JPH04209824A - Dyeable polyolefinic fiber and its production - Google Patents

Abstract

PURPOSE:To provide the subject fiber capable of being dyed with disperse dyes, etc., and having excellent water repellency and non-moisture-absorbing property by preliminarily kneading a dyeable polymer with a compatibilizing agent in a melted state, adding a polyolefin to the kneaded product in the melted state, and subsequently melt-spinning the melted mixture. CONSTITUTION:A dyeable polymer such as a polyester or polyamide is preliminarily mixed with a compatibilizing agent in a melted state, mixed with a polyolefin in the melted state, and subsequently melt-spun to provide the subject fiber comprising a polyolefinic polymer alloy containing the polyolefin as a sea component and the dyeable polymer having an average diameter of <1mum in the cross section of the fiber as an island component.

Description

[Detailed description of the invention]

[0001)

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyolefin polymer alloy fiber that can be easily dyed with dyes such as disperse dyes and has excellent water repellency and non-hygroscopicity, and a method for producing the same. [0002]

[Prior Art] Polyolefin fibers have excellent water repellency and non-hygroscopicity, and have low specific gravity and low thermal conductivity, making them lightweight and warm.
Since the main chain is composed only of carbon and hydrogen, it has various features not found in other fibers, such as excellent chemical resistance such as acid resistance and alkali resistance. However, since it does not have a functional group, it cannot be dyed, which limits its use, especially as clothing fibers, so attempts have been made over the past many years to improve its dyeability. For example, dyeable polyolefin fibers kneaded with ethylene-aminoalkyl acrylate copolymer as a dyeable component are found in Japanese Patent Publication No. 63-51453 and Japanese Patent Publication No. 2-42948; Japanese Patent Publication No. 64-85365;
The fibers shown in the above publication are coated with an alkyl phosphate cyclic surfactant to improve dyeability, and the core component is a dyeable thermoplastic resin such as polyester or polyamide, and the sheath component is a polyolefin. There is dyeable ponopholefin fiber, which is made by dyeing the core component of a glass-core composite fiber. [0003]

[Problems to be Solved by the Invention] However, the above-mentioned conventional technology still does not have sufficient dyeability, and when physical force such as washing or friction is applied to the fiber, peeling between the core and sheath easily occurs, and the peeled part This causes light scattering and the color of parts of woven or knitted fabrics that are subjected to physical pressure becomes lighter, resulting in a phenomenon commonly referred to as ``chalk marks.'' This creates the problem of color shading in dyed products even when dyed uniformly. there were. In addition, dyeable polyolefin fibers kneaded with ethylene-aminoalkyl acrylate copolymer use dispersants such as metal soap, so fibers using this will lose the characteristics of polyolefins such as water repellency. There was an issue. [00041] In order to solve the problems of the prior art, it is an object of the present invention to provide a dyeable polyolefin fiber with improved dyeability while taking advantage of the characteristics of polyolefin fibers, and a method for producing the same. [0005]

[Means for Solving the Problems] In order to achieve the above object, the dyeable polyolefin fiber of the present invention is a fiber containing polyolefin as a sea component, and has a dyeable polyolefin fiber having an average diameter of less than 1 μm in the fiber cross section. It is characterized by being made of a polyolefin polymer alloy containing a polymer as an island component. [0006] In the above configuration, it is preferable that the amount of the dyeable polymer present is 5 to 55% by weight. [0007] Furthermore, in the above configuration, it is preferable that the dyeable polymer is at least one type of polymer selected from polyamide and/or polyester, and copolymers thereof. [0008] Furthermore, the method for producing dyeable polyolefin fibers of the present invention is a method for producing polyolefin-based polymer alloy fibers containing polyolefin as a sea component and dyeable polymers having a diameter of less than 1 μm in the fiber cross section as an island component. It is characterized in that the dyeable polymer and the compatibilizer are kneaded in advance in a molten state, then the polyolefin polymer is mixed in a molten state, and then melt-spun. [00091

