% from the viewpoints of softness and swelling. The difference in boiling water shrinkage (B) is more preferably 15 to 30%.

In addition, the thermal shrinkage stress (H) of the highly heat-shrinkable polyamidamine fiber of the present invention and fibers with different shrinkage characteristics is poor, and from the viewpoint of softness and swelling feeling, it is preferably 0.10 to 0.40 cN / dtex. The better heat shrinkage stress (H) difference is 0.15 ~ 0.30cN / dtex.

The mixed fiber yarn of the present invention can be subjected to silk processing according to a known method. The mixed fiber method can be used, for example, spinning mixed fiber, air mixed fiber, twisted yarn, composite false twist, etc., because air mixed fiber is easier to mix fiber and the manufacturing cost is low, so it is better. The air-mixed fiber method may include, for example, stagger processing, Taslan processing, and processing using a swirling airflow.

At least a part of the knitted fabric system of the present invention uses the high heat shrinkable polyamide fiber and / or mixed fiber yarn of the present invention. By weaving and weaving highly heat-shrinkable polyamide fibers and fibers with different shrinkage characteristics, when heat treatment is performed using boiling water, steam, etc., the high heat-shrinkable polyamide fibers will sufficiently shrink, and the fibers with different shrinkage characteristics will be contracted and shrunk. A high-density knitted fabric with a swelled and soft feel can be obtained.

The knitted fabric system of the present invention can be woven and knitted according to a known method. The structure of the knitted fabric is not limited. In the case of fabrics, the structure can be any of plain weave, twill weave, satin weave, and other altered weaves and mixed weaves, depending on the application used. In order to obtain a strong and fluffy fabric, It is a ripstop tissue with a combination of plain weaves or a combination of plain weaves, stone grains, and square plains. In the case of knitted fabrics, the structure is arbitrarily flat stitched, double ribbed, half-knitted, satin, jacquard texture, etc. From the viewpoints that the knitted fabric is thin, stable, and excellent in elongation, it is preferably a semi-tissue of a single tricot knitted fabric, etc. from a viewpoint of changing the structure and the mixed structure.

Some of the sewing products using the knitted fabric of the present invention are not limited in use, and are preferably used for clothing, and more preferably used in, for example, down jackets, windshield jackets, golf apparel, rain wear, etc. Sports and casual clothing; and women's / men's clothing. Particularly suitable for sportswear and down jackets.

    [Example]    

Next, the present invention will be described in detail using embodiments.

    A. Melting point    

A differential scanning calorimeter (DSC) was used for thermal analysis using Q Instrument manufactured by TA Instrument, and data processing was performed using Universal Analysis 2000. The thermal analysis was performed under a nitrogen flow (50 mL / min) at a temperature range of -50 to 300 ° C, a heating rate of 10 ° C / min, and a sample weight of about 5 g (the thermal data was formatted using the weight after measurement). The melting point is determined from the melting spike.

    B. Relative viscosity    

0.25 g of a polyamine sample and 25 ml of a sulfuric acid having a concentration of 98% by mass were dissolved so as to be 1 g / 100 ml, and an Oswald-type viscometer was used to measure the flow-down time (T1) at 25 ° C. Next, the downflow time (T2) with only 98 mass% sulfuric acid was measured. Let the ratio of T1 to T2 (that is, T1 / T2) be the relative viscosity of sulfuric acid.

    C. Total fineness, monofilament fineness    

The total fineness and the monofilament fineness were measured according to JIS L1013. The fiber sample was wound into a length-measuring machine with a tension of 1/30 (g) for 200 turns of a length measuring machine with a circumference of 1.125 m. After drying at 105 ° C for 60 minutes, it was moved to a dryer, and left to cool at 20 ° C and 55RH for 30 minutes. The weight of the coil was measured, and the weight per 10,000m was calculated from the obtained values. The standard moisture regain was set to 4.5%. Calculate the total fineness of the fiber. The measurement system was performed 4 times, and the average value was made into the total fineness. A value obtained by dividing the total fineness by the number of single filaments was defined as the single filament fineness.

    D. Glass transition temperature (Tg)    

A differential scanning calorimeter (DSC) uses Q1000 manufactured by TA Instrument to perform thermal analysis, and uses Universal Analysis 2000 to perform data processing. Thermal analysis is under nitrogen flow (50mL / min), according to temperature range -50 ~ 270 ℃, heating rate 2 ℃ / min, temperature modulation cycle 60 seconds, temperature modulation amplitude ± 1 ℃, sample weight about 5g (calorie data The measurement was performed by formatting the weight after measurement. The endothermic peak temperature observed by the gradient-like baseline deviation was defined as the glass transition temperature (Tg).

