JP2015132039A - polymethylpentene fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymethylpentene fiber that has excellent resistance to oxidation heat generation, does not harm the lightness, water repellancy and heat resistance of the polymethylpentene fiber, and can be suitably adopted as clothing material and has excellent in color tone.SOLUTION: A polymethylpentene fiber has an oxidation induction time (OIT) of 4 minutes or more, and bvalue in Labcolor system in the range of -3 to 3.

Description

  The present invention relates to a polymethylpentene fiber that can be suitably used as a clothing material. More specifically, the present invention relates to a polymethylpentene fiber that is improved in color tone, particularly yellowness, while suppressing oxidation heat generation, and can be suitably used as a clothing material.

  Polypropylene, which is a kind of polyolefin-based polymer, is excellent in light weight, water repellency and chemical resistance, but has a low melting point and a disadvantage of low heat resistance. Therefore, when it is made into a fiber, it cannot be used under high temperature, such as being unable to use an iron, and its use as a clothing material is limited. Polypropylene fiber, which is one of the representative examples of polyolefin fibers, has a phenomenon (oxidation exothermic phenomenon) in which fiber components are oxidized by oxygen in the air and heat is generated. Especially for mixed products of polypropylene fiber and cellulosic fibers (cotton, hemp, rayon, cupra, acetate, etc.), if they are exposed to long-term treatment at high temperatures, such as clothes dryers, cellulose-based materials such as cotton that are used in combination Heat also moves and accumulates in the fibers, which may cause deterioration. Therefore, it is extremely important to suppress this oxidation heat generation phenomenon when developing clothing products for a wide range of uses with polyolefin fibers from the viewpoint of product quality when subjected to long-time treatment at high temperatures, especially in terms of color tone. is there.

  On the other hand, polymethylpentene is mentioned as a polyolefin-based polymer that is light and water-repellent like polypropylene, and has a lower specific gravity than polypropylene and is extremely lightweight. In addition, since the melting point and softening point are higher than other polyolefins, and the heat resistance is excellent, the fiber made of polymethylpentene can use an iron and can be used for a wide range of clothing applications.

  Since these polymethylpentene fibers are highly hydrophobic and difficult to dye, they are often colored by being used as clothing fibers. In that case, if the color tone of the underlying fiber is yellowish, it will affect the coloration of the light color in particular, resulting in a dull color, so polymethylpentene fibers with excellent color tone are required. ing.

  Patent Document 1 proposes a fiber made of polymethylpentene and a method for producing the same.

Japanese Patent Laid-Open No. 11-323657

  However, the above-mentioned Patent Document 1 is not intended to sufficiently prevent the oxidation exothermic phenomenon, and in order to develop as a textile fiber for a wide range of uses, it is a case where it is subjected to a long time treatment at a high temperature. There were problems with the color change and strength reduction of the product.

  Accordingly, an object of the present invention is to provide a polymethylpentene fiber that is excellent in oxidation heat resistance and improved in color tone that can be used in a wide range of applications as a textile fiber.

The above-described problem is caused by the polymethylpentene fiber characterized in that the oxidation induction time (OIT) is 4 minutes or more and the b ^* value in the L ^* a ^* b ^* color system is in the range of -3 to 3. Can be solved.

  ADVANTAGE OF THE INVENTION According to this invention, the polymethylpentene fiber which is excellent in a color tone and fiber strength can be provided, without impairing oxidation heat resistance.

An example of analysis of oxidation induction time (OIT) is shown.

  The polymethylpentene fiber of the present invention has an oxidation induction time (hereinafter abbreviated as OIT) measured by a method described later of 4 minutes or more.

  OIT is a value indicating the degree of oxidation heat resistance of the polymethylpentene fiber of the present invention. The larger the value, the better the oxidation heat resistance. The value of OIT can be calculated by analyzing polymethylpentene fibers with a differential thermal analyzer such as TG-DTA or DSC and analyzing the obtained results.

FIG. 1 is an example when calculating OIT of polymethylpentene fiber by TG-DTA. The polymethylpentene fiber is put in an aluminum container and heated with TG-DTA at a constant temperature increase rate in a nitrogen atmosphere until the sample temperature reaches 260 ° C. When the sample temperature reaches 260 ° C., the atmosphere is switched from nitrogen to air. The T ^1, the time required for the nitrogen atmosphere from the start warm to switch to air. The polymethylpentene fiber is kept heated at a sample temperature of 260 ° C. until the DTA (Differential Thermal Analysis) chart shown in FIG.

After the analysis is completed, the exothermic peak indicated by the DTA chart is analyzed. The analysis method draws a straight line overlapping the DTA chart before the exothermic peak occurs, and further draws an extension of the straight line. Next, with respect to the rise of the peak after the exothermic peak occurs, a straight line overlapping the rising DTA chart is drawn, and further, an extension line of the straight line is drawn. The time at the point where the two extended lines intersect is the time when the exothermic peak occurs. In addition, about the operation | work which calculates the time when this exothermic peak generate | occur | produced, it is also possible to perform the same operation | work with analysis software. The T ^2, the time at which exothermic peak takes to occur from the start heating. Time obtained by subtracting ^{T 1} from T ² is the OIT.