[Function] According to the configuration of the present invention described above, the fiber has polyolefin as a sea component, and the fiber cross section has (
In other words, since it is a polymer alloy containing a dyeable polymer with an average diameter of less than 1 μm (as seen from the fiber cross-sectional direction) as an island component, it maintains the properties of polyolefin fibers.
A dyeable polyolefin fiber with improved dyeability can be obtained. [00103 According to the above-mentioned preferred configuration of the present invention in which the amount of the dyeable polymer is 5 to 55% by weight, the present invention is even more excellent in that the dyeability can be improved while taking advantage of the properties of the polyolefin fiber. It can be done. [0011] Furthermore, according to the preferred configuration of the present invention in which the dyeable polymer is at least one kind of polymer selected from polyamide and/or polyester, and a copolymer thereof, the dyeable polymer can be dispersed using ordinary dyeing conditions. It can be dyed with dyes. [0012] Furthermore, according to the method of the present invention described above, the dyeable polymer and the compatibilizer are kneaded in advance in a molten state, and then the polyolefin polymer is mixed in a molten state, and then melt-spun, so that polyolefin fibers A dyeable polymer can be finely dispersed therein. [0013] [0013] The present invention will be explained in more detail below using Examples. Note that the present invention is not limited to the following examples. [0014] The present inventors used a polymer alloy containing hydrophobic polyolefin as a sea component and dyeable polyamide or polyester as an island component, and formed fibers by a melt spinning method extruded into the air. It was found that most of the polyolefins are made up of sea-based polyolefins. The fibers obtained in this way do not lose the characteristics of polyolefin fibers such as water repellency, and can be dyed well in deep colors when high-pressure dyed using disperse dyes. The present inventors have discovered that the anti-thread properties and stretchability are comparable to those of ordinary polyolefin fibers, leading to the present invention. [0015] The dyeable polymer used as the island component of the present invention has a shape similar to an elongated capsule of medicine, and the diameter in the fiber cross section is less than 1 μm, that is, the volume of one island component is approximately It is preferably less than 10 μm3, and even if the average value is 1 μm or less, it is 3 μm.
The presence of island components exceeding m is not preferable because the fiber formability is poor. The island component used is thermoplastic nylon 6.
Conveniently, homopolymers and copolymers of polyamides such as , nylon 66 and nylon 12, and polyesters such as polyethylene terephthalate and polybutylene terephthalate, and modified products thereof, as well as dyeable thermoplastic resins such as polycarbonate. can be used. In the above, for example, when polyethylene terephthalate is used, the fiber can be dyed with a disperse dye. For example, polyethylene terephthalate has 2°4
If ~10 mol% of 5-sodium sulfoisophthalic acid component units are copolymerized, a basic dyeable type fiber can be obtained, especially if it is a copolymer of about 2.4 to 4.0 mol%. For example, a pressure dyeable type can be used, and a pressure dyeable type can be used if the copolymer is about 5 to 10 mol%. [0016] The dyeable polymer has a melting point of 100 to 28
A temperature in the range of 0°C is preferable for processing the polymer alloy. If the melting point exceeds 280°C, the fiber forming temperature must be 300°C or higher, and in this case, thermal deterioration of the stabilizer in the polyolefin increases. Furthermore, if the melting point is 100° C. or less, it is difficult to process the fibers, which is not preferable. [00171 The sea-component polyolefin used in the present invention is conveniently a homopolymer, a copolymer, or a modified product thereof of an α-polyolefin having a melting point of 100°C or higher, such as polypropylene, polyethylene, polybutene-1, or polymethylthene, and is suitable for fiber molding. Particularly preferred is polypropylene. [0018] Also, a compatibilizer is used for convenience of finely dispersing the island components. As the compatibilizing agent, for example, a copolymer of ethylene-acrylic acid or a derivative thereof is used. More specifically, there are the following. (1) Ethylene-methyl acrylate copolymer (EMA) containing 15 to 35 wt% of methyl acrylate. (2) Ethylene-ethyl acrylate copolymer (EMA) containing 15 to 35 wt% of ethyl acrylate. (3) An ethylene-acrylic acid-methyl acrylate terpolymer containing 5 to 15 wt% of acrylic acid, 5 to 15 wt% of methyl acrylate, and 85 to 65 wt% of ethylene. (4) Ethylene containing 10 to 20 wt% methacrylic acid
An ionomer in which 15 to 50 mol% of the carboxylic acid of methacrylic acid copolymer (EMAA) is zinc or alkali metal salt. (5) Methacrylic acid and acrylic acid total 10-20
wt% ethylene-methacrylic acid-acrylic acid copolymer ionomer. [0019] In addition, °°Atomer°゛ (manufactured by Mikata Petrochemical Co., Ltd.) used in the adhesive layer of coextruded multilayer film
