JP2003064529A - Polyketone fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyketone fiber that is chromatically or achromatically colored intrinsically in no need of a long hour operation of dyeing, washing and waste solution treatment and is useful as an industrial material of high strength, high elastic modulus and high melting point. SOLUTION: The polyketone fiber includes dyes and/or pigments in an amount of 0.1-10 mass % where the size of the fine particles of the dyes and/or pigments is <=2 μm in the fiber, while the length at the longest part of the crude particles is >=5 μm and the number of the crude particles is <=3 per 10,000 μm<2> of the fiber cross section. This fiber is produced by using a dope that is prepared by dissolving the polyketone polymer in a solvent in which the dyes and/or the pigments are dispersed.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polyketone fiber containing a coloring substance (dye and / or pigment). More specifically, the present invention relates to a polyketone-colored fiber containing a chromatic or achromatic dye and / or pigment, having a structure of high crystallinity and a high degree of orientation, and exhibiting properties of high strength, high elastic modulus and high melting point. .

[0002]

2. Description of the Related Art Polyketone fiber obtained by completely alternating copolymerization of carbon monoxide and olefin has characteristics of high strength, high elastic modulus and high melting point, and is widely used in a wide range of fields such as industrial material field, daily life material field and clothing field. Expected to be deployed. In particular, polyketone having an alternating copolymer of ethylene and carbon monoxide as a main repeating unit has high crystallinity and melting point, and has a highly crystallized and highly oriented fiber structure when formed into a fiber, In particular, it is a material that can exhibit high strength, elastic modulus, and melting point.

However, since such a polyketone fiber has a structure with a high degree of crystallinity and a high degree of orientation, it is very difficult for the dye to penetrate into the inside of the fiber, and it can be dyed in any color tone by dyeing. Was very difficult. Regarding dyeing of polyketone fiber, it has been described in US Pat. No. 5,597,389 that polyketone fiber can be dyed with a disperse dye. However, what is described in this document is a dyeing technique for polyketone fibers consisting of an ethylene-propylene-carbon monoxide terpolymer. With this technology,
It is difficult to dye a highly crystalline polyketone fiber whose main component is an ethylene-carbon monoxide alternating copolymer,
There is a problem that it takes an extremely long dyeing time to penetrate the dye, and it is still difficult to give a sufficient color.

The present inventors have found that polyketone fibers having an anion group can be dyed with a cationic dye (Japanese Patent Laid-Open No. 2001-73225). However, when a polyketone fiber is manufactured by a wet spinning method using a dope in which a polyketone is dissolved in a metal salt-containing solvent,
The metal used as a solvent forms a salt with an anion group, and a long-term acid washing treatment is required to sufficiently remove the metal remaining in the fiber. When the amount is increased, there is a problem that the strength and heat resistance of the fiber are deteriorated, and when dyed with a cationic dye, the dyeing pot is easily soiled and waste liquid is complicated to collect.

As a method of coloring the fibers at the polymer stage instead of coloring the fibers, a method of adding a pigment to a polymer solution or a polymer melt is known. Regarding the polyketone, a technique (US Pat. No. 4,851,470, Japanese Unexamined Patent Publication No. Hei 2-302463, etc.) in which inorganic fine particles and carbun black are blended with a polyketone resin is disclosed. However, in all of these techniques, a polyketone composed of an ethylene-propylene-carbon monoxide terpolymer having a low crystallinity and a low melting point is melted to mix an additive. Highly crystalline and high melting point polyketone fibers having an alternating copolymer of ethylene and carbon monoxide as a main repeating unit undergo thermal deterioration during melting, and thus cannot be formed into fibers by a melt molding method. Therefore, this technique did not give any useful knowledge about the present invention.

As a method for producing a polyketone fiber having a high crystallinity and a high melting point, a wet spinning method is known in which a polyketone is dissolved in an organic solvent or a concentrated salt solution and then formed into a fiber (for example, Japanese Unexamined Patent Publication (Kokai) No. No. 228613, Japanese Patent Publication No. 4-505344, Japanese Patent Publication No. 7-508317
Publication, Tokuyohei 8-507328, International Publication 99
/ 18143 Pamphlet, International Publication 00/0961
No. 1 pamphlet etc.) However, even these prior arts do not disclose any technology relating to a polyketone colored fiber to which a pigment or a dye is added and a method for producing the same.

In the known wet spinning method used for producing viscose rayon, polyacrylonitrile fiber, etc., a so-called undiluted coloring spinning method in which a pigment is added to a dope for spinning is known. However, the present inventors have studied a method of adding a pigment or a dye to a dope in which a polyketone is dissolved in a metal salt solvent, and when the dye or the pigment is added to the metal salt solvent dope, they cause agglomeration, and spinnability or It was found that the polyketone fiber having practical strength could not be obtained because the drawability was remarkably lowered. Therefore, the conventional stock solution coloring and spinning method cannot be directly applied to the production of polyketone fibers.