  The above test is a forced oxidation test of polymethylpentene fibers. The polymethylpentene fiber is forcibly induced to oxidize by heating the polymethylpentene fiber to the melting point or higher and exposing it to the air. If the polymethylpentene fiber is subjected to some kind of anti-oxidation technology, the heat generation due to the oxidation reaction is delayed, so the OIT is large and the oxidation resistance of the polymethylpentene fiber is excellent. Judgment can be made. In addition, setting the nitrogen atmosphere around the polymethylpentene fiber during heating until the target sample temperature is reached is carried out in order to suppress the oxidation reaction of the polymethylpentene fiber during temperature rise and accurately calculate OIT. doing.

  By setting the oxidation induction time (OIT) to 4 minutes or more, the oxidation heat generation of polyolefin during storage or dry heat drying is suppressed, so that coloring and deterioration of the fiber due to oxidation heat generation can be suppressed, and as a clothing material It can be used suitably. The higher the OIT, the better, preferably 5 minutes or more, more preferably 8 minutes or more, and even more preferably 10 minutes or more.

  An example of a method for controlling OIT includes a method of adding an antioxidant during production. It has been found that by using an appropriate amount of a specific antioxidant, the oxidation induction time can be greatly extended without impairing the properties required for clothing fibers, that is, the oxidation exothermic phenomenon can be suppressed, and the present invention has been achieved. did. In particular, various additives such as antioxidants significantly reduce the color tone and fiber strength when added in excess. However, by adding an appropriate amount of a specific antioxidant, it has important characteristics as a textile fiber. It has been found that the oxidation heat generation phenomenon can be suppressed without impairing a certain color tone or fiber strength.

  Examples of the antioxidant in the present invention include a phenolic antioxidant (hereinafter referred to as “A” as an abbreviation) having a phenol skeleton (not containing a nitrogen atom in the benzene ring) in the molecular structure, and a phosphorus atom in the molecular structure. A phosphorus-containing antioxidant (hereinafter, abbreviated as B agent), a high molecular weight hindered amine antioxidant (hereinafter abbreviated as 2,000 ° C.) having a triazine skeleton and a piperidyl group and having a molecular weight of 2000 or more and a 1 wt% weight loss temperature of 270 ° C. or more. C)) is preferred. In addition, some compounds have both a phenol skeleton and a phosphorus atom. In that case, the compounds are classified into phenolic antioxidants in the present invention. Preferred examples of the agent A [phenolic antioxidant] include ADEKA Adeka Stub AO-80, Sumitomo Chemical Sumilizer GA-80, and Sumilizer GP. Preferred examples of the B agent [phosphorus antioxidant] include Adeka Stab PEP36 manufactured by ADEKA, IRGAFOS 168 manufactured by BASF, and the like. Examples of suitable C agents [high molecular weight hindered amine antioxidants] include CHIMASSORB 944 and CHIMASSORB 2020 manufactured by BASF.

As these antioxidants, any one of Agent A and Agent B may be used, or two or more of Agent A, Agent B and Agent C may be used. The total amount of agent A, agent B, and agent C may be added in order to achieve the target OIT, but if added excessively, the mechanical properties of the fiber may be reduced, or the color tone b ^* In order to increase the value, it is preferably 3% by weight or less of the total weight of the polymethylpentene fiber. More preferably, it is 2 weight% or less, More preferably, it is 1 weight% or less, Most preferably, it is 0.5 weight% or less. At least the addition amount necessary to achieve the target OIT is 0.01% by weight or more. More preferably, it is 0.03 weight% or more, More preferably, it is 0.05 weight% or more.

In the polymethylpentene fiber of the present invention, the b ^* value in the L ^* a ^* b ^* color system measured by the method described later is in the range of -3 to 3. By setting the b ^* value within this range, a beautiful white color can be exhibited when used as a clothing material without being dyed. Further, since the polymethylpentene fiber may be colored by original deposition as described above, the b ^* value is more preferably in the range of −2 to 2, and when dyed with a light color, the value of −1 to 1 More preferably, it is in the range.

  The polymethylpentene fiber of the present invention contains at least one polymethylpentene resin. Examples of the polymethylpentene resin in the present invention include a 4-methyl-1-pentene polymer. Even if it is a homopolymer of 4-methyl-1-pentene, 4-methyl-1-pentene and others It may be a copolymer with an α-olefin. These other α-olefins (hereinafter referred to as α-olefins) can be copolymerized by one kind or two or more kinds.

  These α-olefins preferably have 2 to 20 carbon atoms, and the molecular chain of the α-olefin may be linear or branched. Specific examples of these α-olefins include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1 -Eicosene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 3-ethyl-1-hexene and the like.

  The polymethylpentene fiber in the present invention preferably contains 90% by weight or more of a polymethylpentene resin. If the polymethylpentene-based resin is 90% by weight or more, it is preferable because both the mechanical strength and light weight of the fiber can be achieved. More preferably, the polymethylpentene resin is contained in an amount of 93% by weight or more, and more preferably 95% by weight or more.

  The melting point of the polymethylpentene resin in the present invention is preferably 200 to 250 ° C. If the melting point of the polymethylpentene resin is 200 ° C. or higher, it is preferable because the heat resistance of the polymethylpentene fiber is improved. On the other hand, if the melting point of the polymethylpentene resin is 250 ° C. or lower, it is preferable because the spinning manipulability becomes good during melt spinning. The melting point of the polymethylpentene resin is more preferably 210 to 245 ° C, and further preferably 220 to 240 ° C.