, Modic °° (manufactured by Mitsubishi Yuka Co., Ltd.) can also be used. In addition, in the acrylic acid-based or methacrylic acid-based ethylene copolymer, it is preferable that the carboxylic acid in the side chain is in the form of an ester or an ionomer type salt from the viewpoint of heat resistance. [00201 Note that the ratio of the sea component to the island component is at least 5 wt% or more, preferably 10 to 4 wt% of the island component in terms of dyeability.
It is preferable to add 0 wt%, and if it exceeds 55 wt%, the seabird component tends to be reversed, which is not preferable. [00211 The spinning temperature (T'C) of the dyeable polyolefin fiber used in the present invention is Ts+10≦, assuming that the melting point of the sea component polyolefin is Ts°C and the melting point of the island component is 11°C.
T<360 is possible, and it is more preferable to use a polymer alloy with a combination of Ts<T+ and adopt a range of TI +5≦T≦320. If the spinning temperature exceeds 360°C, the polyolefin of the sea component will decompose, which is undesirable.
Considering the heat resistance of various stabilizers in polyolefin, 3
More preferably, the temperature is 20°C or lower. The melt viscosity of the polymer alloy used is determined according to JISK7210, where the spinning temperature is the measurement temperature.
Melt flow rate (MFR; g/10 min) measured according to (weighted 2169 g) 10≦MF R<30
0 is convenient, and 30 to 30 for fineness of 2 to 0.5 denier.
100g/10 minutes, 1 for thick fineness of 30-15 denier
Particularly preferred is 0 to 30 g/10 minutes, and more preferably around 10 g/10 minutes for large fineness. For MFR>300,
Since fiber formation is lost due to excessive fluidity, it is preferable to lower the spinning temperature to form fibers. [002233 The spun yarn of the present invention generally has a 0. It is obtained in exactly the same manner as ordinary polypropylene fibers using the above-mentioned 5-4 denyl fibers, and the spinnability is the same as that of ordinary polypropylene fibers. Furthermore, since the spun yarn of the present invention has the same applicability to weaving and knitting machines as ordinary polypropylene spun yarn, there is no problem in making it into woven or knitted fabrics. When dyed, if the content of the fiber of the present invention is less than 20%, uneven dyeing will be noticeable, which is not preferable. The same applies even if the fiber used in the present invention is in the form of a multifilament. [00231 The polyolefin fiber made of the polyolefin polymer alloy of the present invention is such that the island component finely dispersed in the fiber can be easily dyed by a high-pressure dyeing method using a disperse dye, and the fiber surface has a sea component polyolefin. Since it is dominated by , it exhibits good water repellency and also has good fiber properties such as fastness to friction. In addition, because the island component has a fine diameter of less than 1 μm in the fiber cross section, it is much thinner than the core diameter of conventional sheath-core composite fibers, and peeling between the sea-island components due to external physical factors is less likely to occur (for example, due to fibrillation). etc.), even when the dyeable polyolefin fiber of the present invention is used as a spun yarn, a woven or knitted fabric thereof, or a multifilament woven or knitted fabric, it is possible to provide a uniformly deep-dyed product without producing chalk marks. [0024] Specific experimental examples will be explained below. [0025] Examples 1 to 7, Comparative Examples 1 to 2 100 parts by weight of nylon-6 with a number average molecular weight of 18,000 and a melting point of 220°C and 10 parts by weight of an ethylene acrylic ester copolymer compatibilizer were heated at 280°C biaxially. After kneading with an extruder, nylon
MFR at 230°C is 8 g/10 min, melting point 16 so that 6 is 30 wt%, 20 wt%, 10 wt%, 0 wt%.
While adding polypropylene powder (diameter 1.5 mm, length 4-5 mm) at 2°C, mix again using a twin screw extruder.
Made of polymer alloy. This polymer alloy was processed using a spinneret with 400 spinneret holes at a discharge rate of 125 g/min.
Melt-spun at a spinning temperature of 285°C to obtain a 4.5 denier (d
) and 43 d of undrawn yarn, and 3.5
Stretched to double size, mechanically crimped using a stuffer box, and then dried using a net conveyor dryer at 120°C.
It was cut into 1.5 d and 15 d staples. The fiber cross section of the obtained staple was extracted with formic acid, and the diameter was measured using a scanning electron microscope. (0026) Also, the obtained staple was made into a web using a parallel roller card flat card, and then made into a felt of 60 g/m2 using a needle punching machine. TH3-100 (dispersant) 0.3g
/liter, and ammonium sulfate (buffer) 200
g/liter and acetic acid 3.3 ml/liter pH adjusting solution 10 ml/liter and high-pressure dyeing at 130°C for 30 minutes. 5 inside
