JP6914200B2 - Polyamide fibers with improved dyeing properties, methods for obtaining such fibers, and polyamide products made from them. - Google Patents

Description

Abstract The present invention relates to polyamide fibers having improved dyeing properties. Polyamide fibers are suitable for low temperature dyeing and short dyeing cycles. The present invention also discloses methods for obtaining such fibers. The polyamide fiber shall be at least polyamide during melt spinning extrusion of the polyamide fiber. It is obtained by blending X (X is an integer of 4 to 16) with an aliphatic polyamide. The blended polyamide fibers and the products made from them can be dyed at temperatures below normal boiling points, and the dyeing time is half the time of a standard dyeing cycle. The dyed polyamide fibers and products also exhibit improved toughness to washing and sweat.

Priorities Commercial interest in fiber and yarn-based polyamides used in textile products, especially underwear, sportswear, leisurewear, and nightwear, is easy to care for, quick-drying properties, and high durability. Due to their advantages in these areas, such as excellent physical properties, abrasion resistance, well-balanced hygroscopicity, good elasticity, light weight, comfort, and flexibility, they are greatly enhanced.

Polyamide, also known as nylon, is a linear condensed polymer consisting of repeated main bonds of amide groups. Polyamide fibers are usually produced by melt spinning extrusion and are available in staple fiber, tow, monofilament, multifilament, flat or false twisted forms. Polyamide is a semi-crystalline polymer. The amide group-(-CO-NH-)-imparts hydrogen bonds between the intermolecular chains of the polyamide, which results in high strength at high temperatures, toughness at low temperatures, wear resistance and abrasion resistance, and low friction coefficient. , As well as good chemical resistance. These properties have made polyamide the strongest of all available artificial fibers.

The dyeing efficiency of polyamide fibers is related to carboxyl-terminal group-COOH and particularly amine-terminal group-NH2, which are polar and hydrophilic. Diffusion of dye into fibers is related to amorphous and crystalline balance, molecular orientation, molecular weight, intermolecular and intramolecular bonds, and available hydroxyl or polar groups.

Dye color uptake, dyeing rate, uniformity, and fastness depend on dyeing conditions such as temperature, time, and pH, and also on dyeing equipment such as exhaustion equipment or padding equipment. Auxiliary agents such as leveling agents, surfactants, slow dyeing agents and fixing agents are also important for efficient dyeing.

Dyes are classified according to their chemical composition, reaction mechanism, molecular size, and the like. The most common types of dyes are reactive dyes, direct dyes, basic dyes, acidic dyes, metal dyes, azo dyes, disperse dyes, and vat dyes. Polyamides have a primary amino-terminal group that is more suitable for acid dyes, so that the best dye uptake and fastness can be obtained. Acid dyes are better dyed by containing a hydrophilic group, which is a _{sodium sulfonate radical (-SO 3} Na), which can be bonded to the amino group (-NH +) of the polyamide fiber by ionic bonding or electrostatic force. Gives ability and more vibrant colors. The rest of the dyes mentioned above combine with the polyamide fibers by hydrogen bonding or van der Waals forces to give a lighter color. For example, when the polyamide is dyed with a disperse dye, the color build-up property is not affected by the chemical differences in the fibers, thus giving a more uniform color. However, since disperse dyes are insoluble dyes that diffuse inside the fibers without binding due to chemical interactions, the use of disperse dyes with respect to polyamides results in poor color build-up and fastness properties. Limited to pale colors.

Typical temperatures and treatment times for dyeing polyamide are boiling point (about 100 ° C.) and treatment time of 60 minutes. This temperature creates a structure in the swollen form of the fiber by breaking the intermolecular bonds at intervals between the molecules so that the dye can diffuse inside the fiber and form permanent chemical bonds. Known to be essential to. The 60 minute time is known to be needed to obtain a deep, consistent and uniform color. However, these temperatures and times consume energy and are not environmentally friendly.

Many attempts have been made to optimize the dyeing process to reduce time, temperature, energy, auxiliaries, and water for the purpose of improving efficiency and productivity, as well as reducing carbon dioxide emissions. In addition, strategies have been made to make the dye more sustainable and efficient under optimized dyeing conditions by changing the chemical composition of the dye. Experiments have also been conducted to increase the affinity of aliphatic polyamides for anionic dyes by increasing the amino-terminal group content. These techniques produce deeper, darker colors, but are not aimed at lowering the dyeing temperature and shortening the dyeing time.

Considering the above items, there has been no solution so far for improving the dyeing properties of polyamide such as essential low temperature dyeing properties and faster dyeing properties.

Therefore, it is an object of the present invention to find a solution for obtaining a polyamide product, which is dyed at a significantly lower temperature and in a shorter time to produce a dark, uniform, durable color, and surprisingly. The present inventors have found that a specific polyamide fiber blend has improved dyeing ability such as low temperature dyeing of dark and light colors and shortened dyeing time.