  In the present invention, the melting point can be measured by the following method. The melting point of the polymethylpentene resin can be measured using a differential scanning calorimeter (DSC) (for example, a differential scanning calorimeter DSC7 manufactured by PerkinElmer). Specifically, in a nitrogen atmosphere, about 10 mg of the sample is heated from 30 ° C. to 280 ° C. at a rate of temperature increase of 15 ° C./min and then held at 280 ° C. for 3 minutes to remove the thermal history of the sample. Thereafter, the temperature was lowered from 280 ° C. to 30 ° C. at a temperature drop rate of 15 ° C./min and held at 30 ° C. for 3 minutes, and then the temperature was raised from 30 ° C. to 280 ° C. at a temperature rise rate of 15 ° C./min. The peak temperature of the endothermic peak observed during the process is defined as the melting point (° C.). The measurement is performed 3 times per sample, and the average value is taken as the melting point.

  The polymethylpentene resin in the present invention preferably has a melt flow rate (MFR) of 5 to 200 g / 10 minutes measured under conditions of a temperature of 260 ° C. and a load of 5.0 kg according to ASTM D1238 (Method B). . A melt flow rate of the polymethylpentene resin of 5 g / 10 min or more is preferable because of high heat fluidity and good moldability. On the other hand, when the melt flow rate of the polymethylpentene resin is 200 g / 10 min or less, polymethylpentene fibers having good mechanical properties can be obtained, which is preferable. The melt flow rate of the polymethylpentene resin is more preferably 10 to 190 g / 10 minutes, and further preferably 20 to 180 g / 10 minutes.

  The polymethylpentene resin in the present invention may have been subjected to various modifications by adding secondary additives. Specific examples of secondary additives include compatibilizers, plasticizers, UV absorbers, infrared absorbers, fluorescent brighteners, mold release agents, antibacterial agents, nucleating agents, thermal stabilizers, antioxidants, and charging Inhibitors, anti-coloring agents, regulators, matting agents, antifoaming agents, preservatives, gelling agents, latexes, fillers, inks, coloring agents, dyes, pigments, fragrances and the like can be mentioned. These secondary additives may be used alone or in combination.

  The specific gravity of the polymethylpentene fiber of the present invention is preferably 0.4 to 1.0. The polymethylpentene resin has a specific gravity of 0.83, and even when it is made into a single fiber, a fiber having a certain degree of lightness can be obtained. If the specific gravity of the polymethylpentene fiber is 0.4 or more, it is preferable because functions such as fiber mechanical strength and light weight can be achieved. On the other hand, if the specific gravity of the polymethylpentene fiber is 1.0 or less, it is preferable because the lightweight property of the fiber can be maintained. The specific gravity of the polymethylpentene fiber is more preferably 0.5 to 0.95, and further preferably 0.6 to 0.9.

  The strength of the polymethylpentene fiber of the present invention is preferably 1.0 cN / dtex or more. The strength of the polymethylpentene fiber is preferably as high as possible from the viewpoint of mechanical properties, but in reality, it is difficult to obtain a strength higher than 5.0 cN / dtex. If the strength of the polymethylpentene fiber is 1.0 cN / dtex or more, it is preferable because the thread breakage is small, the process passability is good, and the durability is excellent. From the viewpoint of process passability and durability, the strength of the polymethylpentene fiber is more preferably 1.3 cN / dtex or more, and further preferably 1.5 cN / dtex or more.

  The elongation of the polymethylpentene fiber of the present invention can be appropriately selected according to the application and required characteristics, but is preferably 5 to 100%. If the elongation of the polymethylpentene fiber is 5% or more, the abrasion resistance of the fiber and the fiber structure is good, the generation of fluff is small, and the durability is good. On the other hand, if the elongation of the polymethylpentene fiber is 100% or less, it is preferable because the dimensional stability of the fiber becomes good. The elongation is more preferably 8 to 85%, further preferably 10 to 70%.

  The total fineness of the polymethylpentene fiber of the present invention is preferably 10 to 500 dtex. If the total fineness of the polymethylpentene fiber is 10 dtex or more, it is preferable because yarn breakage is small and processability is good, and there is little fluffing during use and excellent durability. On the other hand, if the total fineness of the polymethylpentene fiber is 500 dtex or less, the flexibility of the fiber is not impaired, which is preferable. The total fineness of the polymethylpentene fiber is more preferably 20 to 400 dtex, and further preferably 30 to 300 dtex.

  The single yarn fineness of the polymethylpentene fiber of the present invention is preferably 0.2 to 10 dtex. If the single yarn fineness of the polymethylpentene fiber is 0.2 dtex or more, the process passability and handleability are good and the durability is excellent, which is preferable. On the other hand, if the single yarn fineness of the polymethylpentene fiber is 10 dtex or less, the flexibility of the fiber is not impaired, which is preferable. The single yarn fineness of the polymethylpentene fiber is more preferably 0.2 to 8 dtex, and further preferably 0.3 to 5 dtex.

  The polymethylpentene fiber of the present invention is not particularly limited with respect to the cross-sectional shape of the fiber. From the viewpoint of fiber strength, a perfect circular cross section is preferable, but a non-circular cross section may also be used. Specific examples of the non-circular cross section include multilobal, polygonal, flat, elliptical, C-shaped, H-shaped, S-shaped, T-shaped, W-shaped, X-shaped, Y-shaped, and the like.