[0008] However, the prior art documents up to now do not disclose any technology relating to the aggregation problem in the undiluted solution spinning method, the problem that a high-strength polyketone fiber cannot be obtained, and a solution to these problems. As described above, in a polyketone fiber mainly composed of an alternating copolymer of ethylene and carbon monoxide, a polyketone colored in an achromatic color or a chromatic color while having the characteristics of high strength, high elastic modulus and high melting point. Nothing is known so far about fibers and the technology for producing them efficiently.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems, (1) to provide a polyketone fiber colored at the stage of a raw yarn, and (2) to prevent aggregation of a coloring substance.
To provide a polyketone fiber having excellent mechanical properties such as high spinnability and stretchability, high strength and high elastic modulus, and (3) dyeing an achromatic or chromatically colored polyketone fiber for a long time. It is an object of the present invention to provide an efficient and highly productive method without performing a cleaning process and a waste liquid process.

[0010]

In order to achieve the above object, the inventors of the present invention investigated a method of finely dispersing a coloring substance inside the fiber before highly crystallizing in the wet spinning method of polyketone, 1) by adding the coloring substance to the solvent before dissolving the polyketone without agglomerating, or 2) adding the coloring substance in the form of fine particles or solution to the polyketone fiber which is solidified in the coagulation bath and swollen. The inventors have found that there is a possibility of industrially producing colored polyketone fibers having high strength and high elastic modulus, and completed the present invention.

That is, the present invention is as follows. (1) A polyketone fiber composed of a polyketone in which 95 to 100% by mass of the repeating unit is 1-oxotrimethylene, containing 0.1 to 10% by mass of a dye and / or a pigment based on the polyketone fiber. The average particle diameter of the dye and / or pigment fine particles in the fiber is 2 μm or less, and the number of coarse particles having the longest length of the fine particles of 5 μm or more is 3 or less per 10000 μm ^{2 of} fiber cross section. Characteristic polyketone fiber. (2) Dye and / or pigment fine particles have an average particle size of 1 μm
The number of coarse particles having a length of 5 μm or more is 1 per 10,000 μm ^{2 of} fiber cross section.
The polyketone fiber according to (1), wherein the number of the polyketone fibers is not more than one.

(3) The crystallinity of the polyketone fiber is 70%
As described above, the crystal orientation degree is 95% or more, and the melting point is 260 ° C.
It is above, The polyketone fiber as described in (1) or (2) characterized by the above-mentioned. (4) Tensile strength of polyketone fiber is 10 cN / dt
Ex or more and tensile elastic modulus of 250 cN / dte
It is x or more, The polyketone fiber as described in any one of (1)-(3). (5) It contains 0.02 to 5 mass% of an ultraviolet absorber and a hindered amine-based light stabilizer with respect to the polyketone fiber, and the mass ratio of the ultraviolet absorber and the hindered amine-based light stabilizer is 1: 1 to 1: 5. Characterized by being (1)-
The polyketone fiber according to any one of (4).

(6) 95-100% by mass of the repeating unit
Polyketone fiber comprising a step of dissolving a polyketone consisting of 1-oxotrimethylene in a solvent containing 10 to 80% by mass of zinc halide to produce a dope, and extruding the dope into a coagulating bath through a spinneret to solidify the dope. In the method for producing, a zinc halide solvent containing a dye and / or a pigment dispersed in an average particle size of 2 μm or less is prepared, and subsequently, the polyketone is dissolved in a solvent containing zinc halide to form a dope, This dope has an average pore size of 5
A process for producing a polyketone fiber, which comprises passing one or more stages of a filtration layer of -50 μm and then extruding it through a spinneret into a coagulation bath. (7) A polyketone containing 95 to 100% by mass of the repeating unit of 1-oxotrimethylene is used as a zinc halide.
In a method for producing a polyketone fiber, which comprises a step of dissolving in a solution containing 0 to 80% by mass to produce a dope, extruding the dope through a spinneret into a coagulation bath to solidify the dope, followed by washing, drying and stretching. In any one of the steps of coagulation, washing, and drying, a liquid containing a dye and / or pigment dispersed in an average particle size of 2 μm or less is applied in a state where the swelling degree of the polyketone fiber is 10% by mass or more. A method for producing a polyketone fiber, which comprises:

The polyketone fiber of the present invention comprises 95 to 100% by mass, preferably 97% by mass or more, and more preferably 100% by mass of the repeating unit represented by the chemical formula (1). Is a fiber.

[0015]

[Chemical 1]

The higher the proportion of 1-oxotrimethylene in the repeating unit, the more regular the molecular chains are, resulting in highly crystalline and highly oriented fibers, resulting in high strength, high elastic modulus and high heat resistance. A high-performance polyketone fiber having properties is obtained. Within the range of less than 5% by mass, there may be a component obtained by copolymerizing carbon monoxide and a compound other than ethylene, for example, an olefin such as propene or hexene, or styrene. The polyketone fiber of the present invention contains a dye and / or a pigment in an amount of 0.1 to 10% by mass based on the polyketone fiber.