Thus, the present invention is a polyamide fiber with improved dyeing properties, which is a blend of at least two different polyamides, a first polyamide and a second polyamide.
-The first polyamide is polyamide 6, polyamide 6.6, polyamide 6.9, polyamide 6.12, polyamide 6.10, polyamide 11, polyamide 12, polyamide 10.10, polyamide 4.6, polyamide 4.10. , Polyamide 12.12, Polyamide 10.12, and an aliphatic polyamide selected from the group consisting of a mixture thereof.
-The second polyamide is polyamide 5. Selected from X (where X is an integer of 4-16) and mixtures thereof,
Provided is a polyamide fiber.

Surprisingly, it modifies the inherent morphological properties of polyamides, which are primarily intermolecular amide bonds, which facilitates swelling of polyamide fibers at low temperatures and facilitates chemical interactions. Therefore, it is possible to obtain uniform, dark and durable colors in a more efficient and environmentally friendly way.

The present invention is a method for obtaining said polyamide fibers having improved dyeing properties, wherein the polyamide fibers melt-spin and extrude at least the first and second polyamides as defined above and below. The method obtained by doing so is also aimed at.

The present invention also proposes, in the above and subsequent paragraphs, polyamide products containing polyamide fibers with improved dyeing properties as defined below, and methods for obtaining such polyamide products. The polyamide fiber of the present invention is deformed by false twisting, stretching, warping, knitting, weaving, non-weaving, sewing, or a combination thereof.

Another object of the present invention is to improve the dyeing characteristics of the polyamide fibers produced from these, in order to improve the dyeing characteristics of the polyamide fibers 6, polyamide 6.6, polyamide 6.9, polyamide 6.12, polyamide 6.10, and so on. At least the first aliphatic polyamide selected from the group consisting of polyamide 11, polyamide 12, polyamide 10.10, polyamide 4.6, polyamide 4.10, polyamide 12.12, polyamide 10.12, and mixtures thereof. Polyamide 5. X (X is an integer of 4 to 16) or a second polyamide that is a mixture thereof is used.

Definitions The expression "polyamide fiber" in the sense of the present invention is a conventional term that includes the following spinning products: fibers, monofilaments, multifilaments, and yarns. The "polyamide product" of the present invention is a converted or treated polyamide fiber, a staple fiber made from the polyamide fiber, any floc or any woven composition, in particular a fabric and / or garment. In the following description, the terms "fiber", "thread", and "filament" may be used independently without changing the meaning of the present invention.

Polyamide Fibers with Improved Dyeing Properties The present invention provides polyamide fiber blends with improved dyeing abilities such as darker and lighter dyeing at lower temperatures more quickly. The polyamide fiber having the improved dyeing property of the present invention is a blend of at least two kinds of polyamides, a first polyamide and a second polyamide.

First Polyamide The first polyamide is polyamide 6, polyamide 6.6, polyamide 6.9, polyamide 6.12, polyamide 6.10, polyamide 11, polyamide 12, polyamide 10.10, polyamide 4.6, polyamide. An aliphatic polyamide consisting of AB and / or AABB type selected from the group consisting of 4.10, polyamide 12.12, polyamide 10.12, and mixtures thereof.
It is preferably selected from the group consisting of polyamide 6 or polyamide 6.6 and mixtures thereof, and more preferably poly (hexamethylene adipamide) (polyamide 6.6 or nylon 6.6).

The above-mentioned polyamides are well known in the art and can be obtained by polycondensation of a mixture of a diacid and a diamine monomer or a salt thereof, and these are commercially available. Polyamide AABB type diamines and diacids are tetramethylenediamine (1,4-diaminobutane or putrescine), hexamethylenediamine (1,6-hexamethylenediamine), dodecamethylenediamine (1,12-diaminododecane), hexane. It belongs to the group of diacid (adipic acid), nonanedioic acid (azereic acid), decanedioic acid (sevacinic acid), undecanedioic acid, and dodecanedioic acid. Polyamide AB type monomers belong to the group of caprolactam, 11-aminoundecanoamide, dodecanolactam, or laurolactam.

In the case of poly (hexamethylene adipamide) (polyamide 6.6), the main monomers are hexamethylenediamine and adipic acid. However, these monomers may contain up to 25% of other diamine or diacid monomers, or even amino acids or lactam monomers.

