JP5148959B2 - Polyamide fiber - Google Patents

Description

  The present invention is a polyamide fiber composed of a copolymerized polyamide as a main component and having a specific oil agent applied to the fiber surface, and is excellent in adhesiveness at a relatively low temperature, such as various fiber materials and films. The present invention relates to a polyamide fiber suitable for use in bonding the material.

  Conventionally, hot-melt adhesives have been used in various fields because of their quick bonding, ease of handling that they are solid at room temperature, and rationalization and labor saving of the bonding process. In particular, polyamide-based hot melt adhesives are generally excellent in solvent resistance and heat resistance, and are widely used for bonding fibers, buildings, electrical and electronic parts, and the like.

  In general, a hot melt adhesive is required to melt at a required temperature and to have a high adhesive strength. In particular, when used for bonding a fabric, it is necessary to have a melting temperature lower than the decomposition temperature and melting point of the constituent material of the fabric and have sufficient adhesiveness.

  Conventionally, a hot melt adhesive containing a polylaurolactam component is known as a polyamide-based hot melt adhesive (see, for example, Patent Document 1).

  When such a hot-melt adhesive is made into a fiber, the hot-melt adhesive can be used by being woven into a fabric, so that the fibers and fabrics can be bonded to each other for various garments and interiors such as carpets. This is useful because it can be easily performed.

  Such hot-melt adhesive fibers are often used in combination with other materials as a mixed yarn or as a fabric as described above, and therefore can be used in combination with many types of other materials. Things were sought. That is, in the case where high temperature heat treatment is required at the time of bonding, there is a problem that the performance and texture of other materials are deteriorated and the desired fiber products such as fibers and fabrics cannot be obtained. Things were sought.

On the other hand, the low melting point polymer used for the hot-melt adhesive fiber contains a large amount of monomers and oligomers because it cannot be scoured with boiling water as usual. Since the spinning speed is higher in the one-step method than in the two-step method, the molecules are rapidly oriented when the polymer is discharged, and the monomers and oligomers in the polymer are easily deposited on the fiber surface. The monomer or oligomer thus precipitated on the fiber surface becomes white powder when wound around the roller or passes through the guide, covering the fiber surface or depositing on the roller or guide. And when such white powder accumulates, there is a problem that yarn breakage is likely to occur, and operability and working environment deteriorate.
JP-A-7-157743

  The present invention solves the above-described problems, and is a polyamide fiber that can be heat-treated at the time of bonding at a low temperature and can be suitably used as a hot-melt adhesive fiber. It is a technical problem to provide a polyamide fiber that generates less white powder in the process, can be obtained with good operability, and has excellent strength and elongation characteristics.

As a result of investigations to solve the above problems, the present inventors have reached the present invention.
That is, the present invention is a ternary or higher copolymer polyamide composed of nylon 6, nylon 66, nylon 11, nylon 12, and nylon 610 monomers, having a melting point of 100 to 160 ° C. and a wet melting point of 50. -Fibers made of polyamide at 90 ° C, diluted with mineral oil, containing 75 to 98% by weight of mineral oil lubricant, 1 to 10% by weight of alkyl ether nonion, and 1 to 10% by weight of alkyl phosphate K salt The gist of the present invention is a polyamide fiber obtained by adhering a spinning oil diluted with an agent to the fiber surface.

  The polyamide fiber of the present invention melts by heat treatment and functions as an adhesive, and can be used when bonding various fiber materials and materials such as films. The bonded material is difficult to peel off and has high adhesive strength. It will be a thing. And, since the oil agent having a specific component is attached to the fiber surface, the fiber surface, rollers, guides, etc. due to precipitation of monomers and oligomers that are likely to occur when a low-melting polymer is used in a one-step method. There is little accumulation of white powder. For this reason, the polyamide fiber of the present invention can be obtained with good operability and a good working environment, and the tensile properties are excellent.

Hereinafter, the present invention will be described in detail.
The polyamide fiber of the present invention comprises a ternary or higher copolymer polyamide composed of monomers of nylon 6, nylon 66, nylon 11, nylon 12, and nylon 610. That is, a polyamide copolymerized using three or more of these monomers, a terpolymer polyamide copolymerized using three types of monomers, and a quaternary copolymer polyamide copolymerized using four types of monomers. Examples thereof include five-component copolymerized polyamides copolymerized using five types of monomers.

