JP2971986B2 - Colored polyamide multicomponent fiber - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a colored polyamide-based ultrafine fiber-generating multicomponent fiber containing a polyamide colored with a dye and / or a pigment as one component.

[0002]

2. Description of the Related Art Conventionally, a leather-like sheet made of a non-woven fabric containing polyamide as an ultra-fine fiber component and an elastic polymer is more in comparison with a non-woven fabric made of polyester as an ultra-fine fiber component or a non-woven fabric of a normal denier fiber. It has been highly evaluated as a material that has a texture similar to natural leather, such as being flexible and excellent in texture. As a method for producing a leather-like sheet material using such a polyamide as a microfiber component, a non-woven fabric of sea-island-type or split-type polyamide microfiber-generating fibers is impregnated with an elastic polymer before or after impregnating with a solvent or a solvent. 2. Description of the Related Art A method of dissolving or decomposing and removing one component of a fiber component by treating with a chemical or the like to form a fibrous sheet comprising ultrafine polyamide fibers and an elastic polymer has been widely used. On the other hand, the polyamide ultrafine fiber-generating fiber 1
Many proposals have been made to produce a fibrous sheet by using an elastic polymer as a component, impregnating a solvent or solution of the elastic polymer to dissolve the elastic polymer, and then solidifying the resulting polymer in a nonwoven fabric without extraction and removal. .

[0003] In general, ultrafine fibers are generally inferior in dyeing properties to denier fibers, so a large amount of dye is required when a suede material or the like made of ultrafine fibers is dyed to give a dark color. There are problems in terms of quality such as light fastness and color fastness, and cost. As a countermeasure against this, many proposals have been made to color the ultrafine fibers as a raw material (referred to as "dyeing") to improve the quality such as light fastness and dyeing fastness. For example, Japanese Patent Publication No. 48-11925 discloses a polymer mutual array fiber in which 1% of carbon black is added to polyethylene terephthalate as an island component, and a mixed spun fiber having 6-nylon as an island component and 5% of a red pigment is added. Japanese Patent Publication No. 55-504 discloses a mixed spun fiber containing 6% nylon containing 5% of carbon black as an island component, and Japanese Patent Publication No. 59-12785 discloses a mixed spun fiber containing 5% of a pigment mainly containing carbon black. JP-B-59-44416 discloses a multilayer hollow bonded fiber in which polymerized polyester and polyamide are arranged side by side, and JP-B-62-37152 discloses a three-component fiber including a core-sheath type ultrafine fiber.
JP-A-1-52820 proposes a colored polyurethane-based multicomponent fiber.

However, in the case of ultrafine polyamide fibers, the dyes and pigments must be added in a very large amount (1 to 10%) in order to achieve a sufficient color development. Due to the increase in viscosity, the spinnability has been impaired due to yarn breakage during clogging, clogging of holes, clogging of filters, and the like, and fiber properties have been inevitably reduced.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems, and it is an object of the present invention to provide a multi-component fiber containing a polyamide colored with a dye and / or a pigment as one component. In obtaining the same, a compound having a specific structure is present in a polyamide to minimize the increase in melt viscosity due to the addition of a dye or pigment, and to stably produce a colored polyamide-based ultrafine fiber-generating fiber.

[0006]

In order to solve the above problems, the present invention employs the following configuration. That is, in the present invention, in a multi-component fiber containing a colored polyamide containing a dye and / or a pigment as one component, the compound represented by the following general formula 4 and / or the following general formula It is characterized by containing 0.1 to 10% of the compound represented by 6.

[0007]

Embedded image (Wherein, R ₁ is an alkyl group having ₁ to 21 carbon atoms, R ₂ is an alkylene group having 2 to 4 carbon atoms or a styrene residue, m and n are integers where m + n is 1 to 4, and k is 0 or 1) , a is of _{5, -S -, - SO 2} -, - it is any one of O- here, R _3, R ₄ represents H or alkyl group having 4 or less carbon atoms)..

Embedded image

[0008]

Embedded image (In the formula, R represents an alkyl group having 12 to 40 carbon atoms.)