In particular, the amino acid is aminocaproic acid and the lactam is caprolactam.
The preferred first polyamide may have a viscosity index (IVN) in the range of 100-200 ml / g, preferably about 120-170. This IVN is measured according to the ISO307 standard, which will be described in the following experimental sections.
The amino-terminal group (ATG) content of these polyamides is advantageously 25-60 equivalents / ton and the carboxyl-terminal group (CTG) is advantageously 45-90 equivalents / ton. These amino / carboxy terminal group contents are measured according to the methods described in the following experimental sections.
The opacity of this first polyamide may be brilliant, semi-dull, full-dull, or a mixture thereof. Opacity is related to the amount of titanium dioxide present in the polymer, which is associated with dyeability, gloss, and processability issues. For example, Brilliant has a lower amount of Titanium Dioxide, while Fludal has a higher amount of Titanium Dioxide.

A particularly preferred first polyamide in the present invention is polyamide 6.6 containing 1-5% caprolactam. This polyamide is a fludal polymer, advantageously having an IVN (viscosity index) of 128-132 and an ATG (amino-terminal group) of 40-45.

Second polyamide The second polyamide is polyamide 5. X (X is an integer of 4 to 16) and mixtures thereof. More preferably, the second polyamide is an odd / even polyamide such as polyamide 5.4, 5.6, 5.8, 5.10, 5.12, 5.14. In a preferred embodiment, the second polyamide of the polyamide fiber of the present invention is polyamide 5.6 or polyamide 5.10. When the second polyamide is polyamide 5.6, the best results are obtained in terms of dyeing properties.
Polyamide 5. X is produced from pentamethylenediamine as a raw material and an aliphatic dicarboxylic acid.
The list of leading dicarboxylic acids is as follows: butanedioic acid (succinic acid), pentanedioic acid (glutaric acid), hexanedioic acid (adipic acid), heptanedioic acid (pimelic acid), octanedioic acid (sverin). Acid), nonanedioic acid (azereic acid), decanedioic acid (sevacinic acid), undecanedioic acid, dodecanedioic acid, brassylic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid.
All these diacids are commercially available. Polyamides 5.6 and 5.10 have the advantage that they can be produced from biomass according to ASTM6866. Since pentamethylenediamine can also be produced from biological resources according to ASTM6866, the resulting polyamides may be at least 45% biogenic and up to 100% bioresources.
Polyamide 5.6 is also known as poly (pentamethylene adipamide), which consists of the raw materials pentamethylenediamine and adipic acid.

Preferred polyamide 5.6 can have a viscosity index (IVN) in the range of 100-200 ml / g, preferably about 120-170. This IVN is measured according to the ISO307 standard, which will be described in the following experimental sections.
The amino-terminal group (ATG) content is advantageously 25-60 equivalents / ton, and the carboxyl-terminal group (CTG) content is preferably 45-90 equivalents / ton.
These amino / carboxy terminal group contents are measured according to the methods described in the following experimental sections.
The opacity of the second polyamide may be brilliant, semi-dal, full-dull, or a mixture thereof, as described above for the first polyamide.

A particularly preferred polyamide 5.6 in the present invention has an IVN (viscosity index) of 138-142 and an ATG (amino-terminal group) of 38-42 and is a brilliant polymer. That is, the polyamide does not contain titanium dioxide.

The polyamide fiber of the present invention is used when the second polyamide is present in an amount of about 1.0% by weight to 40.0% by weight, preferably about 5.0 to 20.0% by weight, based on the total weight of the polyamide fiber. Especially advantageous. The best form is when a second polyamide, especially polyamide 5.6, is present in an amount of 5% to 10% by weight of the total weight of the polyamide fibers.

The polyamide fibers of the present invention advantageously have a total decitex (dtex) of about 40-300 and a dpf (dtex per filament) of about 1-5. The tensile strength (break elongation) is 30 to 80 cN / dtex. The elongation at break is 20% to 90%.

In fact, the combination of the above-mentioned preferred technical features of the first and second polyamides provides even better dyeing behavior combined with the sufficient and satisfactory mechanical properties of the fibers for textile products applications. Can be done.

Methods for Obtaining Polyamide Fibers with Improved Dyeing Properties The present invention also provides methods for obtaining polyamide fibers as described above. The method comprises forming a blend of polyamide fibers by melt spinning extrusion using at least the first and second polyamides described above.

In the present invention, the expression "molten spinning" is understood to mean an extrusion process that converts molten polyamide into polyamide fibers. The polyamide can be supplied to the melt spinning apparatus in pellet, powder, or melt form. Methods include any conventional extrusion spinning means suitable for melt spinning extrusion of polyamides such as uniaxial screw extruders, twin screw extruders, two component extruders, and lattice spinning heads, these means of which are skilled in the art. Is well known. Melt spinning extrusion is performed as LOY (low drawn yarn), POY (semi-drawn yarn), FDY (completely drawn yarn), FOY (completely drawn yarn), LDI (for low denier industry), or HDI (for high denier industry). Further defined.