Next, the manufacturing method of the polymethylpentene fiber of this invention is demonstrated.
The polymethylpentene fiber of the present invention can be obtained by melt-spinning a polymethylpentene-based resin into a fiber. When polymethylpentene fibers contain phenolic antioxidants, phosphorus antioxidants, and various other secondary additives, the desired additives are supplied together with the polymethylpentene resin during melt spinning. If they are mixed in a molten state, a method using a polymethylpentene resin and these additives previously melt-kneaded with a biaxial kneader or the like and pelletized, or 2 during melt spinning. A method in which a polymethylpentene resin and a desired additive are melt-kneaded and spun as it is using a spinning machine connected to a shaft kneader is preferable.

  As a method of melt spinning, a known method can be used, but the method shown below is preferable. After the chips are dried as necessary, the chips are supplied to a melt spinning machine such as an extruder type or a pressure melter type and melted, and measured with a metering pump. Then, after introducing into the spinning pack heated in the spinning block and filtering the molten polymer in the spinning pack, it is discharged from the spinneret to form fiber yarns. The fiber yarn discharged from the spinneret is cooled and solidified by a cooling device, taken up by a first godet roller, wound up by a winder through a second godet roller, and taken up as a wound yarn. In addition, in order to improve the spinning maneuverability, productivity, and mechanical properties of the fiber, a heater, a heating cylinder, a heat retaining cylinder, and the like may be installed below the spinneret as necessary. Moreover, you may supply oil to a fiber yarn using an oil supply apparatus, and you may give an entanglement to a fiber yarn using an entanglement apparatus.

  The spinning temperature in melt spinning can be appropriately selected according to the melting point and heat resistance of the polymethylpentene resin, but is preferably in the range of 250 to 320 ° C. The spinning speed in melt spinning can be appropriately selected according to the type of thermoplastic resin, the composite ratio, the spinning temperature, etc., but is preferably 100 to 5000 m / min. A spinning speed of 100 m / min or more is preferable because the running yarn is stable and yarn breakage can be suppressed. On the other hand, a spinning speed of 5000 m / min or less is preferable because the fiber yarn can be sufficiently cooled and stable spinning can be performed. The spinning speed is more preferably 300 to 4500 m / min, and further preferably 500 to 4000 m / min.

  Fibers drawn by melt spinning may be drawn to obtain polymethylpentene fibers having the desired fiber properties. When stretching is performed, either a two-step method of stretching a fiber once taken or a direct spinning drawing method of continuously drawing without drawing may be used. In the case of performing stretching, there is no particular limitation as long as it is an apparatus or method that can directly or indirectly heat the traveling yarn. Either a one-stage stretching method or a two-stage or more multi-stage stretching method may be used, but a one-stage stretching method or a two-stage stretching method is preferred. Examples of the heating method in stretching include a heating roller, a hot pin, a hot plate, a heating cylinder, a liquid bath such as hot water and hot water, a hot air, a gas bath such as steam, and a laser. These heating methods may be used alone, or may be used in combination, but from the viewpoint of controlling the heating temperature, uniform heating to the running yarn, and not complicating the device, contact with the heating roller, Contact with a hot pin, contact with a hot plate, or immersion in a liquid bath can be suitably employed.

  Although the draw ratio in the case of drawing can be appropriately selected according to the strength and elongation of the polymethylpentene fiber after drawing, it is preferably 1.02 to 6.0 times. A draw ratio of 1.02 or more is preferable because mechanical properties such as strength and elongation of the polymethylpentene fiber can be improved by drawing. On the other hand, if the draw ratio is 6.0 times or less, yarn breakage during drawing is suppressed, and stable drawing can be performed. The draw ratio is more preferably 1.05 to 5.0 times, and even more preferably 1.1 to 4.0 times.

  The stretching temperature for stretching can be appropriately selected according to the strength and elongation of the polymethylpentene fiber after stretching, but is preferably 50 to 200 ° C. A drawing temperature of 50 ° C. or higher is preferable because the yarn supplied to the drawing is sufficiently preheated, the thermal deformation during drawing becomes uniform, and the occurrence of fineness spots can be suppressed. On the other hand, when the stretching temperature is 200 ° C. or lower, the slipperiness of the fiber with respect to the stretching roller is improved, and therefore, yarn breakage is suppressed and stable stretching can be performed. The stretching temperature is more preferably 60 to 190 ° C, and further preferably 70 to 180 ° C. Moreover, you may perform a 50-200 degreeC heat setting as needed.

  Hereinafter, the present invention will be described in more detail with reference to examples. In addition, each characteristic value in an Example is calculated | required with the following method.

(A) Oxidation induction time (OIT)
0.1 g of casserole was prepared from the polymethylpentene fibers obtained in the examples. The obtained casserole was washed three times by immersing it in 100 ml of ethanol, then immersed in 500 ml of water, washed and air-dried. 5 mg of polymethylpentene fiber was collected from the dried case and used as a sample.

  Place the sample in an aluminum container and heat it with a TG-DTA (EXSTAR TG / DTA6200) manufactured by Seiko Instruments Inc. under a nitrogen atmosphere (flow rate 200 ml / min) at a heating rate of 30 ° C./min until the sample temperature reaches 260 ° C. did. The atmosphere was switched from nitrogen to air (flow rate 200 ml / min) and the sample continued to be heated at a sample temperature of 260 ° C. until the DTA (Differential Thermal Analysis) chart showed an exothermic peak.