[0009]

The carbon number of R _{1 and} the number of added moles m + n of alkylene oxide in the compound of formula 4 according to the present invention can be arbitrarily selected within the above range. If the number of carbon atoms in R ₁ exceeds 21, the effect is insufficient due to poor compatibility with the resin, and if the number of moles of added alkylene oxide exceeds 4, the degree of polymerization of the resin is significantly reduced.

The compound represented by formula 4 according to the present invention is
With respect to the bisphenol represented by Chemical formula 7, ethylene oxide,
It can be easily obtained by adding propylene oxide, styrene oxide and the like, and then acylating with a fatty acid having 2 to 22 carbon atoms.

Embedded image

Specific examples of the compound represented by the general formula 4 according to the present invention are as follows.

Embedded image (M + n = 2, hereinafter abbreviated as compound (I-1) of the present invention)

Embedded image (M + n = 2, hereinafter abbreviated as compound (I-2) of the present invention)

Embedded image (M + n = 4, hereinafter abbreviated as compound (I-3) of the present invention)

Embedded image (M + n = 4, hereinafter abbreviated as compound (I-4) of the present invention)

On the other hand, in the compound of formula 6 according to the present invention, the carbon number of R can be arbitrarily selected within the above range. If the number of carbon atoms of R is less than 12, the molecular weight is too low and boiling occurs at the melting temperature of the polyamide to form air bubbles, which adversely affects the fiber. If it exceeds 40, the compatibility with the resin becomes poor, and the effect is insufficient. It is. R is specifically n-dodecyl, n-hexadecyl, n-octadecyl, n
-Docosyl group, linear alkyl group such as n-triacosyl group, 2-hexadecyl group, 2-decyltetradecyl group,
And a branched alkyl group such as a methyl branched octadecyl group.

The compound represented by the general formula 6 according to the present invention is obtained by reacting 1 mole of phthalic anhydride with an equimolar alkylamine having 12 to 40 carbon atoms to form a monocarboxylic acid monoamide compound, followed by dehydration condensation. Can be easily obtained.

Specific examples of the compound represented by the general formula 6 according to the present invention are as follows.

Embedded image (Hereinafter abbreviated as the present compound (II-1))

Embedded image (Hereinafter abbreviated as the present compound (II-2))

Embedded image (Hereinafter abbreviated as the present compound (II-3))

Embedded image (Hereinafter abbreviated as the present compound (II-4))

The compounds represented by the general formulas (4) and (6) are added to the polyamide resin and hardly smoke or color even when exposed to high temperatures during spinning, and have excellent heat resistance. It has the characteristic that the melt viscosity of the polyamide resin is reduced and the degree of polymerization of the polyamide resin is not substantially reduced. Therefore, the melt viscosity of the polyamide, which has been increased by the addition of the dye / pigment, can be reduced to the level at which the polyamide is not added, and the spinning can be performed in the same manner as the non-added polyamide-based multicomponent fiber. Can be produced.

The compounds represented by the general formulas (4) and (6) are used in an amount of 0.1 to 10 parts, preferably 0.5 to 10 parts, per 100 parts of the polyamide resin in order to exhibit the intended performance.
It is necessary to add 5 parts. It is necessary to change the amount depending on the type and amount of dyes and pigments added. However, if the amount is less than 0.1 part, the effect is hardly expected. If the amount exceeds 10 parts, the resin properties and spinnability are adversely affected. The compound may be added to the polyamide resin during the production of the resin or in an appropriate step after the production, or may be mixed and added to the resin pellets during spinning. In the present invention, it is preferable to use a dye-pigment-added polyamide as a masterbatch.
May be added.

The ultrafine fiber-generating multicomponent fiber used in the present invention is, for example, a fiber having a chrysanthemum cross section in which one component is radially interposed between other components, a multilayer bimetallic fiber,
Alternatively, a multi-layer bimetallic fiber having a donut-shaped cross section, or a sea-island mixed spun fiber spun by melting and mixing two or more components, or a large number of ultrafine fibers continuous in the fiber axis direction are aggregated and combined with other components. And / or a polymer array fiber partially bonded to form one fiber, and two or more of these fibers may be used in combination or in combination. Further, when at least one component is dissolved and removed, an ultrafine fiber-generating multicomponent fiber composed of multiple components is obtained which gives a bundle of fibers mainly composed of ultrafine fibers of 0.5 denier or less, preferably 0.1 denier or less. It is particularly preferably used because a good texture and appearance can be obtained as a preparation material.