  Among them, preferred copolymer polyamides are ternary copolymer polyamides composed of nylon 6, nylon 66, and nylon 12, and quaternary copolymer polyamides composed of nylon 6, nylon 66, nylon 11, and nylon 12.

  The copolymerized polyamide has a melting point of 80 to 160 ° C, and preferably 100 to 140 ° C. Furthermore, the melting point when wet is 50 to 100 ° C, and preferably 60 to 90 ° C. In the case of the copolymerized polyamide, adjustment is performed by changing the composition ratio of the copolymerization component so that the target melting point and the melting point when wet are obtained.

  Usually, in order to increase the adhesive strength, it is desirable that the processing temperature in the bonding process is 20 ° C. or more higher than the melting point of the polymer constituting the fiber. However, due to the heat treatment during the bonding process, there are few materials to be bonded. After a heat history, it causes deterioration and performance degradation. For this reason, it is desirable that the melting point of the polymer serving as the adhesive component is low.

  Therefore, the melting point of the copolymerized polyamide in the present invention is 160 ° C. or less. Thereby, the heat processing temperature at the time of an adhesive process can be made low, and the quality change and performance fall of a to-be-adhered material can be reduced to the minimum. Further, from the viewpoint of energy consumption and cost, it is preferable that the heat treatment temperature during the bonding process is low.

  Furthermore, the melting point of the copolymerized polyamide in the present invention when wet is 50 to 100 ° C. Depending on the application, heat treatment may be performed under wet heat conditions, such as when heat treatment is performed while applying steam. In such a case, the melting point when wet is set to 100 ° C so that processing by steam heat treatment that is normally performed can be easily performed. It is as follows.

  On the other hand, if the melting point is less than 80 ° C. or the wet melting point is less than 50 ° C., it becomes a high temperature and humidity environment during storage or transportation, and the polyamide fiber yarns are fused with each other, resulting in poor unwinding. In addition, there is a possibility that the yarn quality may be deteriorated, and it is not preferable to perform a heat treatment on the bonded material that has been subjected to the bonding process because the durability becomes poor, such as peeling.

  The melting point of the copolymerized polyamide in the present invention was measured at a rate of temperature increase of 20 ° C./minute using a differential scanning calorimeter DSC-2 manufactured by Perkin Elmer, in accordance with the method described in JIS-K7121. (DSC method).

  In the present invention, the melting point when wet is measured by the following method. A clip-shaped load with a fineness of 1/30 g is attached to the tip of the polyamide fiber of the present invention (length: 30 cm), and the length of the polyamide fiber load attached in a water bath at a water temperature of 20 ° C. Suspend completely. Next, the water temperature is raised at 12 ° C./min, the polyamide fiber is melted, and the water temperature at the time when the load is dropped is set as the melting point when wet.

  In addition, in the copolyamide used in the present invention, various additions such as an antiblocking agent, an inorganic filler, a reinforcing agent, an antioxidant, a plasticizer, a flame retardant, and a matting agent are provided as long as the effects are not impaired. An agent may be contained.

  The polyamide fiber of the present invention may be a multifilament or a monofilament. That is, when the polyamide fiber of the present invention is composed of only one single yarn M1, it is a monofilament, and an assembly of a plurality of single yarns M is a multifilament.

  And the single yarn M which comprises the polyamide fiber of this invention consists only of 1 type of the ternary or more copolymer polyamide comprised by the monomer of nylon 6, nylon 66, nylon 11, nylon 12, nylon 610 ( It is preferable to use a single type (which occupies 100% by mass of the entire fiber), but it may be a composite fiber using a plurality of types of terpolymers of three or more different types, or terpolymers of three or more types. And a composite fiber of other components. When it is set as the composite fiber, it is preferable that the proportion of the ternary or higher copolymer polyamide is 30% by mass or more of the entire fiber.

  In the case of a composite fiber, it is preferable that a ternary or higher copolymer polyamide composed of monomers of nylon 6, nylon 66, nylon 11, nylon 12, and nylon 610 exist on the fiber surface. It is preferable that the copolyamide is a core-sheath type composite fiber in which the sheath part is formed.

  Further, the cross-sectional shape of the fiber is not particularly limited, and may be not only a round cross-section but also a fiber having an irregular shape or a hollow shape.