    E. Boiling water shrinkage (B)    

The fiber sample was formed into a loop of 50 cm, and the initial load of 1/30 (g) of the fineness was applied to obtain the length A. Then, the fiber sample was immersed in boiling water for 30 minutes under no application state, and then dried naturally. (g) Initial load and length B are calculated, and boiling water shrinkage (B) is calculated according to the following formula.

Boiling water shrinkage (B) (%) = [(A-B) / A] × 100

    F. Heat shrinkage stress (H), heat shrinkage stress (H2) over time    

A KE-2 type heat shrinkage stress measuring machine manufactured by Kanebo Engineering was used to connect the fiber yarns unwound from the taken-up bobbin into a loop with a circumference of 16 cm. An initial load of 1/30 g of the yarn fineness was applied to measure The thermal stress when the temperature changes from room temperature to 100 ° C. according to the heating rate of 100 ° C./min, and the peak value (maximum value) of the obtained thermal stress curve is set as the heat shrinkage stress (H). In addition, the fiber yarn unwound from the wound bobbin was connected to form a ring with a circumference of 16 cm, and it was maintained at 20 ° C and 65% relative humidity for 24 hours under no load. The initial load was 30 g, and the thermal stress when the temperature was changed from room temperature to 100 ° C. at a heating rate of 100 ° C./minute was measured. The peak value of the obtained thermal stress curve was set as the heat shrinkage stress (H2).

    G. Weight ratio of crystalline polyamidoamine to amorphous polyamidoamine    

The repeat ratio of crystalline polyamine and amorphous polyamine was calculated from the NMR measurement, and the repeating unit mass of each polyamine was calculated from the mass analysis, and the weight ratio was calculated.

    (a) NMR measurement    

The measurement was performed by using nuclear magnetic resonance spectrometry ( ¹ H-NMR) with tetramethylsilane (TMS) as an internal standard substance (0 ppm). From the peak area (A) of the hydrogen signal at the carboxyl alpha position that forms the amidine bond (usually around 3 ppm) and the peak area (B) of the signal from the aromatic hydrocarbon (usually around 7 ppm), a crystalline polymer is obtained. Repetition ratio of fluorene and amorphous polyfluorene (A = Crystalline polyamine repeat number × 2 + Amorphous polyfluorene repeat number × 2, B = Amorphous polyamine repeat number × 4).

    (b) Quality analysis    

Use matrix-assisted laser desorption / free mass spectrometry (MALDI-MS), time-of-flight mass spectrometry (TOF-MS), time-of-flight matrix-assisted laser desorption / free mass spectrometry (MALDI-TOF-MS), decide The mass of the repeating unit.

    (c) Weight ratio    

Weight ratio of crystalline polyamide (%) = (A / 2) × (mass of crystalline polyamide)

Weight ratio of amorphous polyamide (%) = (A / 2-B / 4) × (mass of amorphous polyamide)

    H. Miscibility    

The silk thread is exposed to RuO ₄ vapor, and the application line is applied so that the boundary between the silk and the storage resin is clearly defined. Then, thin sections were stored in the resin, and stained with a phosphotungstic acid (PTA) aqueous solution for 15 minutes. A thin section was observed using a transmission electron microscope (H-7100 manufactured by Hitachi, Ltd.) at a voltage of 100 kV using the observation object obtained as described above. Observe the cross section of the fiber at an observation magnification of 3000 times. In the TEM observation results, when an island phase separation structure having a dispersed phase with a diameter of 10 nm or more was observed, it was judged to be an "immiscible system"(×; incompatible). When an island phase separation structure with a dispersed phase having a diameter of 10 nm or more was not observed, It was judged as "miscible system"(○; compatible).

    I. Strength and elongation    

The fiber sample was measured using "TENSILON" (registered trademark) manufactured by ORIENTEC Co., Ltd. and UCT-100 under the constant-speed elongation conditions shown in JIS L1013 (chemical fiber yarn test method, 2010). The elongation is calculated from the stretch at the maximum strength in the tensile strength-extension curve. The intensity is a value obtained by dividing the maximum strength by the fineness. The measurement system was performed 10 times, and the average value was made into intensity and elongation.

    J. Unevenness (U%)    

The fiber sample was measured by USTER TESTER III manufactured by Zellweger Uster, and the measurement was performed 4 times according to the sample length: 250 m, the measurement wire speed: 50 m / min, the measurement range (12.5% HI), and 1/2 Inert. The average value was U%. value.