Preferred polyamides constituting one component in the multicomponent fibers according to the present invention include nylon 4, nylon 6, nylon 7, nylon 11, nylon 12, nylon 66, nylon 6/10 copolymerized nylon and the like. Aliphatic polyamides and aromatic polyamides are selected, and when polyurethane is used as another component,
Terminal amino group concentration of terminal blocked with aliphatic carboxylic acid 3
× 10 ⁻⁵ eq / g or less, more preferably 1.5 × 10 ⁻⁵ eq
/ G or less of an aliphatic polyamide.

The coloring agent used for the deposition of the polyamide of the present invention includes carbon black, lead red, graphite, ultramarine,
Inorganic pigments such as navy blue, iron oxide, molybdenum red, cadmium yellow, Guinea green, cobalt blue, titanium oxide, etc., azo type,
Organic dyes and pigments such as dye chelate, phthalocyanine and quinacdrine, and various dyes and pigments are exemplified. The amount of the colorant to be used is determined depending on the desired color tone, density, and post-treatment dyeing, and is 0.5 to 10%.

On the other hand, a preferred polymer which is used together with the polyamide according to the present invention to constitute the multicomponent fiber is a thermoplastic polymer having a melt flow coefficient (hereinafter referred to as MFR) at a melt spinning temperature larger than that of the polyamide. As the dissolution removal component, for example, polyethylene, polystyrene,
Polyurethane, polyvinyl alcohol obtained by melt polymerization method, copolymerized polyethylene terephthalate, copolymerized polyvinyl alcohol, styrene-acrylonitrile copolymer, higher alcohol ester of styrene and acrylic acid and / or methacrylic acid A copolymer with a higher alcohol ester is used. In particular, low-density polyethylene is preferably used in view of ease of spinning, workability of a nonwoven fabric as a multicomponent fiber, workability of impregnation with polyurethane, and the like. When a multi-component fiber using polyurethane as a dispersion medium component is used, a method in which the polyurethane after dissolution is left in a sheet as it is and solidified in a non-solvent to form a sheet is also preferably used.

The fineness of the ultrafine fiber-generating multicomponent fiber is not particularly limited, but is preferably 1 to 10 denier from the viewpoint of ease of sheet formation such as spinning stability, productivity and card passing property. Is preferred.

The composition ratio of the raw polyamide component to the other polymer component is determined in view of the stability of the fibrous phase, the direction of use of the fiber, and the physical properties of the obtained sheet material. It is in the range of 90%. Outside this range, the spinnability becomes unstable when it exceeds 90%,
%, The quality of a fibrous sheet material intended for a leather-like product is deteriorated, an unfavorable result is felt, the amount of dissolved and removed components is increased, and the cost is increased.

Usually, the multicomponent fiber is stretched 1.5 to 10 times by wet heat stretching or dry heat stretching, and if necessary, heat-fixed and mechanically crimped to be used. The obtained multicomponent fiber is used alone or mixed with other fibers to form a cross-wrap web or a random web. The weight is required depending on the intended product orientation.
A web of 00 g / m ² is used. Next, a fiber-entangled nonwoven fabric is formed by needle punching or jetting of a liquid or gas. Further, it may be a woven or knitted fabric or a raised fabric of those fabrics. After making these fiber aggregates, before or after removing the dispersion medium component in the multi-component fiber, impregnated with a solution in which a coloring agent, an activator, a filler, and other additives are added to the polyurethane as needed. After the treatment and coagulation in the non-solvent of the polyurethane, if the dispersion medium component in the multi-component fiber is not removed, the removal operation is performed to obtain a fibrous sheet material. Further, for a nonwoven fabric obtained from a multicomponent fiber having a polyurethane as a dispersion medium, a part or all of the polyurethane constituting the multicomponent fiber is dissolved,
The melt is retained in the fiber aggregate and wet coagulated to obtain a fibrous sheet.