First Embodiment According to the first embodiment, the melt spinning extrusion is performed by the following step:
a1. The step of feeding the first polyamide as a melt, pellet, or powder into the inlet of a screw extruder or lattice spinning head;
a2. The process of melting, homogenizing, and pressurizing the polyamide;
a3. The process of spinning molten polyamide into fibers;
a4. The process of cooling and winding the fibers;
Including
The second polyamide is continuously introduced as pellets or powders during step a1, preferably using an administration device.

As mentioned above, the second polyamide is preferably continuously introduced during step a1 of the uniaxial screw extruder. It may be added as a polyamide pellet or powder by an administration device such as an administration pump or a weight measurement supply device, preferably by a weight measurement supply device. According to this embodiment, the second polyamide is melt-mixed with the first polyamide prior to fiber formation. The second polyamide may optionally be dried before being introduced into step a1.

In a specific embodiment of the present invention, the second polyamide is continuously supplied as pellets by a weight analysis feeder, and the amount added is 5% by weight of the total weight of the polyamide fibers.
The best results are obtained in a preferred embodiment in which the second polyamide is continuously supplied as pellets by a weight analysis feeder and the amount added is 10% by weight of the total weight of the polyamide fibers.

Second Embodiment According to the second embodiment, the melt spinning extrusion is performed by the following step:
a'1. The step of feeding at least a blend of the first and second polyamides as a melt, pellet, or powder into the inlet of a screw extruder or lattice spinning head;
a2. The process of melting, homogenizing, and pressurizing the polyamide;
a3. The process of spinning molten polyamide into fibers;
a4. The process of cooling and winding the fibers;
Including
The blend of at least the first and second polyamides is obtained by step a0 prior to step a'1, which comprises polymerizing at least the diacid and diamine monomers corresponding to the first and second polyamides or salts thereof. Be done.

The polymerization in step a0 is usually the following step: 1-concentration step of nylon salt by evaporation of water, in which the nylon salt corresponds to at least the first and second polyamides, a monomer of diacid and diamine, or a monomer thereof. A step of combining salts; 2-a step of polymerizing a concentrated nylon salt under pressure; 3-a step of reducing the pressure of the polymerization medium to remove residual water by evaporation; 4-a desired degree of polymerization. The step of optionally maintaining the temperature of the polymer under atmospheric pressure or reduced pressure; 5-recovering the polyamide as a melt or converting the molten polyamide into pellets;

Third Embodiment According to the third embodiment, the melt spinning extrusion is performed by the following step:
a1. The step of feeding the first polyamide as a melt, pellet, or powder into the inlet of a screw extruder or lattice spinning head;
a2. The process of melting, homogenizing, and pressurizing the polyamide;
a3. The process of spinning molten polyamide into fibers;
a4. The process of cooling and winding the fibers;
including.
Among them, the second polyamide is continuously introduced as a polyamide melt, preferably during step a3 of the screw extruder, preferably the uniaxial screw extruder. This is added by an additional screw extruder, preferably a uniaxial screw extruder. According to this embodiment, the second polyamide is blended with the first polyamide after exiting the spin pack cap during fiber formation, thereby forming binary fibers.

All Embodiments In the method of the invention according to any of the first, second or third embodiments described above, the second polyamide is advantageously from 1.0% by weight of the total weight of the polyamide fibers. It is introduced in an amount of 40.0% by weight, preferably 5.0 to 20.0% by weight.

In steps a2 and a3, the term "polyamide" also means a "polyamide blend" in which at least both the first and second polyamides are present.

In step a2, the polyamide (or polyamide blend) melts in a screw extruder, preferably at a temperature of 280-310 ° C. above the melting points of the first and second polyamides, and at an extrusion pressure of 30-70 bar. , Homogenization, and pressurization.

Subsequent steps a3, the molten polyamide (or polyamide blend) uses a spinning screen pack containing a filter element and a spinneret, preferably at a temperature of 260-310 ° C., a spinning pack pressure of 150-250, and 3 It is spun into fibers (or yarns or filaments) at a spinning pack flow rate of ~ 8 kg / h.

Step a4 is a step of cooling the fiber (or thread or filament) to a solidified form and winding the polyamide fiber onto the bobbin. Spinning oil may be added on the fibers in this step.

In the present invention, the extruder is a metering system and / or to introduce the polymer and optional additives (masterbatch, etc.) into the main component polymer in steps a1 and / or a3 and / or a4. It may be equipped with an additional uniaxial screw extruder.

Additives may be introduced into the methods of the invention or may be present in the first and second polyamide pellets. Additives include antioxidants, stabilizers such as heat or light stabilizers, colorants, pigments, nucleating agents such as talc, matting agents such as titanium dioxide and zinc sulfide, processing aids, and biocidal agents. , Viscosity modifiers, catalysts, far infrared emitting minerals, biodegradable "converters", antistatics, functional additives, optical brighteners, nanocapsules, antibacterial agents, acaricides, antifungal agents, or others Selected from conventional additives. These additives are usually added to the polymer or in melt spinning extrusion steps a1 and / or a4 in an amount of 0.001% to 10% by weight of the polyamide product.