    K. Knit Evaluation         (a) Manufacturing of nylon 6 silk thread    

Polycaprolactam (N6) with a relative viscosity of 2.70 was melt-discharged at a spinning temperature of 275 ° C from a spinning spinneret provided with 60 spinneret discharge holes. After being melted and discharged, the yarn was cooled, oiled, and entangled, then pulled by a 2560m / min godet roller, and then stretched 1.7 times, then thermally fixed at 155 ° C, and 80dte × 60 was obtained at a winding speed of 4000m / min. Monofilament nylon 6 silk thread. In addition, the obtained nylon 6 yarn had a fineness of 78.8 dtex, a strength of 4.0 cN / dtex, a elongation of 59%, a boiling water shrinkage of 10%, and a heat shrinkage stress of 0.09 cN / dtex.

    (b) Manufacturing of mixed filament    

The nylon 6 yarn obtained in the above (a) and the polyamide yarn obtained in Examples 1 to 7 and Comparative Examples 1 to 6 were subjected to an interlacing treatment with an interlacing pressure of 2.0 kg / cm ² using an interlaced processing machine, and then executed. Mixed fiber processing to obtain 113dtex or 122dtex mixed fiber yarn.

    (c) Tube knitting    

The mixed-fiber yarn sample obtained in the above (b) was adjusted to a state of the eye 50 with a tubular knitting machine to prepare a tubular knitted fabric.

The obtained tube knitting was refined at 80 ° C for 20 minutes, then Kayanol Yellow N5G 1% owf, acetic acid was used to adjust the pH to 4, the dyeing was performed at 100 ° C for 30 minutes, and then the setting treatment was performed at 80 ° C for 20 minutes. Heat treatment was performed at 170 ° C for 30 seconds with improved hand feel.

    (d) Evaluation of knitted fabrics    

With regard to the tube knitted fabric obtained in the above (c), the evaluation of the fluffy feeling (swelling feeling) was performed in accordance with the following five steps by using the touch of a skilled person (5 persons). The decimal point of the average of the evaluation scores of the various technicians is rounded up, 5 points are rated as ◎ (excellent), 4 points are rated as ○ (good), 3 points are rated as △ (passable), and 1 to 2 points Rated × (bad).

5 points: Excellent

4 points: slightly better

3 points: Fair

2 points: slightly worse

1 point: poor

    L. Fabric Evaluation         (a) Manufacturing of warp yarns    

Polycaprolactam (N6) with a relative viscosity of 2.70 was melt-discharged from a spinning spinneret provided with 20 spinneret ejection holes at a spinning temperature of 275 ° C. After being melted and discharged, the yarn was cooled, supplied with oil, and entangled, then pulled by a 2560m / min godet roller, and then stretched 1.7 times, then thermally fixed at 155 ° C, and 22dte × 20 was obtained at a winding speed of 4000m / min. Monofilament nylon 6 silk thread.

    (b) Fabrication    

The nylon 6 yarns obtained in (a) above were used as warp yarns (warp yarn density 90 pieces / 2.54cm), and the polyamide yarns obtained in the examples and comparative examples were used as weft yarns to weave plain fabrics (appearance Density: 40 g / cm ² ).

The obtained fabric was refined at 80 ° C for 20 minutes, then adjusted to pH 4 with Kayanol Yellow N5G 1% owf and acetic acid, dyeed at 100 ° C for 30 minutes, and then set at 80 ° C for 20 minutes. A heat treatment was performed at 170 ° C for 30 seconds.

    (c) Fabric evaluation    

With respect to the fabric obtained in (b) above, high-density feeling, soft feeling, and swelling feeling were evaluated in accordance with the following five steps by using the touch of a skilled person (fifth). The decimal point of the average of the evaluation scores of the various technicians is rounded up, 5 points are rated as ◎ (excellent), 4 points are rated as ○ (good), 3 points are rated as △ (passable), and 1 to 2 points Rated × (bad).