In the present invention, the dye is the dyeing and processing of chemical fiber, edited by The Society of Polymer Science, Jichijin Shokan Publishing, p. As defined in 4, means an organic compound that strongly absorbs visible light, even if it is colorless by itself,
Dyes include those which form a main body which exhibits similar properties by being combined with other dyes. The dye that can be used in the present invention is not limited, for example, known dyes such as acid dyes, cationic dyes, direct dyes, sulfur dyes, mordant dyes, vat dyes, azoic dyes, reactive dyes, fluorescent white dyes and disperse dyes. Examples include dyes. Dispersibility in the polyketone fiber, heat resistance of the dye during hot drawing, from the viewpoint of the mechanical properties of the resulting polyketone fiber and the fastness of dyeing, direct dye, mordant dye, vat dye, azoic dye and disperse dye are preferable, Disperse dyes are more preferred. Specific examples of the dye include a benzine-based azo dye as a direct dye, an anthraquinone-based vat dye as a vat dye, and an azo dye as a disperse dye.

In the present invention, the term “pigment” refers to “Pigment Handbook” edited by Japan Pigment Technology Association, published by Seibundo Shinkosha p. As defined in No. 1, it is an inorganic or organic compound in the form of colored fine particles, which is insoluble in water or a solvent, and is mixed with a color-developing agent to give a color to a coating film or a molded product. The pigment used in the present invention is not limited, and examples thereof include known pigments such as chromatic pigments, fluorescent pigments, metal powder pigments, black pigments, white pigments and extender pigments. Specific examples of pigments include yellow iron oxide (red iron oxide) and cobalt blue as chromatic pigments.
Examples of the fluorescent pigment include a daylight fluorescent pigment, aluminum powder as a metal powder pigment, carbon black and graphite as a black pigment, titanium oxide as a white pigment, and silica as an extender pigment.

In the present specification, the dye and the pigment may be collectively referred to as a coloring substance. The polyketone fiber of the present invention may contain a plurality of types of dyes or a plurality of types of pigments, or a mixture of dyes and pigments. It is important that the ratio of the coloring substance contained in the polyketone fiber is 0.1 to 10 mass% with respect to the polyketone fiber, preferably 0.2 to 5 mass%, more preferably 0.3 to 2 mass%. %. Coloring material ratio is 0.1
When the content is less than mass%, it becomes difficult to obtain a polyketone fiber having sufficient color developability. In addition, the ratio of coloring substances is 1
If it exceeds 0% by mass, the presence of a coloring substance greatly reduces the physical properties of the polyketone fiber, particularly the strength.

The coloring substance exists as a foreign substance in the polyketone fiber, and depending on the form of the foreign substance, the physical properties of the fiber may be impaired even in a small amount. In particular, when the coloring substance is aggregated in the fiber and exists as coarse particles, the strength is greatly reduced. Therefore, the average particle size of the coloring substance in the polyketone fiber needs to be 2 μm or less, and preferably 1 μm or less.
It is less than or equal to μm, and more preferably less than or equal to 0.1 μm. Even if the average particle size is small, the fiber strength is greatly impaired by a very small number of coarse aggregates. Therefore, the number of coarse particles having the longest length of the coloring substance particles in the fiber of 5 μm or more is 10000 μm ^{2 of} polyketone fiber. It is necessary to be 3 or less per 1 μm ² , preferably 1 or less per 10000 μm ² , and most preferably 0 per 10000 μm ² .

In order to widely utilize the polyketone fiber of the present invention for industrial materials such as ropes and sewing threads, it is desired that it has excellent mechanical properties. For that purpose, the polyketone fiber preferably has a crystallinity of 60% or more and a crystal orientation of 90% or more, more preferably a crystallinity of 70%.
As described above, the crystal orientation degree is 95% or more. The polyketone fiber preferably has a high melting point, high strength, and high elastic modulus. Specifically, the melting point is preferably 255 ° C. or higher, more preferably 260 ° C. or higher. The tensile strength is preferably 7 cN / dtex or more, more preferably 10 cN / dtex or more,
Most preferably, it is 12 cN / dtex or more. The tensile elastic modulus is preferably 200 cN / dtex or more, more preferably 250 cN / dtex, and most preferably 300 cN / dtex or more.

The polyketone fiber may be in the form of long fiber or short fiber. In the case of long fibers, it may be either a multifilament or a monofilament, and may be processed by crimping or false twisting. The fineness is not limited, but the single yarn fineness is 0.5 to 10d
The tex and total fineness are preferably 50 to 10,000 dtex. The cross-sectional shape of the fiber is also not limited, and can be any shape such as circular, elliptical, rectangular, triangular, and alphabetical.

In the polyketone fiber of the present invention, if necessary, various additives such as a heat stabilizer, a defoaming agent, a color stabilizer, a flame retardant, an antioxidant, an ultraviolet absorber, an infrared absorber, A crystal nucleating agent, an oil agent, a surfactant and the like may be contained. When a dye or an organic pigment is used as the coloring substance, it is preferable to include an ultraviolet absorber and a hindered amine light stabilizer from the viewpoint of light fastness. The ultraviolet absorber that can be used in the present invention is not limited, and examples thereof include benzophenone compounds, benzotriazole compounds, triazine compounds, oxalic acid anilide compounds, cyanoacrylate compounds paraaminobenzoic acid, salicylic acid compounds, and cinnamic acid. Known compounds such as system compounds can be used. The proportion of these ultraviolet absorbers is preferably 0.01 to 3 mass% with respect to the polyketone fiber. As the hindered amine light stabilizer, known compounds such as Adeka Stab (registered trademark, manufactured by Asahi Denka Co., Ltd.) LA-77, Tinuvin (registered trademark, manufactured by Ciba Specialty Chemicals Co., Ltd.) 144, and the like can be used. The amount of the hindered amine light stabilizer is preferably 0.01 to 3% by mass based on the polyketone fiber.