The resulting polyamide fibers obtained by the first, second, and third embodiments described above can be dyed.

The improved dyeing properties are usually obtained with dyes consisting of reactive dyes, direct dyes, acid dyes, and metal dyes, preferably reactive dyes or acid dyes.
These dyes bind to the polyamide fibers by a chemical reaction, thus having a faster and cooler benefit of dyeing, in which the molecular structure can form chemical bonds. In a preferred embodiment of the invention, acid dyes are advantageously used because of their high compatibility with polyamide amine end groups.

When the polyamide fiber obtained by the first, second, or third embodiment described above is dyed, the dyeing is performed at a temperature of 40 ° C. to 80 ° C., preferably 60 ° C. ± 5 ° C.

When the polyamide fibers obtained by the first, second, or third embodiment described above are dyed, the dyeing is preferably carried out in a dyeing cycle of 20 to 40 minutes, preferably 30 minutes ± 5 minutes.

Polyamide products The polyamide fibers of the present invention can then be converted into polyamide products, especially woven fabrics and / or garments.
The polyamide product of the present invention is produced from the polyamide fiber of the present invention (as defined above) or the polyamide fiber obtained by the method of the present invention, preferably fibers, staple fibers, flocs, woven fabrics, knitted fabrics, etc. It is a non-woven fabric or a textile product.

The textile product may be any textile product known in the art, such as, but not limited to, woven fabric, knitted fabric, non-woven fabric, rope, string, sewing thread, and the like.

Polyamide products are preferably dyed, especially with acid dyes.

Improved dyeing properties are usually obtained with dyes consisting of reactive dyes, direct dyes, acid dyes, and metallic dyes. These dyes bind to the polyamide fibers by a chemical reaction, thus having a faster and cooler benefit of dyeing, in which the molecular structure can form chemical bonds. Most preferred are reactive dyes and acid dyes. In a preferred embodiment of the invention, acid dyes are advantageously used because of their high compatibility with polyamide amine end groups.

Methods for Obtaining Polyamide Products Methods for converting polyamide fibers into polyamide products such as woven fabrics or clothing are well known to those of skill in the art. In fact, polyamide fibers can be converted into polyamide products by false twisting, stretching, warping, knitting, weaving, non-weaving, sewing, or a combination thereof.

The method for obtaining the polyamide product may further include a dyeing step.
Improved dyeing properties are usually obtained with dyes consisting of reactive dyes, direct dyes, acid dyes, and metallic dyes. These dyes bind to the polyamide fibers by a chemical reaction, thus having a faster and cooler benefit of dyeing, in which the molecular structure can form chemical bonds. Most preferably, reactive dyes and acid dyes are selected for the dyeing process. In a preferred embodiment of the invention, acid dyes are advantageously used because of their high compatibility with polyamide amine end groups.

When the polyamide product obtained by the present invention is dyed, the dyeing is carried out at a temperature of 40 ° C. to 80 ° C., preferably 60 ° C. ± 5 ° C.
When the polyamide product obtained by the present invention is dyed, the dyeing is carried out in a dyeing cycle of 20 to 40 minutes, preferably 30 minutes ± 5 minutes.

These products are subsequently used in a number of applications, especially in carpets, rugs, interior materials, parachutes, tents, bags, socks, underwear, sportswear, outerwear and the like.

The advantage of the polyamide products of the present invention and the products produced from them is that they have improved dyeing ability such as low temperature dyeing of dark and light colors and shortened dyeing time. As such, dyeing can result in uniform, dark and durable colors in a more efficient and environmentally friendly way.

Other details or advantages of the present invention will become even more apparent with the following examples.

Forming a series of polyamide products (Examples 1-12), including comparative polyamide products (Examples 1-9 and 12), wash fastness, alkaline and acidic sweat fastness, CIE Lab color intensity "L" , IVN (viscosity index), and ATG (terminal amino group) were evaluated.

Amino end group content (ATG)
The amino terminal group (ATG) content was determined by potentiometric titration. 2 g of polyamide is added to about 70 ml of about 90 wt% phenol. Keep the mixture at a temperature of 40 ° C. with continued stirring until the polyamide is completely dissolved. The solution is then titrated with 0.1 N HCl at about 25 ° C. Results are reported in equivalents / tonnes (eq / ton). When analyzing fibers and products, all residues or spinning finishes must be removed beforehand.

Solution viscosity (IVN)
The solution viscosity (IVN) is determined according to ISO307. Polyamide is dissolved in 90% by weight formic acid at 25 ° C. at a concentration of 0.005 g / ml and its flow time is measured. Results are reported as ml / g.