5 points: Excellent

4 points: slightly better

3 points: Fair

2 points: slightly worse

1 point: poor

    [Example 1]    

The polycaprolactam (N6) of crystalline polyamine (relative viscosity ηr: 2.62, melting point 222 ° C), the isophthalic acid (6I) / terephthalic acid (6T) / adipamide of non-crystalline polyamine A polycondensate of amine and a copolymer of isophthalic acid / terephthalic acid with a copolymerization ratio of 7/3 (relative viscosity ηr: 2.10), according to the weight ratio of crystalline polyamine / amorphous polyamine to 70/30 A single-screw extruder was used to perform melt-kneading at 265 ° C, and a spinning spinneret having a discharge hole with 26 circular holes was used to perform melt-discharge (spinning temperature: 265 ° C). After being melted and discharged, the yarn is cooled, supplied with oil, and entangled, and then pulled by a 1500m / min first godet roller (extension temperature: 150 ° C), and then extended 2.4 times, and then heat-fixed at 165 ° C, and then A winding speed of 3500 m / min was used to obtain a 33 dtex 26 monofilament polyamide yarn (relative viscosity ηr: 2.46, glass transition temperature (Tg): 91 ° C).

    [Example 2]    

Spinning was performed in the same manner as in Example 1 except that the weight ratio of the crystalline polyamide / amorphous polyamide was 85/15, and a 33 dtex 26 monofilament polyamide yarn (relative viscosity) was obtained. ηr: 2.54, glass transition temperature (Tg): 87 ° C).

    [Example 3]    

Except that the weight ratio of the crystalline polyamide / amorphous polyamide was 55/45, spinning was performed in the same manner as in Example 1 to obtain a 33 dtex 26 monofilament polyamide yarn (relative viscosity). ηr: 2.39, glass transition temperature (Tg): 92 ° C).

    [Example 4]    

Except for using hexamethylenehexamethylene diamine (N66) as the crystalline polyamine (relative viscosity ηr: 2.80, melting point: 263 ° C) and changing the spinning temperature to 285 ° C, the rest are in accordance with the examples. 1 Spinning was performed in the same manner to obtain a polyamide yarn of 33 dtex 26 monofilament (relative viscosity ηr: 2.59, glass transition temperature (Tg): 92 ° C).

    [Example 5]    

Except that the crystalline polyamidine system used polyhexamethylene cytaramide (N610) (relative viscosity ηr: 2.80, melting point 219 ° C), spinning was performed in the same manner as in Example 1 to obtain a 33 dtex 26 unit. Polyamide silk thread (relative viscosity ηr: 2.59, glass transition temperature (Tg): 93 ° C).

    [Example 6]    

Except that the stretching ratio was set to 2.8 times, spinning was performed in the same manner as in Example 1 to obtain a 33 dtex 26 monofilament polyamide yarn (relative viscosity ηr: 2.59, glass transition temperature (Tg): 92 ° C). .

    [Example 7]    

Spinning was performed in the same manner as in Example 1 except that the weight ratio of the crystalline polyamine / amorphous polyamine was set to 85/15, and the discharge amount was changed to obtain 54 dtex26 monofilament polyfluorene. Amine filament (relative viscosity ηr: 2.54, glass transition temperature (Tg): 85 ° C).

    [Comparative Example 1]    

Except that the weight ratio of crystalline polyamide / amorphous polyamide was 95/5, spinning was performed in the same manner as in Example 1 to obtain a 33 dtex 26 monofilament polyamide yarn (relative viscosity). ηr: 2.59, glass transition temperature (Tg): 22 ° C).

    [Comparative Example 2]    

Except that the weight ratio of crystalline polyamide / amorphous polyamide was 30/70, spinning was performed in the same manner as in Example 1 to obtain a 33 dtex 26 monofilament polyamide yarn (relative viscosity). ηr: 2.26, glass transition temperature (Tg): 23 ° C).

    [Comparative Example 3]    

Except that melt-kneading was performed using a biaxial extruder, and the first godet roller was set to non-heating (elongation temperature: room temperature), spinning was performed in the same manner as in Example 1 to obtain a 33 dtex 26 monofilament. Polyamide silk (relative viscosity ηr: 2.96, glass transition temperature (Tg): 102 ° C).

    [Comparative Example 4]    

Except that melt-kneading was performed using a biaxial extruder and the extension temperature of the first godet roller was set to 90 ° C, the spinning was performed in the same manner as in Example 1 to obtain a 33dtex26 monofilament polyamide yarn. (Relative viscosity ηr: 2.96, glass transition temperature (Tg): 102 ° C).

    [Comparative Example 5]    

In addition to the crystalline polyamine, a copolymer of polycaprolactam and hexamethylene adipamide and a copolymerization ratio of polycaprolactam and hexamethylene adipamide is 85/15 (N6 / N66 copolymer) (relative viscosity ηr: 2.69, melting point: 198 ° C), and the extension temperature of the first godet roller was set to 120 ° C, and the rest were spun in the same manner as in Example 1. A 33 dtex 26 monofilament polyamide filament was obtained (relative viscosity ηr: 2.66, glass transition temperature (Tg): 29 ° C).