A plurality of these stabilizers may be blended and used. It is preferable to use an ultraviolet absorber and a hindered amine light stabilizer in combination. In this case, the mass ratio of the ultraviolet absorber: the hindered amine light stabilizer is preferably 1: 1 to 1: 5, and the total of both is preferably 0.02 to 5 mass% with respect to the polyketone fiber. .

Next, the method for producing the polyketone fiber of the present invention will be described. The polyketone fiber of the present invention is produced using a dope in which a polyketone is dissolved in a solvent. The polyketone used in the present invention has a repeating unit of 95 to 100.
The mass% is 1-oxotrimethylene, and the intrinsic viscosity is preferably 2 to 10 in view of spinnability and drawability, mechanical properties of the resulting polyketone fiber, and the like in the production. As the solvent for the polyketone, known organic solvents and inorganic solvents can be used, but a metal salt solution is preferable from the viewpoint of solvent toxicity, safety, recovery cost, and physical properties of the obtained fiber. Examples of the metal salt solution include a solution containing zinc halide, an alkali metal halide, an alkaline earth metal halide, and the like, and a solution containing 10 to 80% by mass of zinc halide (for example, zinc chloride / Calcium chloride / water = 23/40/37 aqueous solution) is preferably used. Add polyketone to this solution 6
A dope is obtained by heating and stirring at 0 to 150 ° C. to dissolve the polyketone.

In the wet spinning method using a metal salt solution, in order to obtain a polyketone fiber in which the coloring substance of the present invention is present in a finely dispersed state, the coloring substance is dispersed in an average particle size in any step from the dissolution to the stretching. It is necessary to add it in a state where the diameter is 2 μm or less. The addition position of the coloring material is
(1) Addition in the dope preparation step, (2) Addition in any step of coagulation, washing and drying steps, or (3)
It is preferable to add in both steps (1) and (2). (1) Addition in the dope preparation step In the case of addition in the dope preparation step, when coarse particles are present due to aggregation of the coloring matter in the dope or when the average particle diameter of the coloring matter is large, the physical properties of the obtained polyketone fiber In addition to the above-mentioned deterioration, the filter clogging during spinning, ejection failure, and yarn breakage occur, and the process passability is greatly impaired.
Therefore, when a coloring substance is added to the dope, it is important to finely disperse the coloring substance. Specifically, the average particle diameter of the coloring substance in the dope is 2 μm or less, preferably 1 μm or less.
The length of the longest part of the fine particles is 5 μm or more, and coarse particles having a length of 5 μm or more are used in the fiber cross section of 10,000 μm ²
It is important that the number is 3 or less, preferably 1 or less, and more preferably 0.

When the coloring substance is finely dispersed in the dope, a method in which the coloring substance is added after the dope is once prepared tends to form aggregates, and the polyketone may be insolubilized and deposited. To prevent this, (a)
The method of dispersing the coloring substance in the metal salt solvent or the method of adding the mixture of (b) polyketone and the coloring substance to the metal salt solvent is preferable, and the method (a) is more preferable from the viewpoint of dispersibility and productivity. The addition amount of the coloring substance at this time is 0.1 to 10% by mass with respect to the polyketone.

In the method (a), it is preferable to finely disperse the coloring substance in a solution in which the metal salt is dissolved (water when the metal salt aqueous solution is used as a solvent) to an average particle size of 2 μm or less in advance. A dope having dispersibility can be efficiently obtained. In this case, if necessary, the surface of the colored substance may be made hydrophilic by using a surface treatment agent (hydrophilization in the case of an aqueous solution), or a surfactant may be added to improve the dispersibility and to agglomerate the particles. And the colorant is finely dispersed to an average particle size of 2 μm or less, and the number of coarse particles having the longest length of the fine particles of 5 μm or more is 10000 μm in the fiber cross section.
It can be 3 or less per ² and more preferably 0.

Examples of the surface treatment agent include known compounds such as silane coupling agent, titanium coupling agent, zirconium coupling agent, aluminum coupling agent, and the like, and surfactants include known anionic surfactants, A cationic surfactant, an amphoteric surfactant, a nonionic surfactant, etc. can be used. When a surfactant is used, the amount of the surfactant used is 0.
1 to 5 mass% is preferable.

As the coloring substance, a substance soluble in a metal salt solvent may be used. For example, when a water-soluble dye is used in a metal salt aqueous solution solvent, a dope in which the coloring substance is uniformly finely dispersed is used. Is preferred, which is preferable.
The polyketone dope thus obtained is discharged into the coagulation bath from the spinneret into a fibrous form, and then the metal salt is washed off with an acid aqueous solution such as hydrochloric acid, and then dried to remove the liquid in the polyketone fiber. To do. At this time, coarse particles and agglomerated particles can be removed in advance through one or more steps of filtration before being discharged from the spinneret. Although there is no limitation on the method of filtration, the number of coarse particles having a longest length of fine particles of 5 μm or more per 10000 μm ^{2 of} fiber cross section can be obtained by passing one or more stages through a filtration layer having an average pore size of 5 to 50 μm. Three
The number can be less than or equal to 0, more preferably 0.