In the present invention, a specific compound is added to a polyamide when producing a colored polyamide-based ultrafine fiber-generating multi-component fiber having a polyamide containing a dye and / or a pigment as a dispersing component. By lowering the melt viscosity, an increase in the melt viscosity of the polyamide due to the addition of a dye or pigment is suppressed as much as possible, and a polyamide-based multicomponent fiber having good spinnability, yarn physical properties, and fiber cross-sectional shape can be stably produced.

[0025]

Next, embodiments of the present invention will be described with reference to specific examples. The parts and percentages in the examples relate to weight unless otherwise specified.

The method of measuring a product in the present invention is as follows. (1) Relative viscosity (η _r ) of polyamide: JIS K681
0, 98% sulfuric acid solvent, sample concentration 1.00 W / V
The solution was used, and the temperature was 25.0 ± 0.
Measure at 1 ° C.

(2) Melt flow coefficient (MFR): ASTM-D-1238 using a melt indexer manufactured by Toyo Seiki Co., Ltd.
Based on Q, it is measured as a molten resin amount extruded from an orifice having a diameter of 2 mm and a length of 8 mm under a load of 325 g at a predetermined measurement temperature for 10 minutes.

(3) Tensile strength of fiber: Measured at a sample length of 10 cm and a tensile speed of 10 cm / min using Tensilon manufactured by Orientec Co., Ltd.

(4) Spinning stability: The spinning and drawing conditions were observed and evaluated in three stages. …: Good spinning and stretching can be performed. Δ: A little fusion yarn and screws are generated. ×: Screw breakage, numerous breakage, poor stretchability.

Examples 1-3, Comparative Examples 1-2, Reference Example Nylon-6 (Polymer A) having a relative viscosity η _r = 2.60 and a melt viscosity MFR = 18.0 measured at a temperature of 285 ° C. 20 parts of carbon black having a particle diameter of 16 μm was added, and the mixture was melt-mixed by a melt extruder. The obtained strand was cooled with water and cut to obtain a polyamide-colored spinning master pellet (). On the other hand, 20 parts of carbon black having a particle diameter of 16 μm were added to nylon-6 (polymer A), and
Was added and melt-mixed in the same manner to obtain polyamide colored spinning master pellets (-).

40 parts of natural pellet nylon-6 (polymer B) having a relative viscosity η ^r = 3.17 and a melt viscosity MFR = 6.0 measured at a temperature of 285 ° C., and 10 parts of the obtained master pellet (ペ レ ッ ト) 50 parts of low-density polyethylene (Polymer C) having a melt viscosity MFR = 34 measured at a temperature of 285 ° C. are mixed with a chip and supplied to an extruder. The temperature of the melting portion and the tip of the screw is 285 ° C., the spinning head and the spinneret. At a temperature of 290 ° C., a spinneret having 1,000 discharge holes having a hole diameter of 0.3 mm was mounted and mixed melt-spinning was performed, and a sea-island type multi-layer having nylon-6 as an island component, which was soaked with 9.0 denier carbon black, was used. Component fibers were produced. On the other hand, in order to lower the melt viscosity during mixing, 40 parts of nylon-6 (polymer A) having a high MFR and
10 parts of a master pellet () to which no compound was added and 50 parts of low-density polyethylene (polymer C) were mixed with chips and mixed and melt-spun in the same manner, and a sea island containing 9.0 denier nylon-6 as an island component Molded multicomponent fibers were produced. Further, 50 parts of nylon-6 (Polymer B) and 50 parts of low-density polyethylene (Polymer C) were mixed with chips and mixed and melt-spun in the same manner to obtain 9.0 denier nylon-6 containing no carbon flux. A sea-island type multicomponent fiber as a component was produced as a reference example. Each of the obtained undrawn fiber tows was drawn 2.5 times in a hot water bath at 82 ° C.