    [Comparative Example 6]    

In addition to crystalline polyfluorene, polycaprolactam (N6) (relative viscosity ηr: 2.62, melting point: 222 ° C) and nylon MXD6 (made by Mitsubishi Gas Chemical, relative viscosity ηr: 2.70, melting point: 237 ° C), The weight ratio of polycaprolactam / nylon MXD6 was set to 50/50, and the extension temperature of the first godet roller was set to 85 ° C. The rest were spun in the same manner as in Example 1 to obtain 33dtex26. Monofilament polyamide thread (relative viscosity ηr: 2.66, glass transition temperature (Tg): 32 ° C).

The polymer composition, yarn-making property (compatibility), and elongation conditions of the polyamide yarn are summarized in Table 1. The raw yarn characteristics, knitted fabric evaluation, and fabric evaluation results of the obtained polyamide yarn are summarized in Table 2.

From the results in Table 2, it is known that a part of the weft yarns is a fabric using the polyamide yarns according to Examples 1 to 7 of the present invention. Through the heat treatment step, the shrinkage effect of the weft yarn caused by the shrinkage difference between the warp yarn and the weft yarn, The multiplying effect of the contraction of the warp yarns by the weft yarns exhibits excellent shrinkage, and a high-density fabric having a soft and swellable feeling suitable for clothing can be obtained.

From the results in Table 1, it is known that a part of them is the mixed fiber using the polyamide yarns of Examples 1 to 7 of the present invention. After the heat treatment step, the shrinkage of the core yarn caused by the difference between the core yarn and the sheath yarn is used. The synergistic effect of the action and the action of the core wire contracting the sheath wire and shrinking the sheath wire shows excellent shrinkage, and a fluffy mixed fiber can be obtained.

In Comparative Example 1, since the weight ratio of amorphous polyamide was relatively small, both the heat shrinkage stress (H) and boiling water shrinkage (B) were low, and a mixed fiber with poor bulk was exhibited. In addition, it was not possible to obtain a sufficient high-density feeling, and it was a woven fabric with poor swelling and softness.

In Comparative Example 2, since the weight ratio of the amorphous polyamide was too large, the yarn was poor in yarn drawability, and the yarn could not be customized. It also belongs to mixed fiber yarns with low heat shrinkage stress (H) and poor fluffy feeling. In addition, it was not possible to obtain a sufficient high-density feeling, and it was a woven fabric with poor swelling and softness.

In Comparative Examples 3 and 4, since the glass transition temperature (Tg) exceeded 95 ° C, the amorphous polyamide and the crystalline polyamide were overreacted. If the polyamide fibers were stored in a state where no tension was applied, they were heated with time. The shrinkage stress (H2) is reduced, so it belongs to the mixed fiber with poor bulkiness. In addition, it was not possible to obtain a sufficient high-density feeling, and it was a woven fabric with poor swelling and softness.

Comparative Example 5 Because the crystalline polyamide and amorphous polyamide lack compatibility, and the glass transition temperature (Tg) is near room temperature, if the polyamide fiber is stored in a state without tension over time, , The shrinkage stress will decrease over time, so a higher heat shrinkage stress (H2) over time cannot be obtained, which is a mixed fiber with poor fluffy feeling. In addition, it was not possible to obtain a sufficient high-density feeling, and it was a woven fabric with poor swelling and softness.

Comparative Example 6 Since the polyamide yarn is composed of two kinds of crystalline polyamides, and the glass transition temperature (Tg) is around room temperature, if the polyamide fibers are stored in a state without tension over time, Over time, the heat shrinkage stress (H2) decreases, so a high heat shrinkage stress (H) cannot be obtained, which belongs to a mixed fiber yarn with poor fluffy feel. In addition, it was not possible to obtain a sufficient high-density feeling, and it was a woven fabric with poor swelling and softness.

Claims (4)

    A high heat-shrinkable polyamidamine fiber, which has a glass transition temperature (Tg): 85 to 95 ° C, boiling water shrinkage (B): 25 to 50%, and thermal shrinkage stress (H): 0.20 cN / dtex or more.         For example, the high heat-shrinkable polyamide fiber of claim 1, wherein the total fineness is 5 to 80 dtex, and the monofilament fineness is 0.9 to 3.0 dtex.         A mixed-fiber yarn using at least a part of the high heat-shrinkable polyamide fiber of claim 1 or 2.         A knitted fabric using at least a part of the high heat-shrinkable polyamide fiber of claim 1 or 2 and / or the mixed filament of claim 3.