Washing fastness ISO105-C06
Samples are washed at 40 ° C. for 30 minutes using a conventional detergent (4 g / l). Then rinse this 3 times in separate 100 ml of water. Samples are evaluated according to the grayscale associated with discoloration (ISO105-A02) and contamination of the attached white cloth (ISO105-A03). The grade varies from 0 to 5, with 0 being "low" and 5 being "high".

Sweat resistance fastness ISO105-E04
The sweat resistance in acidity and alkalinity was evaluated. Place the sample in contact with the attached white cloth (for color transfer), immerse it in simulated alkaline and acidic solutions (pH 8.0 and 5.5, respectively), drain, and test equipment (sweat evaluation tester). Placed between the two plates under predetermined pressure, temperature, and time (37 ± 2 ° C., 4 hours, 5 kg pressure). The color change of the sample and the contamination of the attached white cloth are evaluated on a gray scale for the discoloration (ISO105-A02) and the contamination (ISO105-A03). The grade varies from 0 to 5, with 0 being "low" and 5 being "high".

Color Intensity-CIE15: 2004
The color intensity “L” of the polyamide product ^{was measured by the standardization method CIE L *} a ^* b ^* (Standard CIE 15: 2004 of the International Commission on Illumination). In this method, the polyamide product is evaluated using a spectrophotometer or a colorimetric system and the coordinates of ^{L *} a ^* and b ^{* are obtained from the device.} The brightness coordinate "L" changes from 0 to 100, where 0 is "black" and 100 is "white". The measurement uses a D65 type light source and an observation angle of 10 °. The lower this parameter, the darker the color.

1. 1. Investigation of the effects of dyeing temperature and cycle time Comparative Example 1-4-100% Polyamide 5.6BR
Synthesis or Source of Polyamide 5.6BR Polyamide Polyamide 5.6 pellets are polyamides commercially available from Cathay Biotech under the Trademark Terryl®. This is a brilliant polyamide that does not contain titanium dioxide. IVNs (viscosity indexes) measured by the methods disclosed herein are 138-142 and ATGs (amine-terminated groups) are 38-42.

Synthesis of Fibers and Products Mainly Containing Polyamide 5.6BR Polyamide fibers were obtained during melt spinning extrusion of the above-mentioned polyamide 5.6BR (brilliant).
The obtained multifilament polyamide fiber was further false-twisted to a fineness of 2x80f68dtex, and the fabric was knitted. The obtained tensile strength was 30.0 cN / tex and the elongation was 28.6%. The knitted fabric was dyed in the exhaust device under the following conditions:
Comparative Example 1-100 ° C.-60 minutes Comparative Example 2-70 ° C.-30 minutes Comparative Example 3-60 ° C.-30 minutes Comparative Example 4-50 ° C.-30 minutes.
The amounts used were 3.5% by weight of black acid dye and 1% by weight of leveling agent. The pH of the solution was adjusted to 3-4 with ammonium sulfate and acetic acid. The bath relationship was 1:30. That is, one part of the dough was used for every 30 parts of water.

Comparative Example 5-8-100% Polyamide 6.6BR
Synthesis or Source of Polyamide 6.6BR Polyamide 6.6 pellets were made in Rhodia Polyamida e Especialidades Ltd. This is a brilliant polyamide (without titanium dioxide) produced mainly by polymerizing a nylon salt containing hexamethylenediamine and adipic acid. The IVN (viscosity index) measured by the methods disclosed herein is 128-132 and the ATG (amine terminal group) is 40-45.

Synthesis of Fibers and Products Mainly Containing Polyamide 6.6BR Polyamide fibers were obtained during melt spinning extrusion of the above-mentioned polyamide 6.6BR (brilliant).
The obtained multifilament polyamide fiber was further false-twisted to a fineness of 2x80f68dtex, and the fabric was knitted. The obtained tensile strength was 31.5 cN / tex and the elongation was 28.8%.
The knitted fabric was dyed in the exhaust device under the following conditions:
Comparative Example 5-100 ° C.-60 minutes Comparative Example 6-70 ° C.-30 minutes Comparative Example 7-60 ° C.-30 minutes Comparative Example 8-50 ° C.-30 minutes.
The amounts used were 3.5% by weight of black acid dye and 1% by weight of leveling agent. The pH of the solution was adjusted to 3-4 with ammonium sulfate and acetic acid. The bath relationship was 1:30. That is, one part of the dough was used for every 30 parts of water.

Evaluation Each Comparative Example (1-8) was evaluated for wash fastness, alkaline and acidic sweat fastness, CIE Lab color intensity "L", IVN (viscosity index), and ATG (terminal amino group). NS. The results are shown in Table 1 below.