The sea-island type multicomponent fiber using the master pellet to which the compound of the formula (4) or (6) is added has excellent spinnability comparable to that of the sea-island type multicomponent fiber containing no carbon black.
Although stretchability and yarn physical properties were shown, when the compound of Chemical formula 4 or Chemical formula 6 was not added, increase in nozzle pack pressure due to thickening and melt fracture occurred, the sea-island structure was disturbed, and the spinning condition was extremely poor. A spun yarn that could withstand the evaluation could not be collected. In addition, sea-island type multicomponent fibers using nylon-6 (polymer A) having a high MFR have good spinnability,
Although stretchability and sea-island structure were shown, the fiber properties were poor because the viscosity of the polyamide was too low. Table 1 shows the spinning stability, the state of the fiber phase, and the yarn physical properties of each fiber.

[0033]

[Table 1]

Examples 4 to 7, Comparative Example 3 To the nylon-6 (Polymer A) of Example 1, 5 parts of the compound represented by Chemical Formula 6 and 4 to 20 parts of various dyes and pigments shown in Table 2 were added. The resulting strands were melt-mixed with a melt extruder, and the obtained strands were cooled with water and then cut to obtain polyamide colored spinning master pellets (〜). On the other hand, ultramarine, which is the pigment used in Example-7, was added to nylon-6 (polymer A).
0 parts were added and melt-mixed in the same manner to obtain a polyamide colored spinning master pellet ().

A mixture of natural pellets nylon-6 (polymer B) and the obtained master pellets (-) so that the dye / pigment content was 1% based on the weight of the polyamide was mixed with 50 parts of low-density polyethylene (polymer C). ) 50
The mixture was melt-spun in the same manner as in Example 1 to produce a sea-island type multi-component fiber having nylon-6 as an island component. Each of the obtained undrawn fiber tows was drawn 2.5 times in a hot water bath at 82 ° C. (II-
By adding the compound of 2), there is no increase in the pressure of the nozzle pack and no occurrence of melt fracture, the sea-island structure is uniform, the spinning condition is good, and the spinning is as good as the sea-island type multicomponent fiber containing no dye and pigment. Although the compound showed good properties, stretchability and yarn properties, when the compound of (II-2) was not added, the nozzle pack pressure increased due to thickening and melt fracture occurred, the sea-island structure was disturbed, and the spinning condition was remarkable. A spun yarn that was poor and could withstand the evaluation could not be collected. Table 2 shows the spinning stability, fiber phase state, and yarn physical properties of each fiber.

[0036]

[Table 2]

Examples -8 to 11, Comparative Example-4 573 parts of a polyester diol having an average molecular weight of 1500 obtained from 3-methyl-1,5 pentanediol and adipic acid, 573 parts of 1,4-butanediol, and 4,
339 parts of 4'-diphenylmethane diisocyanate were reacted to obtain a thermoplastic polyurethane pellet (polymer D) having a nitrogen content of 3.8% and an MFR at 250 ° C of 70 g / 10 minutes based on an isocyanate group.

The terminal amino group was blocked with acetic acid to change the terminal amino group concentration to 1.1 × 10 ⁻⁵ eq / g and the relative viscosity η
_r = 2.36 6-nylon pellets (Polymer E)
I got In the obtained pellets after polymerization (polymer E),
5% by weight of a compound represented by Chemical Formula 4 or Chemical Formula 6 shown in Table 3 was added,
The resulting strands were melt-mixed with an extruder, and the obtained strands were cooled with water and cut to obtain sample pellets (polymers FI).