(2) Addition in Coagulation Step, Washing Step, and Drying Step The present inventors have found that the polyketone fiber that has become fibrous in the coagulation bath is swollen with about 2 to 6 times the solution of polyketone. It was found that, when the coloring substance is applied at the stage where the polyketone is swollen, the coloring substance is easily dispersed and penetrated into the fiber at room temperature and normal pressure. According to this method, it is possible to switch between the production of various colored fibers and the production of non-colored fibers without replacing the dissolver, the extrusion device, the spinneret, etc., and the productivity is extremely higher than that of the method (1). It is a high and excellent method.

In this method, the swelling degree of the polyketone fiber and the dispersibility of the coloring substance are important in order to efficiently and promptly add the coloring substance to the fiber. The degree of swelling of the polyketone fiber is a value obtained by the method described below, and is a percentage of the ratio of (liquid amount / polyketone fiber amount) in the polyketone fiber swollen with a liquid. The degree of swelling of the polyketone fiber when applying the coloring substance is preferably 10% by mass or more, more preferably 50% by mass or more, and most preferably 100% by mass or more. Swelling degree is 10% by mass
If it is less than the above, the permeation rate of the coloring substance into the fiber becomes slow, and it becomes difficult to efficiently produce the colored fiber.

In order to quickly add the coloring substance to the swollen polyketone fiber, it is preferable to dissolve or disperse the coloring substance in a liquid having a good affinity with the liquid in which the polyketone fiber is swollen. For example, when the polyketone fiber is swollen with water, a method of adding a coloring substance as a solution, an emulsion or a suspension to a hydrophilic solvent such as water, methanol or acetone can be mentioned. At this time, the addition ratio of the coloring substance is 0.1 to 10 relative to the polyketone fiber.
It needs to be mass%.

The average particle diameter of the coloring substance in the liquid to which the coloring substance is added is 2 μm or less, and the number of coarse particles having a length of 5 μm or more is 3 or less, preferably 0, per 10000 μm ^{2 of the} fiber cross section. As such, it is particularly important to disperse the coloring material with a surfactant. When the coloring substance is dispersed using a surfactant, the total amount of the surfactant added is preferably 2% by mass based on the polyketone fiber from the viewpoints of stretchability and strength of the resulting polyketone fiber.
Hereafter, it is more preferably 0.5% by mass or less. Also,
If necessary, the liquid to be added has an average pore size of 5 to 50 μm.
The number of coarse particles is 10,000 in cross section through the filtration layer of m.
The number can be 3 or less, preferably 0 per μm ² .

The polyketone fiber containing the coloring substance thus obtained is dried and drawn. The drying method is not limited, but in order to obtain a polyketone fiber having high crystallinity and high strength, the drying condition is 100 to 260 ° C.
Treatment for 0 to 120 seconds is preferable, 160 to 240 ° C., 1
5 to 60 seconds is more preferable. Furthermore, 200-
Hot drawing is performed at a temperature of 280 ° C. for a factor of 5 or more. From the viewpoint of the crystal structure, melting point and fiber physical properties of the obtained polyketone fiber, it is preferable to set the total draw ratio to 10 times or more, more preferably 12 times or more, and to perform multi-step drawing of two or more steps. When performing multi-stage stretching, it is desirable to gradually increase the stretching temperature as the number of stretching stages increases.

[0036]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described by way of Examples, which do not limit the scope of the present invention. The measuring method of each measured value used in the present invention is as follows. (1) Intrinsic viscosity Intrinsic viscosity [η] is a value obtained based on the following defining equation. In the definition formula, t and T are the passage times of a viscous tube at 25 ° C. of hexafluoroisopropanol having a purity of 98% or more and a dilute solution of polyketone dissolved in hexafluoroisopropanol. C is the solute mass value in grams in 100 ml above.

[0037] (2) the composition ¹ H-NMR method polyketone determine the amount ratio of 1-oxo-trimethylene group. (3) Content of coloring substance in polyketone fiber 3-A: Dye 0.1 g of hexafluoroisopropanol 100
After dissolving in ml, acetone was added, the absorbance of the solution diluted to a predetermined concentration was A, and 1.0 g of polyketone fiber was dissolved in 100 ml of hexafluoroisopropanol,
Absorbance a of a solution added with acetone and diluted to a predetermined concentration
Is determined from a spectrophotometer (V-530, manufactured by JASCO Corporation), and (a / A) / 10 is defined as the dye content rate. For the absorbance, the value at the maximum absorption wavelength of the dye (for the dye used in the examples, the value at 580 nm) is adopted. 3-B: Pigment By high frequency plasma emission spectroscopy, the amount of the pigment element in the fiber is measured by a known method. In the examples, the amount of Ti element was measured.