The exothermic peak indicated by the DTA chart was analyzed using analysis software (Muse, manufactured by Seiko Instruments Inc.). The time required from the start of temperature rise to switching the atmosphere to air is T ¹ , the time required for the exothermic peak generation calculated by the analysis software is T ^2, and the time obtained by subtracting T ¹ from T ² is the oxidation induction time ( OIT). The measurement was performed 5 times per sample, and the average value was defined as OIT.

(B) Color tone measurement Tube knitting was produced with a circular knitting machine using the polymethylpentene fibers obtained in the examples, and the tube knitting was used as a sample. Scouring was performed at 80 ° C. for 20 minutes using sodium carbonate and a surfactant, and the sample was dried with a hot air dryer at 60 ° C. Samples were measured for L ^* , a ^* , and b ^* values using a Minolta spectrophotometer CM-3700d model with a D65 light source, a viewing angle of 10 °, and an optical condition of SCE (regular reflection light removal method). In addition, the measurement was performed 3 times per sample, and the average value was taken as L ^* , a ^* , b ^* value.

(C) Strength and elongation The strength and elongation were calculated according to JIS L1013: 1999 (chemical fiber filament yarn test method) 8.5 using the polymethylpentene fiber obtained in the examples as a sample. In an environment of a temperature of 20 ° C. and a humidity of 65% RH, a tensile test was performed using an autograph AG-50NISMS type manufactured by Shimadzu Corporation under the conditions of an initial sample length of 20 cm and a tensile speed of 20 cm / min. The strength (cN / dtex) is calculated by dividing the stress (cN) at the point indicating the maximum load by the fineness (dtex), and using the elongation (L1) and the initial sample length (L0) at the point indicating the maximum load, The elongation (%) was calculated by the formula. The measurement was carried out 10 times per sample, and the average values were taken as the strength and elongation.
Elongation (%) = {(L1-L0) / L0} × 100.

(D) Specific gravity The specific gravity was calculated according to the floatation / sink method of JIS L1013: 1999 (chemical fiber filament yarn test method) 8.17. A specific gravity measurement liquid was prepared using water as a heavy liquid and ethyl alcohol as a light liquid. In a constant temperature bath at a temperature of 20 ± 0.1 ° C., about 0.1 g of the fiber sample was left in the specific gravity measurement liquid for 30 minutes, and then the state of the sample was observed. After adding heavy liquid or light liquid according to the state of floatation, the sample was allowed to stand for 30 minutes, and after confirming that the sample was in the state of floatation and sedimentation, the specific gravity of the specific gravity measurement liquid was measured and the specific gravity of the sample was calculated. . In addition, the measurement was performed 5 times per sample and the average value was made into specific gravity.

(E) Total fineness, single yarn fineness In an environment of a temperature of 20 ° C. and a humidity of 65% RH, 100 m of polymethylpentene fiber was scraped using an electric measuring machine manufactured by INTEC. The weight of the obtained skein was measured, and the fineness (dtex) was calculated using the following formula. In addition, the measurement was performed 5 times per sample and the average value was made into the total fineness.
Total fineness (dtex) = weight of fiber 100 m (g) × 100
The obtained fineness value was divided by the number of filaments of polymethylpentene fiber, and the value was defined as the single yarn fineness.

(F) Confirmation of discoloration after high-temperature treatment Using a polymethylpentene fiber obtained in the examples, a cylindrical knitting was produced with a circular knitting machine, and the cylindrical knitting was subjected to a high-temperature treatment at 150 ° C. for 1 hour using a hot air dryer. The presence or absence of discoloration of the polymethylpentene fiber was confirmed visually.

(G) Strength and elongation after high-temperature treatment The polymethylpentene fibers obtained in the examples were made into 100 m cassettes using an electric measuring instrument made by INTEC. The casserole was hung on a hook with a weight of [total fineness of polymethylpentene fiber] × [0.02] g, and then subjected to high temperature treatment at 180 ° C. for 15 minutes using a hot air dryer. The strength and elongation of methylpentene fiber were measured. About the measuring method of intensity | strength and elongation, it carried out similarly to above-mentioned (C) intensity | strength and elongation.

(H) 1 wt% weight loss temperature of C agent 5 mg of C agent is put in an aluminum container, and is heated in an air atmosphere (flow rate 200 ml / min) and a heating rate of 20 ° C. with TG-DTA (EXSTAR TG / DTA6200) manufactured by Seiko Instruments Inc. / Min. At that time, the weight of the C agent before heating was set to 100 wt%, and the temperature at the time when the weight of the C agent decreased by 1 wt% by heating was defined as a 1 wt% weight loss temperature.

[Example 1]
DX820 as a polymethylpentene-based resin (manufactured by Mitsui Chemicals, chemical name 4-methyl-1-pentene / decene-1 copolymer, melting point 232 ° C., MFR 180 g / 10 min) 99.925 parts by weight; 0.05 parts by weight (manufactured by Sumitomo Chemical Co., Ltd.) and 0.025 parts by weight of Adekastab PEP36 (manufactured by ADEKA) as the B agent were kneaded at a kneading temperature of 260 ° C. using a biaxial extruder. The strand discharged from the biaxial extruder was water-cooled and then cut into a length of about 5 mm by a pelletizer to obtain a pellet.