Conclusion From Comparative Examples 1 to 4 (Polyamide 5.6), the intensity of black color begins to decrease at a temperature of ≦ 60 ° C. This means that this is the lowest temperature for dark stains such as black used in the experiment. On the other hand, for Comparative Examples 5 to 8 (polyamide 6.6), a significant decrease in color intensity already occurs at 70 ° C. When Examples 4 and 6 that achieved the same intensity were compared (Example 4 = 15.1 and Example 6 = 15.2), the dyeing behavior between the polyamide 5.6 and the polyamide 6.6. It can be concluded that there is a difference of 20 ° C. Therefore, 60 ° C. is the optimum temperature for dyeing polyamide 5.6 in a dark color.

The above Examples 1 to 8 cannot be directly compared with the lower Examples 9 to 12 due to the difference in opacity. Fludal polymers contain large amounts of titanium dioxide, which makes them lighter in color than brilliant polymers using the same amount of dye. Examples 1-8 are comparable within themselves and are important for setting the optimum dyeing temperature and time for the present invention. On the other hand, Examples 9-12 are comparable within themselves, demonstrating the advantages obtained by the present invention with respect to color uptake and fastness.

2. Testing at Lower Dyeing Temperatures and Shorter Cycle Times Examples 10 and 11-Polyamide Blends of the Invention Polyamide fiber blends were obtained during melt spinning extrusion. The first polyamide was polyamide 6.6FD (fludal). This polyamide was synthesized in the same manner as in Comparative Examples 5-8, which is furdal (containing about 1.5% titanium dioxide).
The second polyamide was polyamide 5.6 (brilliant) as described above with respect to Comparative Examples 1 to 4.
The second polyamide was continuously introduced as polyamide pellets in step a1 of the uniaxial screw extruder by a weight measurement feeder. In step a2, the polyamide blend was melted, homogenized, and pressurized in a screw extruder at a temperature of about 290 ° C. and an extrusion pressure of about 50 bar. Then, in step a3, the molten polyamide blend was spun into a multifilament yarn at a spinning pack pressure of about 200 bar and a spinning pack flow rate of about 5 kg / h. In step a4, the polyamide fiber blend was solidified and wound on a bobbin at 4200 m / min.

In Example 10, polyamide 5.6 was continuously added in step a1 as 5% by weight of the total polyamide blend.
In Example 11, polyamide 5.6 was continuously added in step a1 as 10% by weight of the total polyamide blend.
The obtained multifilament polyamide blend was further tack-twisted to a fineness of 2x80f68dtex to knit the dough. The knitted fabric was dyed at 60 ° C. for 30 minutes in an exhaust device. The amounts used were 3.5% by weight of black acid dye and 1% by weight of leveling agent. The pH of the solution was adjusted to 3-4 with ammonium sulfate and acetic acid. The bath relationship was 1:30. That is, one part of the dough was used for every 30 parts of water.

Comparative Example 9-100% Polyamide 6.6FD
Polyamide fibers were obtained during melt spinning extrusion. The polyamide was 6.6 FD (Fludal) as synthesized / described above for Examples 10 and 11.
The obtained multifilament polyamide fiber was further false-twisted to a fineness of 2x80f68dtex, and the fabric was knitted. The knitted fabric was dyed at 60 ° C. for 30 minutes in an exhaust device. The amounts used were 3.5% by weight of black acid dye and 1% by weight of leveling agent. The pH of the solution was adjusted to 3-4 with ammonium sulfate and acetic acid. The bath relationship was 1:30. That is, one part of the dough was used for every 30 parts of water.

Comparative Example 12-100% Polyamide 6FD
The polyamide was polyamide 6, FD (full dull). This false twisted polyamide yarn was obtained as a bobbin from Antix Ltd.
Multifilament polyamide fibers are knitted into a fabric. The knitted fabric was dyed at 60 ° C. for 30 minutes in an exhaust device. The amounts used were 3.5% by weight of black acid dye and 1% by weight of leveling agent. The pH of the solution was adjusted to 3-4 with ammonium sulfate and acetic acid. The bath relationship was 1:30. That is, one part of the dough was used for every 30 parts of water.

In all of the above examples, a post-fixing step was performed at 80 ° C. for 30 minutes using 3% by weight fixing agent.

evaluation:
Each Example (Examples 9-12) was evaluated for wash fastness, alkaline and acidic sweat fastness, CIE Lab color intensity "L", IVN (viscosity index), and ATG (terminal amino group). Will be done. The results are shown in Table 2 below.