(4) The crystallinity differential thermal analyzer Pyris1 (trademark) (manufactured by Perkin Elmer Co., Ltd.) is used for the measurement under the following conditions. A fiber obtained by cutting the yarn length to 5 mm is used as a sample. Mass of sample: 1 mg Measurement temperature: 30 ° C. → 300 ° C. Temperature rising rate: 20 ° C./min Atmosphere: Nitrogen, flow rate = 200 mL / min In the obtained endothermic curve, the maximum observed in the range of 200 to 300 ° C. The crystallinity is calculated by the following formula using the heat quantity ΔH (J / g) calculated from the area of the endothermic peak. Crystallinity = (ΔH / 225) × 100 (%)

(5) Crystal orientation degree Imaging plate X-ray diffractometer manufactured by Rigaku Corporation,
RINT (registered trademark) 2000 is used to capture the diffraction image of the fiber under the following conditions: X-ray source: CuKα ray output: 40 KV 152 mA Camera length: 94.5 mm Measurement time: 3 minutes 2θ = 21 ° of the obtained image Observed nearby (11
The degree of crystal orientation is calculated from the half width H of the intensity distribution obtained by scanning the 0) plane in the circumferential direction by the following formula. Crystal orientation degree = [(180−H) / 180] × 100 (%)

(6) Melting point The melting point is the peak top temperature of the maximum endothermic peak observed in the range of 200 to 300 ° C. in the endothermic curve obtained in (4). (7) Tensile strength and tensile elastic modulus It is measured based on JIS-L-1013. As the elastic modulus, the value of the initial elastic modulus calculated from the load at the elongation of 0.1% and the load at the elongation of 0.2% is adopted.

(8) Swelling degree Polyketone fiber is centrifuged (KOKUSAN-H-2).
00 (trademark), manufactured by Domestic Centrifuge Co., Ltd. 450
Centrifugal dehydration is carried out at 0 rpm for 10 minutes to remove the liquid component adhering to the fiber surface or between the fibers. 10 of this polyketone fiber
Dry at 5 ° C. for 5 hours to remove the liquid content inside the fiber. The degree of swelling is calculated from the following formula, where the weights of the fibers before and after drying are Ma and Md, respectively. Swelling degree = [(Ma-Md) / Md] x 100 (%)

(9) Average Particle Size of Coloring Substance in Fiber Polyketone fiber is dipped in liquid nitrogen and cut in a cooled state to prepare a longitudinal section of the fiber. The sample is treated with osmium tetroxide. Electron microscope (JEM2000F
X (trademark) manufactured by JEOL Ltd.) is used to take a photograph (image) of the obtained section at a magnification of 500 to 50,000. An image analysis device (IP1000-
It is measured by the following method using PC (trademark), manufactured by Asahi Kasei Corporation. Use a scanner (JX-330 (trademark), manufactured by Sharp Corporation) to print a negative image in black and white 256
Capture with gradation (gamma correction value is 2.2). The capture area is selected according to the photographing magnification. Binarization processing is performed on the captured 256 gradation image. Particle analysis of the obtained binarized image is performed to determine the equivalent circle diameter of the colored substance. After measuring 5 fields of view, an arithmetic average value is calculated for the measured circle-equivalent diameters of all colored substances to obtain an average particle diameter.

(10) A photograph of 100 μm squares of coarse particles in the fiber is made into a binarized image by the apparatus and method of (9), particle analysis is performed to find the maximum length of each particle, and the maximum length is 5 μm or more. Measure the number of coarse particles. At the same time, the fiber cross-sectional area measured in each image is calculated, and the fiber cross-sectional area is 10,000
If it is less than μm ² , the measured fiber cross-sectional area is 10
The measurement is performed on a plurality of images until it becomes 000 μm ² or more. The sum of the number of particles having a maximum length of 5 μm or more measured from all images is N and the sum of the fiber cross-sectional areas is S (μm ² ), and the number of coarse particles per 10,000 μm ² is calculated by the following formula. (N / S) × 10000 (pieces / 10,000 μm ² )

(11) Stabilizer content in fiber Determined from the peak area ratio of polyketone and stabilizer by the ¹ H-NMR method.

[0045]

Example 1 By a conventional method, 100% by mass of the repeating unit was used.
A polyketone having an intrinsic viscosity of 5.9 in which is 1-oxotrimethylene was prepared. This polyketone was added to an aqueous solution containing 40% by mass of calcium chloride / 22% by mass of zinc chloride to obtain a dope having a polymer concentration of 6.8% by mass. The obtained dope was discharged from a spinneret having 50 holes into a coagulation bath made of water at −2 ° C. containing 2% by mass of calcium chloride, 1.1% by mass of zinc chloride and 0.1% by mass of hydrochloric acid. Sequentially, swelling degree 380
% Polyketone fiber was produced. This swollen polyketone fiber was impregnated with an acetone solution of a disperse dye [Kayaron (registered trademark) Polyester Blue 3R-SF (manufactured by Nippon Kayaku Co., Ltd.)] in an amount of 0.3% by mass (to polyketone),
Subsequently, stabilizers [antioxidants: IRGANOX (registered trademark), 565 (manufactured by Ciba Specialty Chemicals), Adeka Stab (registered trademark), AO23 (manufactured by Asahi Denka Co., Ltd.), UV absorbers: Adeka Stab (registered trademark) , LA31 (manufactured by Asahi Denka Co., Ltd.), hindered amine light stabilizer: ADEKA STAB (registered trademark, LA-63P)
(Manufactured by Asahi Denka Co., Ltd.) is 0.025 / 0.025 / 0.
1 / 0.2 mass% (to polyketone) dissolved solution], and after washing with water, continue at 1 at 225 ° C.
Dry for a fixed length of time. 225 ℃ / 240 ℃ /
7.0 / 1.5 / 1.3 at 253 ° C / 257 ° C, respectively
Multi-stage stretching of /1.25 times was performed.