  The obtained pellets were vacuum-dried at 95 ° C. for 12 hours, and then supplied to an extruder type melt spinning machine to be melted. At a spinning temperature of 300 ° C., a spinneret (discharge hole diameter 0.23 mm, discharge hole length 0.3 mm, hole 48, round holes) to obtain a spun yarn. The spun yarn is cooled by cooling air with an air temperature of 20 ° C. and an air speed of 20 m / min, applied with an oil agent by a lubricating device, converged, and taken up by a first godet roller rotating at 3000 m / min. A polymethylpentene fiber having a total fineness of 102 dtex-48 filaments (single yarn fineness of 2.13 dtex) was obtained by winding with a winder via a second godet roller rotating at the same speed as the dead roller.

  The evaluation results of the fiber characteristics of the obtained polymethylpentene fiber are shown in Table 1. Moreover, when the obtained polymethylpentene fiber was subjected to a high temperature treatment, no discoloration of the polymethylpentene fiber was observed. Furthermore, the strength after high temperature treatment was also good.

[Examples 2-3]
A polymethylpentene fiber was obtained in the same manner as in Example 1 except that the ratio of the addition amount of the polymethylpentene resin, the A agent and the B agent was changed as shown in Table 1.

  The evaluation results of the fiber properties of the obtained polymethylpentene fibers are shown in Table 1. Moreover, when the obtained polymethylpentene fiber was subjected to a high temperature treatment, no discoloration of the polymethylpentene fiber was observed. Furthermore, the strength after high temperature treatment was also good.

[Example 4]
In the same manner as in Example 1, except that the agent A was changed to ADK STAB AO-80 (manufactured by ADEKA) and the ratio of the addition amount of the polymethylpentene resin, the agent A and the agent B was changed as shown in Table 1. Methyl pentene fiber was obtained. The evaluation results of the fiber properties of the obtained polymethylpentene fibers are shown in Table 1. Moreover, when the obtained polymethylpentene fiber was subjected to a high temperature treatment, no discoloration of the polymethylpentene fiber was observed. Furthermore, the strength after high temperature treatment was also good.

[Example 5]
The same procedure as in Example 1 was performed except that the polymethylpentene resin was changed to DX231 (manufactured by Mitsui Chemicals, chemical name 4-methyl-1-pentene / hexadecene / octadecene copolymer, melting point 232 ° C., MFR 100 g / 10 min). Thus, polymethylpentene fiber was obtained.

  The evaluation results of the fiber properties of the obtained polymethylpentene fibers are shown in Table 1. Moreover, when the obtained polymethylpentene fiber was subjected to a high temperature treatment, no discoloration of the polymethylpentene fiber was observed. Furthermore, the strength after high temperature treatment was also good.

[Examples 6 to 7]
A polymethylpentene fiber was obtained in the same manner as in Example 5 except that the ratio of the addition amount of the polymethylpentene resin, the A agent, and the B agent was changed as shown in Table 1.

  The evaluation results of the fiber properties of the obtained polymethylpentene fibers are shown in Table 1. Moreover, when the obtained polymethylpentene fiber was subjected to a high temperature treatment, no discoloration of the polymethylpentene fiber was observed. Furthermore, the strength after high temperature treatment was also good.

[Examples 8 to 10]
Polymethylpentene fibers were obtained in the same manner as in Example 1 except that the ratio of the addition amount of the polymethylpentene resin and the A agent was changed as shown in Table 2, and the B agent was not added.

The evaluation results of the fiber properties of the obtained polymethylpentene fibers are shown in Table 2. Since the B agent was not added, the contrast color tone b ^* value of Examples 2 and 3 slightly increased. Moreover, when the obtained polymethylpentene fiber was subjected to a high temperature treatment, no discoloration of the polymethylpentene fiber was observed. Moreover, the strength after high-temperature treatment was also good.

[Examples 11 to 13]
Polymethylpentene fibers were obtained in the same manner as in Example 1 except that the ratio of the addition amount of the polymethylpentene resin and the B agent was changed as shown in Table 2, and the A agent was not added.

The evaluation results of the fiber properties of the obtained polymethylpentene fibers are shown in Table 2. Since the A agent was not added, the color tone b ^* value slightly increased as compared with Example 3. Moreover, when the obtained polymethylpentene fiber was subjected to a high temperature treatment, no discoloration of the polymethylpentene fiber was observed. Furthermore, the strength after high temperature treatment was also good.

[Examples 14 to 16]
As in Example 1, except that IRGAFOS168 (manufactured by BASF) was used as agent B, the ratio of the addition amount of polymethylpentene resin and agent B was changed as shown in Table 3, and agent A was not added. Methyl pentene fiber was obtained.

  Table 3 shows the evaluation results of the fiber properties of the obtained polymethylpentene fibers. Moreover, when the obtained polymethylpentene fiber was subjected to a high temperature treatment, no discoloration of the polymethylpentene fiber was observed. Furthermore, the strength after high temperature treatment was also good.

[Example 17]
Adeka Stub AO-80 (manufactured by ADEKA) was used as the A agent, the ratio of the addition amount of the polymethylpentene resin and the A agent was changed as shown in Table 3, and the same as in Example 1 except that the B agent was not added. Thus, polymethylpentene fiber was obtained.