  And the polyamide fiber of this invention has the oil agent containing a mineral oil lubricant, an alkyl ether nonion, and an alkyl phosphate K salt adhering to the fiber surface.

  Since the oil containing these components adheres to the fiber surface, precipitation of oligomers and monomers that are likely to occur when melt spinning using a low melting point polymer can be prevented, and generation of white powder can be prevented. .

As the mineral oil lubricant, those having a viscosity of 10 to 50 mm ² / s are preferably used, and those having a viscosity of 15 to 30 mm ² / s are more preferable.

  As the alkyl ether nonion, those having 10 to 16 carbon atoms in the raw alcohol are preferable, and those having 11 to 14 carbon atoms in the raw alcohol are particularly preferable. Examples of such alkyl ether nonions include polyalkylene oxides obtained by addition reaction of alkylene oxide to saturated or unsaturated aliphatic monohydric alcohols having 10 to 16 carbon atoms such as 2-ethylhexyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol and the like. And oxyalkylene alkyl (or alkenyl) ether.

  As the alkyl phosphate K salt, those having 14 to 20 carbon atoms in the raw alcohol are preferable, and those having 16 to 18 carbon atoms are particularly preferable. Examples of the alkyl phosphate K salt include octyl phosphate K salt, decyl phosphate K salt, lauryl phosphate K salt, isocetyl phosphate K salt, stearyl phosphate K salt, isostearyl phosphate K salt, oleyl phosphate K salt, and 5 mol of ethylene oxide. And lauryl phosphate K salt.

  And the ratio of the mineral oil lubricant in the oil agent, the alkyl ether nonion and the alkyl phosphate K salt is 75 to 98% by mass for the mineral oil lubricant, 1 to 10% by mass for the alkyl ether nonion, and 1 to 1 for the alkyl phosphate K salt. It is preferable that it is 10 mass%. By setting such a content ratio, it is possible to prevent precipitation of oligomers and monomers that are likely to occur when melt spinning using a low-melting polymer as described above, and to prevent generation of white powder Can be fully played.

  The above-mentioned oil can be diluted with a low-viscosity mineral oil diluent or used in the form of a water emulsion. However, in the polyamide fiber of the present invention, it should be diluted with a low-viscosity mineral oil diluent. Is preferred.

  In other words, when adopting a one-step method to produce the polyamide fiber of the present invention with high productivity, if an emulsion oil is used, the fibers are welded together by frictional heat between the winder's friction roller and the take-off bobbin. Defects occur. This is because the melting point of the low melting point polymer when wet is lower by 20 ° C. or more than the melting point when dried.

  Therefore, an oil agent diluted with a low-viscosity mineral oil diluent and having a moisture content of 1% or less can be used to scrape fibers in a state close to drying, The fibers are not welded even by frictional heat with the take-off bobbin, and the unwinding property is improved.

  Furthermore, it is not clear why the oil containing the mineral oil lubricant of the present invention, the alkyl ether nonion and the alkyl phosphate K salt can prevent the precipitation of oligomers and monomers in the polymer and suppress the generation of white powder. The present inventors consider as follows. In other words, it is an oil agent diluted with a mineral oil diluent with low viscosity, and is used as a spinning oil as an oil agent having a moisture content of 1% or less, thereby suppressing precipitation of monomers and oligomers on the filament surface immediately after melt spinning. In addition, the monomer and oligomer precipitated on the fiber surface with the passage of time have the effect of reducing the viscosity and promoting the drying, so that it is considered that the accumulation of white dust can be suppressed.

  The polyamide fiber of the present invention preferably has a strength of 2.0 cN / dtex or more and a cut elongation of 135% or less. Among them, the strength is 2.5 to 4.0 cN / dtex and the cut elongation is 100 to 50%. It is preferable that In the present invention, since the oil agent having a specific component is applied to the fiber surface, generation and accumulation of white powder can be suppressed as described above, and it can be obtained with good operability. It is possible to achieve elongation.

  In addition, the use of the polyamide fiber of the present invention as a hot-melt type heat-adhesive fiber includes, for example, mixing a part of a plurality of fibers into a mixed yarn, and melting the polyamide fiber of the present invention by heat treatment. This is used to fix the shape of the blended yarn and use it as a bristle part used in mops, etc., as a pile yarn for carpets, and for some fibers constituting fabrics such as woven and knitted fabrics and nonwoven fabrics. There are applications in which the fibers of the present invention are melted by heat treatment (with a domestic iron or the like), and the fabrics are bonded together or used as a core material.