The proportion of dye in the polyketone fiber is 0.27
% By mass, the average particle diameter of the dye was 0.01 μm or less (no particulate matter was observed by an electron microscope), and coarse particles having a length of 5 μm or more were not observed. The fiber had a blue hue. The crystallinity of the fiber is 80.1%, the crystal orientation is 9
It was 7.2%. The fiber has a melting point of 268 ° C., a strength of 14.6 cN / dtex, and an elastic modulus of 377 cN / dte.
x, and had very excellent physical properties. Tables 1 and 2 collectively show the coloring state, structure and characteristics of the polyketone fiber in Example 1 and the examples and comparative examples described below.

[0047]

Example 2 The amount of disperse dye added in Example 1 was 2
Spinning in the same manner except that the mass% (vs. polyketone),
It was dried and stretched. The dye content of this polyketone fiber was 1.8% by mass, the average particle size was 0.02 μm, and the color tone was dark blue. The crystallinity of this fiber was 77%, and the crystal orientation was 97.0%. The melting point of the fiber is 266
℃, strength 10.2cN / dtex, elastic modulus 345c
It was N / dtex and had excellent physical properties.

[0048]

Example 3 A white pigment (Kronos KA-35 (trademark), manufactured by Titanium Industry Co., Ltd.) composed of titanium dioxide fine particles having an average particle size of 0.3 μm was dispersed in water at a concentration of 4% by mass (titanium). Dispersed water). Calcium chloride and zinc chloride were added to this dispersion to prepare an aqueous solution containing 40% by mass of calcium chloride / 22% by mass of zinc chloride / 38% by mass of titanium-dispersed water. The polyketone prepared in Example 1 was added to this aqueous metal salt solution to give a concentration of 6.8% by mass to prepare a dope. The dispersibility of the titanium dioxide fine particles in the dope was good, and when this dope was filtered through a 20 μm sintered filter, neither filter clogging nor increase in filtration pressure was observed.

The filtered dope was coagulated and washed in the same manner as in Example 1 to obtain swollen polyketone fiber. Stabilizer [antioxidant: IRG
ANOX (registered trademark) 565, manufactured by Ciba Specialty Chemicals Co., Ltd.] and ADEKA STAB (registered trademark) AO
23, manufactured by Asahi Denka Co., Ltd.] in a proportion of 0.025 / 0.025 mass% (relative to polyketone)] was impregnated and subsequently dried at a temperature of 225 ° C. for a fixed length of 1 minute.
This fiber was subjected to multi-stage drawing at 225 ° C / 240 ° C / 253 ° C / 257 ° C by 7.0 / 1.5 / 1.3 / 1.25 times, respectively.

The polyketone fiber thus obtained had a pigment content of 0.25% by mass and an average particle diameter of 0.5 μm, and had a high whiteness. The crystallinity of the fiber was 79.1%, and the crystal orientation was 97.0%. The melting point of the fiber is 26
6 ° C, strength 11.5 cN / dtex, elastic modulus 355
It was cN / dtex, and had excellent physical properties.

[0051]

Comparative Example 1 Spinning, drying and stretching were carried out in the same manner as in Example 1 except that the addition ratio of the dye was 15% by mass based on the polyketone fiber. This fiber was poor in drawability and could not be drawn twice or more at 225 ° C. in the first stage. The polyketone fiber obtained by stretching 1.8 times has a strength of 1.3 cN / dtex and an elastic modulus of 35 c.
It was N / dtex, and a fiber having practical performance could not be obtained. When observing the cross section of this fiber with an electron microscope, a large number of aggregates of dyes were confirmed, and the number of coarse particles having a length of 5 μm or more was 3.3 / 10,000.
It was out of the range of the present invention, which was μm ² .

[0052]

Comparative Example 2 Spinning, drying and drawing were performed in the same manner as in Example 1 except that the ultraviolet absorbent, the hindered amine light stabilizer and the disperse dye were not added to the swollen thread after washing. The crystallinity of the obtained polyketone fiber is 80.3.
%, The degree of crystal orientation was 97.8%, and the fiber had a developed structure. The polyketone fiber was dyed with a dyeing solution having the following composition at 120 ° C. for 40 minutes. After dyeing, 4
The dye on the fiber surface was washed off with warm water at 0 ° C. for 10 minutes.

(Dyeing liquid composition) Dye: Kayaron (registered trademark) Polyester Blue 3RSF, manufactured by Nippon Kayaku Co., Ltd., dye owf: 4%, bath ratio: 1:50, dispersant: Nikkasan Salt (registered trademark) ) 7,000, manufactured by Nichika Chemical Co., Ltd., dispersant concentration: 0.5 g / liter, acetic acid 0.25 m
1 / l, sodium acetate 1 g / l. Although the obtained polyketone fiber was bluish, its color tone was insufficient as compared with the fibers obtained in Examples 1 and 2. The proportion of dye in this fiber is 0.05
It was out of the range of the present invention in terms of mass%.