  Table 3 shows the evaluation results of the fiber properties of the obtained polymethylpentene fibers. Moreover, when the obtained polymethylpentene fiber was subjected to a high temperature treatment, no discoloration of the polymethylpentene fiber was observed. Furthermore, the strength after high temperature treatment was also good.

[Example 18]
Example 1 is the same as Table 1 except that Sumiliizer GA-80 (manufactured by Sumitomo Chemical Co., Ltd.) was used as agent A, the ratio of the addition amount of polymethylpentene resin and agent A was changed as shown in Table 3, and agent B was not added. Similarly, polymethylpentene fiber was obtained.

  Table 3 shows the evaluation results of the fiber properties of the obtained polymethylpentene fibers. Moreover, when the obtained polymethylpentene fiber was subjected to a high temperature treatment, no discoloration of the polymethylpentene fiber was observed. Furthermore, the strength after high temperature treatment was also good.

[Example 19]
DX820 (made by Mitsui Chemicals, chemical name 4-methyl-1-pentene / decene-1 copolymer, melting point 232 ° C., MFR 180 g / 10 min) as polymethylpentene resin 99.925 parts by weight, Sumizer GP (Sumitomo) Chemical Co., Ltd.) 0.05 parts by weight and Adeka Stub PEP36 (manufactured by ADEKA) 0.025 part by weight as B agent were kneaded at a kneading temperature of 260 ° C. using a biaxial extruder. The strand discharged from the biaxial extruder was water-cooled and then cut into a length of about 5 mm by a pelletizer to obtain a pellet.

  The obtained pellets were vacuum-dried at 95 ° C. for 12 hours, and then supplied to an extruder type melt spinning machine to be melted. At a spinning temperature of 300 ° C., a spinneret (discharge hole diameter 0.23 mm, discharge hole length 0.3 mm, hole 48, round holes) to obtain a spun yarn. The spun yarn is cooled with cooling air at an air temperature of 20 ° C. and an air speed of 20 m / min, applied with an oil agent by a lubricating device, converged, and taken up by a first godet roller rotating at 1000 m / min. It wound up with the winder via the 2nd godet roller rotated at the same speed as a dead roller, and obtained the polymethylpentene fiber of total fineness 306dtex-48 filament.

  A first heating roller heated to 140 ° C. that rotates polymethylpentene fibers obtained by melt spinning at a speed of 200 m / min, and a second heating roller that is heated to 140 ° C. that rotates at a speed three times that of the first heating roller The polymethylpentene fiber having a total fineness of 102 dtex-48 filament (single yarn fineness of 2.13 dtex) was obtained.

  Table 3 shows the evaluation results of the fiber properties of the obtained polymethylpentene fibers. Moreover, when the obtained polymethylpentene fiber was subjected to a high temperature treatment, no discoloration of the polymethylpentene fiber was observed. Furthermore, the strength after high temperature treatment was also good.

[Examples 20 and 21]
Polymethylpentene fibers were obtained in the same manner as in Example 1 except that the ratio of the addition amount of the polymethylpentene resin, the A agent, the B agent, and the C agent was as shown in Table 3. In addition, CHIMASSORB2020 (molecular weight 3000, 1 wt% weight reduction temperature 300 degreeC) was used for C agent of Example 20, and CHIMASSORB944 (molecular weight 2550, 1 wt% weight loss temperature 300 degreeC) was used for C agent of Example 21.

  Table 3 shows the evaluation results of the fiber properties of the obtained polymethylpentene fibers. Moreover, when the obtained polymethylpentene fiber was subjected to a high temperature treatment, no discoloration of the polymethylpentene fiber was observed. Furthermore, by adding the C agent in addition to the A agent and the B agent, the strength after the high temperature treatment was maintained higher than in the case where the C agent was not added (Example 2).

[Examples 22 and 23]
The ratios of the addition amounts of the polymethylpentene resin, the A agent and the B agent were as shown in Table 4, and the mixture was kneaded at a kneading temperature of 260 ° C. using a biaxial extruder. The strand discharged from the biaxial extruder was water-cooled and then cut into a length of about 5 mm by a pelletizer to obtain a pellet.

  The obtained pellets were vacuum-dried at 95 ° C. for 12 hours, and then supplied to an extruder type melt spinning machine to be melted. At a spinning temperature of 300 ° C., a spinneret (discharge hole diameter 0.18 mm, discharge hole length 0.234 mm, hole (Equation 72, round hole) to give a spun yarn. The spun yarn is cooled by cooling air with an air temperature of 20 ° C. and an air speed of 20 m / min, applied with an oil agent by a lubricating device, converged, and taken up by a first godet roller rotating at 3000 m / min. Winding with a winder via a second godet roller rotating at the same speed as the dead roller, the total fineness of 84 dtex-72 filaments (single yarn fineness 1.17 dtex) in Example 22, and the total fineness 50 dtex- in Example 23 A polymethylpentene fiber having 72 filaments (single yarn fineness 0.69 dtex) was obtained.

  Table 4 shows the evaluation results of the fiber properties of the obtained polymethylpentene fibers. Moreover, when the obtained polymethylpentene fiber was subjected to a high temperature treatment, no discoloration of the polymethylpentene fiber was observed. Furthermore, the strength after high temperature treatment was also good.