  Moreover, the polyamide fiber of the present invention can be used as a binder fiber by using a short fiber as a part of the fiber constituting the nonwoven fabric.

Next, the method for producing the polyamide fiber of the present invention will be described using an example.
Melt spinning is performed by using a nylon 6, nylon 66, nylon 12 copolymer polymer chip, melt kneading using an extruder type melt spinning machine, and spinning from a spinneret at a spinning temperature of 185 ° C. An oil containing a mineral oil lubricant, an alkyl ether nonion and an alkyl phosphate K salt is used as an oil diluted with a low viscosity mineral oil diluent, and after cooling and solidifying the yarn after melt spinning, 2.2 ml / Granted at a min rate. Subsequently, the first roller speed is 3795 m / min and the second roller speed is 3908 m / min, and the film is drawn at 1.03 times, and then wound at a friction roller speed of 3850 m / min to obtain the polyamide fiber of the present invention.

Next, the present invention will be specifically described with reference to examples. In addition, the various characteristic values and evaluation in an Example were performed as follows.
[Melting point, melting point when wet]
Performed as before.
[Strength, cutting elongation]
In accordance with JIS L-1013, measurement was performed using an autograph DSS-500 manufactured by Shimadzu Corporation at a grip interval of 25 cm and a tensile speed of 30 cm / min.
[Adhesive strength]
Using nylon fabrics shown in Table 3 “Composition of single fiber fabric (1)” of the attached white fabric for dyeing fastness test of JIS L0803, prepare two pieces of fabric to be bonded measuring 11 cm in length and 20 cm in width. . Ten samples (11 cm in length of the polyamide fiber of the present invention) are arranged in a vertical direction on one sheet of cloth to be bonded, and another sheet of cloth to be bonded is stacked thereon. Thermocompression bonding is carried out by heating one side of the fabric through a heat roller under conditions of a temperature of 120 ° C. (adhesion processing temperature), a roller speed of 0.5 m / min, and a press pressure of 0.7 kg / cm ² . After thermocompression bonding, it is left at room temperature for 24 hours, and then two sheets of adherend cloth are sandwiched between chucks of Autograph AGS-50D manufactured by Shimadzu Corporation, and the strength is measured at a peeling speed of 25 cm / min. (Polyamide fiber) divided by the fineness.
[White powder evaluation]
During yarn production: Operation was performed for 24 hours, and the occurrence and accumulation of white powder on various rollers and guides during this period were visually evaluated in the following three stages.
○: Almost no white powder is generated.
Δ: Some white powder is generated and accumulated.
X: White powder is generated and accumulated.
After time: The obtained polyamide fiber was aged for 30 days in a high-temperature and high-humidity chamber at room temperature 40 ° C x 80% humidity, and a yarn feed roller and a take-up roller were placed at the top of a 1 mm wide metal comb-shaped guide. I drove for 10 minutes at the speed of min. The following three levels were evaluated according to the amount of white powder deposited on the guide.
○: Deposit amount less than 0.015 mg Δ: Deposit amount less than 0.015 to 0.03 mg ×: Deposit amount of 0.03 mg or more

Example 1
A terpolymer copolymer polyamide (trade name “H005FA”, melting point 118 ° C., melting point 72 ° C. when wet) made of nylon 6, nylon 66, and nylon 12 monomers is used for this copolymer. On the other hand, 0.02% by mass of magnesium stearate was added and melt kneaded using an extruder type melt spinning machine. Melt spinning was performed from a spinneret having a nozzle hole diameter of 0.40 mm and a number of holes of 12 at a discharge rate of 19.5 g / min and a spinning temperature of 185 ° C.
Mineral oil lubricant, oil containing alkyl ether nonion and alkyl phosphate K salt diluted with low viscosity mineral oil diluent (mineral oil diluent 70 mass%, mineral oil lubricant 26.4 mass%, C12 (raw alcohol) 12) Alkyl ether nonion 2.1 mass%, C16-18 (carbon number 16-18 of raw alcohol) alkyl phosphate K salt 1.5 mass%: Takemoto Oil & Fats Co., Ltd. "UTN-2701") 2.2ml from the oil application device / Min and supplied to the cooled and solidified yarn after melt spinning. Subsequently, the film was stretched 1.03 times with a first roller speed of 3795 m / min and a second roller speed of 3908 m / min, and then wound with a friction roller speed of 3850 m / min to obtain a polyamide fiber of 110 dtex / 12f.