After being treated for minutes, the dyed knitted fabric or spun yarn was washed and dried with water and evaluated using the JIS Z8721 standard color chart. [0027] Furthermore, the water repellency of the dyed felt was determined by dropping distilled water from a position 30 cm above the felt and whether it remained as a water sphere on the felt surface (marked with an ○) or not (marked with an x). . The results are shown in Table 1. In Table 1, the spinnability is indicated as × if the undrawn yarn of 12d cannot be pulled off (in that case, the undrawn yarn is pulled off by hand and the cross section is observed), and when each undrawn yarn is pulled off as ○. did. Furthermore, dyeability and water repellency were evaluated using felt. [0028] Example 8 The felt made from the fibers of Example 3 was made in the same manner as in Example 3 to produce Sumikalon S-2RL, S-3RF, and 5E-3G.
stained using L, 5-BDF and 5-BG. As a result, it was possible to dye the product in the same deep color as in Example 3. [0029] Example 9 [η] 0.63 (where [η] is the dilute solution viscosity,
It is a measure of average molecular weight. ), melting point 260℃
20wt% of polyethylene terephthalate as an island component,
A polymer alloy was produced in the same manner as in Example 1 using the polypropylene of Example 1 as the sea component. This polymer alloy was processed using a spinneret with 100 spinneret holes and a discharge rate of 125
g/min at a spinning temperature of 290° C. to obtain a 43 d undrawn yarn, which was drawn 2.8 times in hot water at 95° C. to obtain a 19 d staple in the same manner as in Example 1. [00301 When the obtained fiber was dyed in the same manner as in Example 1, it was dyed in the same deep color as in Example 1. [00311 Examples 10 to 13 Comparative Examples 3 to 4 Nylon 6 with a number average molecular weight of 18,000 and a melting point of 220°C was twin-screw extruded with 100 parts by weight of an ethylene acrylate copolymer compatibilizer at a temperature of 280°C. After mixing using a machine, nylon-6 is 30wt%, 20wt%, 10wt%
While adding polypropylene powder having a MFR of 230° C. of 8 g/10 minutes and a melting point of 162° C., the mixture was mixed again using a twin-screw extruder so as to have a concentration of 0 wt % to obtain a polymer alloy. This polymer alloy was melt-spun using a spinneret with 400 holes at a flow rate of 125 g/min at a spinning temperature of 285°C to obtain undrawn yarns of 4.5 d and 12 d, which were 3.5 times larger in hot water at 95° C. After being mechanically crimped in a stuffer box, it was dried in a net conveyor dryer at 120° C. and cut into 51 mm to obtain staples with thicknesses of 1.5 d, tl, and 4 d. The fiber cross section of the obtained staple was extracted with formic acid, and the diameter was measured using a scanning electron microscope. [0032] Again. The resulting staples were flat carded and spun into approximately 23 count and 5 count yarns. This 23rd spun yarn is 50×18 gauge/i
It was knitted into a cotton jersey fabric with a weight of 60 g/m2 using a sinker circular knitting machine. After degreasing this knit fabric or No. 5 fabric,
Dyeability was determined using Kayalon Polyester BR-31g/liter, Texaton TH3-1000, 3g/liter, ammonium sulfate 200g/liter and acetic acid 3.3m.
It was immersed in a dye solution consisting of 10 ml/liter of a pH adjustment solution of 1/liter, and subjected to high pressure dyeing at a temperature of 130°C for 30 minutes, followed by 2 g/liter of soda ash and 182 g/liter of hydrosulfur.
After treatment for 5 minutes in an 80°C bath containing a
Evaluation was made using 21 standard color charts. [0033] Also, the water repellency of the dyed knit fabric was determined by dropping distilled water from a position 30 cm above the knit fabric surface and whether it remained as a water ball on the knit fabric surface (marked with an ○) or not (marked with an x). I judged it. The results are shown in Table 2. [0034] The spinnability was determined when the undrawn yarn strength of 12d could not be removed. However, in that case, the undrawn yarn was pulled off by hand and the cross section was observed. In addition, the case where each undrawn yarn is taken off is marked as ○. [0035] Example 14 The knit fabric made from the fiber of Example 10 was made in the same manner as in Example 10 to produce Sumikaron S-2RL, S-3RF, and 5E3.
When stained using GL, 5-BDF and 5-BG, the same deep color as in Example 10 could be obtained. [0036] Comparative Example 5 Example 1 was prepared by blending the fibers of Example 10 and Comparative Example 4.
In the same manner as 0, a spun yarn of approximately 23rd count was made, and the amount was 60g/m2.
When we dyed the knitted fabric and observed the uneven dyeing,
When the cotton blend ratio of Example 10 was 15%, uneven dyeing clearly occurred. [0037] Example 15 600 d/400 multifilaments were made in the same manner as in Example 12, and 15 vertical filaments/400 pieces were made using a small manual loom.
A plain woven fabric of 9 widths/in was prepared and dyed in the same manner to obtain a dyed product of 10RP5/12. [00381 As explained above, according to this embodiment,
It is now possible to dye polyolefin fibers, which was previously impossible, and to supply colorful, permanently water-repellent fiber materials at low cost. This fiber can be applied to various fields such as spun yarn, filament yarn, nonwoven fabric, and carpet. It can also be mixed, blended, mixed, mixed, knitted, or interwoven with other fibers, and the mixing ratio can also be selected arbitrarily. Also,
It can be used not only for clothing, but also for a wide range of fields, such as indoor and industrial fields. [0039]