The obtained thermoplastic polyurethane pellets (polymer D), 6-nylon pellets (EI) and polyamide colored spinning obtained in Comparative Example 1 to which no compound of formula 4 or 6 is added. Master pellet ()
Is a spinning raw material, a polymer stream melted by two extruder melting systems is joined at a spinning head, and a mixed stream is formed by a static mixing method in which division-integration is repeated and a melt-spinning composite fiber manufacturing apparatus is manufactured. The polyurethane was charged into one of the molten systems in a dry nitrogen gas atmosphere,
Melt at 0 ° C., charge 6-nylon in the other molten system,
Melting was performed at a melting zone temperature of 240 ° C., and each molten stream was measured by a measuring pump, and 60 parts of a polymer stream obtained by mixing 3 parts of a master pellet () with 57 parts of 6-nylon (E to H);
The polyurethane stream was combined at a spinning head at a ratio of 40 parts, and spun at a spinning temperature of 240 ° C. and a winding speed of 700 m / min.
Denier multicomponent fibers were produced. Each of the obtained undrawn fiber tows was drawn 2.8 times in a warm water bath at 80 ° C. The multicomponent fiber using 6-nylon to which the compound of formula 4 or 6 was added showed good spinnability, stretchability, and yarn physical properties, but the melt viscosity was low when 6-nylon to which no compound was added was used. Since it was too high, both spinnability and yarn properties were poor. Table 3 shows the spinning stability, fiber phase state, and yarn properties of each fiber.

[0040]

[Table 3]

The obtained multicomponent fiber was stretched 2.8 times in hot water at 80 ° C., applied with an oil agent, mechanically crimped, cut into a fiber length of 51 mm, and cut to a denier of 4.1 denier. And passed through the steps of carding, cross wrapping, and needle punching to obtain a nonwoven fabric having an apparent density of 0.160 g / cm ³ . The nonwoven fabric was impregnated with a 12% aqueous solution of polyvinyl alcohol, squeezed at a target squeezing rate of 150%, and dried to obtain a stable nonwoven fabric sheet.

A DMF solution to which 3 parts of a water-soluble silicone was added as a microporous agent was prepared, and the above-mentioned nonwoven fabric sheet was impregnated at an impregnation rate of 300%, and treated for 2 minutes in an atmosphere at a temperature of about 55 ° C. Was dissolved. Then DM
The polyurethane is coagulated by immersion in an aqueous solution containing 30% F, and treated in hot water at 95 ° C. to remove the solvent and polyvinyl alcohol, thereby obtaining a fibrous sheet having an apparent density of 0.35 g / cm ^3. Was.

The sheet was sliced to a thickness of 1.0 mm, the surface side at the time of coagulation was buffed with sandpaper and raised, followed by dyeing with a gold-containing dye, and rubbing and brushing. Finished with a 0.8mm suede-like sheet. When the obtained product is analyzed, carbon black is 1%
It is composed of 60% of nylon fine fibers contained therein and 40% of polyurethane sponge containing 1% of carbon black. When observed with a scanning electron micrograph, the product using the composite fibers of the examples is ultrafine nylon fibers. The fibers and polyurethane sponge were well separated, and the texture and appearance were good.However, in the case of the product using the composite fiber of the comparative example, the separation state of the ultrafine nylon fiber and polyurethane sponge was insufficient, and the texture and appearance Was bad.

[0044]

By adding the specific compound according to the present invention to a polyamide resin containing a dye and / or a pigment, an increase in the melt viscosity of the polyamide resin due to the addition of the dye / pigment can be suppressed. In the melt-spinning of multi-component fiber having the attached polyamide as one component,
A polyamide having a high degree of polymerization can be used, and a colored polyamide-based ultrafine fiber-generating multicomponent fiber having the same quality as a non-originated product can be produced under stable spinning conditions.

Claims (1)

(57) [Claims] 1. A multi-component fiber comprising a colored polyamide blended with a dye and / or a pigment as one component, wherein a compound represented by the following general formula 1 and / or a general formula 3 A polyamide-based multicomponent fiber containing the compound represented by 0.1 to 10%. Embedded image (Wherein, R ₁ is an alkyl group having ₁ to 21 carbon atoms, R ₂ is an alkylene group having 2 to 4 carbon atoms or a styrene residue, m and n are integers where m + n is 1 to 4, and k is 0 or 1) , a is of _{2, -S -, - SO 2} -, - it is any one of O- here, R _3, R ₄ represents H or alkyl group having 4 or less carbon atoms).. Formula 2 Embedded image (In the formula, R represents an alkyl group having 12 to 40 carbon atoms.)