Example 2
Using the same copolymerized polyamide as in Example 1, melt spinning was carried out at a discharge rate of 14.0 g / min and a spinning temperature of 185 ° C. from a spinneret having a nozzle hole diameter of 0.35 mm and 12 holes. The same oil agent as in Example 1 was supplied from the oil agent applicator at a rate of 1.6 ml / min, and after melt spinning, it was applied to the cooled and solidified yarn. Subsequently, the film was stretched 1.03 times with a first roller speed of 3820 m / min and a second roller speed of 3897 m / min, and then wound with a friction roller speed of 3850 m / min to obtain a 78 dtex / 12f polyamide fiber.

Example 3
A quaternary copolymer polyamide (manufactured by Arkema, trade name “M2468”, melting point 105 ° C., melting point 68 ° C. when wet) composed of monomers of nylon 6, nylon 66, nylon 11 and nylon 12 is used. 0.02% by mass of magnesium stearate was added to the polymer and melt kneaded using an extruder type melt spinning machine. Melt spinning was carried out at a discharge rate of 19.5 g / min and a spinning temperature of 155 ° C. from a spinneret having a nozzle hole diameter of 0.40 mm and 12 holes. The same oil agent as in Example 1 was supplied from the oil agent applicator at a rate of 2.2 ml / min. After melt spinning, it was applied to the cooled and solidified yarn. Subsequently, the film was stretched 1.10 times at a first roller speed of 3543 m / min and a second roller speed of 3897 m / min, and then wound up at a friction roller speed of 3850 m / min to obtain 110 dtex / 12f polyamide fiber.

Example 4
Using the same copolymerized polyamide as in Example 3, melt spinning was performed at a discharge rate of 14.0 g / min and a spinning temperature of 155 ° C. from a spinneret having a nozzle hole diameter of 0.35 mm and a hole number of 12. The same oil agent as in Example 1 was supplied from the oil agent applicator at a rate of 1.6 ml / min, and after melt spinning, it was applied to the cooled and solidified yarn. Subsequently, the film was stretched 1.08 times with a first roller speed of 3608 m / min and a second roller speed of 3897 m / min, and then wound with a friction roller speed of 3850 m / min to obtain a 78 dtex / 12f polyamide fiber.

Comparative Example 1
A polyamide fiber was obtained in the same manner as in Example 1 except that an oil agent consisting only of a mineral oil lubricant (“UTN-2701A” manufactured by Takemoto Yushi Co., Ltd.) was used as the oil agent.

Comparative Example 2
In place of the oil used in Example 1, octyl palmitate 96.4% by mass, C12 (carbon number 12 of raw material alcohol) alkyl ether nonion 2.1% by weight, C16-18 (carbon number 16 of raw material alcohol 16) alkyl phosphate K A polyamide fiber was obtained in the same manner as in Example 1 except that the oil agent composed of 1.5% by mass of salt was used.

  Table 1 shows the characteristic values and evaluation results of the polyamide fibers obtained in Examples 1 to 4 and Comparative Examples 1 and 2.

As can be seen from Table 1, the polyamide fibers obtained in Examples 1 to 4 had little white powder accumulation at the time of spinning and after aging, and could be obtained with good operability. Moreover, both strength and elongation were excellent, and adhesion was also good.
On the other hand, since the polyamide fibers of Comparative Examples 1 and 2 were not attached with an oil agent containing a mineral oil lubricant, an alkyl ether nonion and an alkyl phosphate K salt, generation of white powder both at the time of spinning and after aging, A lot of accumulation occurred and the operability deteriorated.

Claims (2)

Nylon 6, nylon 66, nylon 11, nylon 12, and nylon 610 copolymerized polyamide having a melting point of 100 to 160 ° C and a wet melting point of 50 to 90 ° C A spinning oil obtained by diluting an oil containing 75 to 98% by weight of a mineral oil lubricant, 1 to 10% by weight of an alkyl ether nonion and 1 to 10% by weight of an alkyl phosphate K salt with a mineral oil diluent. A polyamide fiber obtained by adhering to a fiber surface. The polyamide fiber according to claim 1, which has a strength of 2.0 cN / dtex or more and a cut elongation of 135% or less.