Effects of the Invention As explained above, according to the present invention, a dyeable polymer which is a fiber containing Boolefin as a sea component and has an average diameter of less than 1 μm in the fiber cross section (that is, viewed from the direction of the fiber cross section) Since it is a polymer alloy containing as an island component, it is possible to make a dyeable polyolefin fiber with improved dyeability while taking advantage of the properties of polyolefin fiber. [00401 Furthermore, according to a preferred configuration of the present invention in which the amount of the dyeable polymer is 5 to 55% by weight, an even better result is achieved in that the dyeability can be improved while taking advantage of the properties of polyolefin fibers. can be taken as a thing. [00411 Furthermore, according to a preferred configuration of the present invention in which the dyeable polymer is at least one kind of polymer selected from polyamide and/or polyester, and copolymers thereof, disperse dyes etc. can be dyed using normal dyeing conditions. Can be dyed with [00421] Furthermore, according to the method of the present invention, the dyeable polymer and the compatibilizer are kneaded in advance in a molten state, and then the polyolefin polymer is mixed in a molten state, and then melt-spun, so that the dyeable polymer and the compatibilizer are mixed in a molten state, and then melt-spun. The dyeable polymer can be finely dispersed.

[Procedural amendment] [Submission date] August 21, 1991

[Procedural amendment 1]

[Document color to be corrected] Specification

[Correction target item name] 0014 [Correction method] Change

[Correction details]

[0014] The present inventors used a polymer alloy containing hydrophobic polyolefin as a sea component and dyeable polyamide or polyester as an island component, and formed fibers by a melt spinning method extruded into the air. It was found that most of the polyolefins are made up of sea-based polyolefins. The fibers obtained in this way do not lose the characteristics of polyolefin fibers such as water repellency, can be dyed well in deep colors when high-pressure dyed using disperse dyes, and are made of polymers with a diameter of less than 1 μm in the fiber cross section of the island component. Alloy is
It was discovered that the spinnability and drawability of this fiber are comparable to those of ordinary polyolefin fibers, leading to the present invention.

[Procedural amendment 2]

[Document color to be corrected] Specification

[Correction target item name] 0032 [Correction method] Change

[Correction details]

[0032] The resulting staples were also flat carded and spun into approximately 23 count and 5 count spun yarns. This 23rd spun yarn is 50×18 gauge/i
A knit fabric of 60 g/m2 was knitted using a sinker circular knitting machine. After degreasing this knit fabric or No. 5 fabric,
The dyeability was determined using Kayalon Polyester BR-3Ig/liter, Texaton TH8-1000, 3g/liter, ammonium sulfate 200g/liter, and acetic acid 3.3m.
It was immersed in a dye solution consisting of 10 ml/liter of a pH adjusting solution and dyed under high pressure for 30 minutes at a temperature of 130°C, followed by 2 g/liter of soda ash and 152 g of hydrosaraf.
/liter for 5 minutes at 80°C, washed with water and dried to obtain dyed knit fabric or spun yarn, JISZ8
Evaluation was made using the 721 standard color chart.

Claims (4)

[Claims] 1. A dyeable polyolefin fiber comprising a polyolefin as a sea component, comprising a polyolefin polymer alloy containing a dyeable polymer having an average diameter of less than 1 μm in the cross section of the fiber as an island component. fiber. 2. The dyeable polyolefin fiber according to claim 1, wherein the amount of the dyeable polymer present is 5 to 55% by weight. 3. The dyeable polyolefin fiber according to claim 1, wherein the dyeable polymer is at least one polymer selected from polyamides, polyesters, and copolymers thereof. 4. A method for producing a polyolefin polymer alloy fiber containing a polyolefin as a sea component and a dyeable polymer having a diameter of less than 1 μm in the cross section of the fiber as an island component, the method comprising: 1. A method for producing dyeable polyolefin fibers, characterized in that the fibers are kneaded in advance in a molten state, then polyolefin is mixed in a molten state, and then melt-spun.