[0054]

Comparative Example 3 The dope was prepared by dissolving polyketone at a concentration of 6.8% by mass in an aqueous solution containing 40% by mass of calcium chloride / 22% by mass of zinc chloride / 38% by mass of water. The spinning was performed in the same manner except that a white pigment having an average particle diameter of 0.3 μm was added to the product in an amount of 4% by mass with respect to water. It was observed that the dispersibility of the white pigment was poor, and that aggregated particles remained in the dope even after stirring for 2 hours.
The obtained dope was filtered through a 20 μm sintered filter,
Subsequently, spinning was performed in the same manner as in Example 1. The spinnability was poor, the discharge pressure increased after the start of discharge, frequent yarn breakage occurred, and continuous spinning was difficult, and fibers could not be obtained. The thread that solidified and settled in the coagulation bath,
After washing with hydrochloric acid and water and drying at 100 ° C for 10 minutes,
When the fiber cross section was observed with a microscope, the average particle size of the white pigment was 4.5 μm, and the number of coarse particles was 5.2 particles / 10000 μ.
m ² was out of the range of the present invention.

[0055]

Comparative Example 4 Spinning, drying and stretching were carried out in the same manner as in Example 1 except that the dye solution was applied after the polyketone fiber was dried (swelling degree 0.2%). Although the obtained polyketone fiber was apparently colored, the color was completely lost by light washing with water, and the fiber became uncolored.

[0056]

[Table 1]

[0057]

[Table 2]

[0058]

INDUSTRIAL APPLICABILITY The polyketone fiber of the present invention is colored in an achromatic color or a chromatic color, and is a fiber having excellent productivity because it does not require dyeing treatment, washing treatment or waste liquid treatment for a long time. In addition, it has excellent properties such as high strength, high elastic modulus, and high melting point, and is required for colored fibers having high strength (industrial fabrics, industrial nonwoven fabrics, ropes, fishing nets, industrial sewing threads, fishing lines, It is extremely useful for spun yarn, etc.).

Continued front page    F-term (reference) 4L035 AA04 AA06 BB03 BB06 BB10                       BB17 BB59 BB66 BB69 BB76                       BB81 BB89 BB94 EE01 EE08                       EE09 EE20 HH10 JJ10 JJ19                       JJ28 KK01 KK05                 4L038 AA14 AB07 AB09 BA25 BB02                       BB05 DA10

Claims (7)

[Claims] 1. 95 to 100% by weight of the repeating unit is 1
A polyketone fiber composed of a polyketone which is oxotrimethylene, containing 0.1 to 10% by mass of a dye and / or a pigment with respect to the polyketone fiber, and having an average particle size of dye and / or pigment fine particles in the fiber. Diameter is 2 μm
The number of coarse particles in which the length of the longest part of the fine particles is 5 μm or more is 3 or less per 10,000 μm ^{2 of the} fiber cross section. Wherein the average particle size of the dye and / or pigment particles is not more 1μm or less, the number is the fiber cross-section of the longest portion of the length 5μm or more coarse particles fine particles 10000 ²
The polyketone fiber according to claim 1, wherein the number of the polyketone fibers is 1 or less. 3. The polyketone fiber according to claim 1, wherein the polyketone fiber has a crystallinity of 70% or more, a crystal orientation of 95% or more, and a melting point of 260 ° C. or more. 4. The tensile strength of the polyketone fiber is 10c.
N / dtex or more and tensile elastic modulus is 250 cN
/ Dtex or more, The polyketone fiber according to any one of claims 1 to 3, which is characterized in that. 5. A polyketone fiber containing 0.02 to 5% by mass of an ultraviolet absorber and a hindered amine light stabilizer, and the mass ratio of the ultraviolet absorber and the hindered amine light stabilizer is 1: 1 to 1: 1. 5. The polyketone fiber according to claim 1, wherein the polyketone fiber is 5. 6. 95 to 100% by weight of the repeating unit is 1
-Production of polyketone fiber comprising a step of dissolving a polyketone composed of oxotrimethylene in a solvent containing 10 to 80% by mass of zinc halide to produce a dope, and extruding the dope into a coagulating bath through a spinneret to solidify the dope. In the method, a zinc halide solvent containing a dye and / or pigment dispersed in an average particle size of 2 μm or less is prepared, and then the above polyketone is dissolved in a solvent containing zinc halide to prepare a dope. The average pore size is 5 to 5
A method for producing a polyketone fiber, which comprises passing one or more stages of a filter layer of 0 μm and then extruding it into a coagulation bath from a spinneret. 7. 95 to 100% by weight of the repeating unit is 1
-A polyketone consisting of oxotrimethylene was dissolved in a solution containing 10 to 80% by mass of zinc halide to produce a dope, which was extruded from a spinneret into a coagulating bath to solidify, followed by washing and drying. In a method for producing a polyketone fiber including a step of drawing later, the degree of swelling of the polyketone fiber is 1 in any of the steps of coagulation, washing and drying.
A process for producing a polyketone fiber, which comprises applying a liquid containing a dye and / or a pigment dispersed in an average particle size of 2 μm or less in an amount of 0% by mass or more.