[Comparative Example 1]
DX820 is used as a polymethylpentene resin, and the pellets of DX820 are vacuum-dried at 95 ° C. for 12 hours, and then supplied to an extruder type melt spinning machine to be melted. At a spinning temperature of 300 ° C., a spinneret (discharge hole diameter 0.23 mm And a discharge hole length of 0.3 mm, a hole count of 48, and a round hole) to obtain a spun yarn. The spun yarn is cooled by cooling air with an air temperature of 20 ° C. and an air speed of 20 m / min, applied with an oil agent by a lubricating device, converged, and taken up by a first godet roller rotating at 3000 m / min. It wound up with the winder through the 2nd godet roller rotated at the same speed as a dead roller, and obtained 102dtex-48f polymethylpentene fiber.

  Table 4 shows the evaluation results of the fiber properties of the obtained polymethylpentene fibers. Since A agent and B agent were not added, OIT did not reach 4 minutes. When the obtained polymethylpentene fiber was subjected to a high temperature treatment, the OIT did not reach 4 minutes, so the polymethylpentene fiber was discolored yellow. Moreover, the strength after the high temperature treatment was lowered to 1.0 cN / dtex or less.

[Comparative Example 2]
Polymethylpentene fibers were obtained in the same manner as Comparative Example 1 except that DX231 was used as the polymethylpentene resin.

  Table 4 shows the evaluation results of fiber characteristics of the obtained polymethylpentene fiber. Since A agent and B agent were not added, OIT did not reach 4 minutes. When the obtained polymethylpentene fiber was subjected to a high temperature treatment, the OIT did not reach 4 minutes, so the polymethylpentene fiber was discolored yellow. Moreover, the strength after the high temperature treatment was lowered to 1.0 cN / dtex or less.

[Comparative Example 3]
IRGAFOS168 (manufactured by BASF) is used as agent B, and as a compound similar to agent C, hindered amine flame retardant CGL-116 (product name: Flamstab NOR 116, formerly manufactured by Ciba Specialty Chemicals, currently manufactured by BASF) , Molecular weight 2260, 1 wt% weight loss temperature 260 ° C.) was added, and the ratio of the addition amount of polymethylpentene resin and B agent was changed as shown in Table 4, and polymethyl was obtained in the same manner as in Example 1. Penten fibers were obtained.

Table 4 shows the evaluation results of the fiber properties of the obtained polymethylpentene fibers. The OIT reached 4 minutes, but the b ^* value exceeded 3 because a large amount of nitrogen-based flame retardant was added. Moreover, although the high temperature process was performed, since b ^* value before a process was high, evaluation of yellowing was not implemented. The strength after the high temperature treatment was reduced to 1.0 cN / dtex or less.

[Comparative Examples 4 to 10]
Example A was used in the same manner as in Example 1 except that the agents shown in Table 5 were used as agent A and agent B, and the ratios of the addition amounts of polymethylpentene resin, agent A and agent B were changed as shown in Table 5. (In Table 5, GM is Sumilizer GM (manufactured by Sumitomo Chemical Co., Ltd.), and GS (F) is Sumilizer GS (F) (manufactured by Sumitomo Chemical Co., Ltd.).)
As a result, in Comparative Examples 4 to 9, polymethylpentene fibers were obtained, but in Comparative Example 10, thread breakage occurred frequently, and polymethylpentene fibers could not be obtained.

  Table 5 shows the evaluation results of the fiber properties of the obtained polymethylpentene fibers. In Comparative Examples 4 to 6, when the obtained polymethylpentene fiber was subjected to a high temperature treatment, the OIT did not reach 4 minutes, so the polymethylpentene fiber was discolored yellow.

In Comparative Examples 7 to 8, the OIT reached 4 minutes, but the b ^* value exceeded 3 because the amount of agent A added was large. Therefore, the yellowing due to the high temperature treatment was not evaluated.

  In Comparative Example 9, when the obtained polymethylpentene fiber was subjected to a high temperature treatment, the OIT did not reach 4 minutes, so the polymethylpentene fiber was discolored yellow. Moreover, the intensity | strength after a high temperature process was falling to 1.0 cN / dtex or less in all of Comparative Examples 4-9.

[Comparative Examples 11 and 12]
The same as in Example 1 except that the agent A and the agent B were not used, the agents shown in Table 6 were used as the agent C, and the ratio of the addition amount of the polymethylpentene resin and the agent C was changed as shown in Table 6. did. When the obtained polymethylpentene fiber was subjected to a high temperature treatment, the OIT did not reach 4 minutes, so the polymethylpentene fiber was discolored yellow. Moreover, the strength after the high temperature treatment was lowered to 1.0 cN / dtex or less.

  The polymethylpentene fiber of the present invention is excellent in oxidation heat resistance, light weight, water repellency, and heat resistance, and therefore can be suitably used as a clothing material.

Claims (3)

A polymethylpentene fiber having an oxidation induction time (OIT) of 4 minutes or more and a b ^* value in the L ^* a ^* b ^* color system ranging from -3 to 3.   2. The polymethylpentene fiber according to claim 1, wherein the ratio of polymethylpentene to fiber is 90% by weight or more.   The polymethylpentene fiber according to claim 1 or 2, wherein the strength of the fiber is 1.0 cN / dtex or more.

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