Conclusion:
In the case of the blends of the present invention (Examples 10 and 11), the polyamide products were also effectively dyed at 60 ° C. for dark colors (eg black). From the results, Examples 10 and 11 took half the time of the normal dyeing cycle (instead of 60 minutes) by adding 5% and 10% polyamide 5.6 during melt spinning extrusion of polyamide 6.6, respectively. In 30 minutes), a stronger black color (L = 24.6 and L = 19.5, respectively) was obtained as compared with Control Example 9 (L = 30.6).
This means a significant reduction compared to the conventional boiling point, and it is shown that the same dyeing advantages exhibited by polyamide 5.6 can also be obtained with a blend of polyamide 5.6 and polyamide 6.6.

In summary, the use of fiber blends of polyamide 5.6 and polyamide 6.6 allows for low temperature dyeing properties and shorter dyeing cycles. The obtained color fastness of the polyamide-blended products (Examples 10 and 11) is also superior to that of the polyamide 5.6 single products (Examples 1 and 3). Furthermore, the dyeing properties of the polyamide fiber blend are better than those of the conventional polyamide 6 (Example 12).

Claims (16)

A polyamide fiber having improved dyeing properties, which is a blend of at least two different polyamides, a first polyamide and a second polyamide.
-The first polyamide is selected from the group consisting of polyamide 6.6 and polyamide 6 and mixtures thereof.
-The second polyamide is polyamide 5.6,
The second polyamide is present in an amount of 1.0 % to 40.0% by weight of the total weight of the polyamide fibers.
The polyamide fiber is a multifilament.
Polyamide fiber. A method for obtaining a polyamide fiber having the improved dyeing characteristics specified in claim 1, wherein the polyamide fiber is obtained by melt spinning extrusion of at least the first and second polyamides specified in claim 1. How to be. The melt spinning extrusion is the next step:
a1. The step of feeding the melt, pellet, or powder of the first polyamide into the inlet of a screw extruder or lattice spinning head;
a2. Steps of melting, homogenizing, and pressurizing the polyamide;
a3. Step of spinning the molten polyamide into fibers;
a4. The process of cooling and winding the fibers;
Including
The method of claim 2, wherein the second polyamide is continuously introduced in step a1 in the form of pellets or powder. The melt spinning extrusion is the next step:
a'1. The step of supplying at least the blend of the first and second polyamides as a melt, pellet, or powder into the inlet of a screw extruder or lattice spinning head;
a2. Steps of melting, homogenizing, and pressurizing the polyamide;
a3. Step of spinning the molten polyamide into fibers;
a4. The process of cooling and winding the fibers;
Including
The blend of at least the first and second polyamides polymerizes at least the diacid and diamine monomers corresponding to the first and second polyamides or salts thereof prior to step a'1. The method according to claim 2, which is obtained by the including step a0. The melt spinning extrusion is the next step:
a1. The step of feeding the melt, pellet, or powder of the first polyamide into the inlet of a screw extruder or lattice spinning head;
a2. Steps of melting, homogenizing, and pressurizing the polyamide;
a3. Step of spinning the molten polyamide into fibers;
a4. The process of cooling and winding the fibers;
Including
The method according to claim 2, wherein the second polyamide is continuously introduced as a polyamide melt during step a3. The method according to any one of claims 2 to 5, wherein the second polyamide is present in an amount of 1.0% by weight to 40.0% by weight of the total weight of the polyamide fibers. The method according to any one of claims 2 to 6, wherein the obtained polyamide fiber is dyed. The method according to claim 7, wherein the polyamide fiber is dyed at a temperature of 40 ° C to 80 ° C. The method of claim 7 or 8, wherein the polyamide fibers are dyed in a dyeing cycle of 20-40 minutes. A polyamide product comprising a polyamide fiber having improved dyeing properties, as defined in claim 1 or obtained by the method according to any one of claims 2-9. Fibers, staples, wherein the polyamide product is made from said polyamide fiber having improved dyeing properties, either as defined in claim 1 or by the method according to any one of claims 2-9. The polyamide product according to claim 10, which is a fiber, floc, woven fabric, knitted fabric, non-woven fabric, or textile product. The polyamide fiber specified in claim 1 or obtained by the method specified in any one of claims 2 to 9 is false-twisted, stretched, warped, knitted, woven, or non-woven. , Sewing, or a method for obtaining the polyamide product according to claim 10 or 11, which is converted by a combination thereof. The method for obtaining a polyamide product according to claim 11, wherein the polyamide product is dyed. The method for obtaining a polyamide product according to claim 12, wherein the polyamide product is dyed at a temperature of 40 ° C. to 80 ° C. The method for obtaining a polyamide product according to claim 12 or 13, wherein the polyamide product is dyed in a dyeing cycle of 20 to 40 minutes. Dyeing properties of the polyamide fibers produced from the second polyamide, which is polyamide 5.6, in combination with at least the first polyamide selected from the group consisting of polyamide 6.6 and polyamide 6 and mixtures thereof. Is used to improve
Use, wherein the second polyamide is present in an amount of 1.0 % to 40.0% by weight of the total weight of the polyamide fibers.