JP4582425B2 - Polyurethane yarn and method for producing the same - Google Patents

Description

  The present invention relates to a polyurethane yarn and a method for producing the same.

  More specifically, when a stretch fabric such as a knitted fabric or a woven fabric is combined with other fibers, the quality of the obtained stretch fabric or garment, such as dark clearness, appearance quality, antistatic properties, and dust adhesion prevention properties, is improved. The present invention relates to a polyurethane yarn that can be made excellent and a method for producing the same.

  Polyurethane yarns are widely used for general clothing applications such as stockings, socks, innerwear, and outerwear as stretch materials due to their excellent stretch function. And since the polyurethane thread | yarn further improves the stretch function of such clothing, the content rate in a fabric is still higher. By using a fabric having a high blending ratio of polyurethane yarns, its stretchability, feeling of wear, etc. can be made better than before.

  However, when the blending ratio of polyurethane yarns is increased, these polyurethane yarns are significantly inferior in dyeability and antistatic properties compared to hard yarns such as polyamide fibers, natural fibers, and polyethylene terephthalate fibers to be mixed, so that the appearance quality of the fabric is hindered. Was a problem. This tendency is particularly noticeable in dark-colored fabrics. Deterioration in appearance quality due to the adhesion of dust due to darkness and darkness, which is the depth of fabric color when used as clothing, occurs. Depending on the application, polyurethane yarn In some cases, the mixing ratio was limited.

  In order to solve this problem, several means have been tried from raw yarn to high-order processing, and in particular, a method of using polyurethane yarn as processed yarn has been frequently used. For example, a coated elastic yarn obtained by coating a polyurethane yarn serving as a core yarn with a hard yarn serving as a sheath yarn is employed. As described above, the coated elastic yarn using the polyurethane yarn as the core yarn is hard to expose the polyurethane yarn as the core yarn, and can form a fabric excellent in dark color sharpness. However, as described above, fabrics that have been designed to increase the blending ratio of polyurethane yarns and increase the amount of expansion and contraction, especially in the case of black formal clothing, which is the case with the highest darkness, at first glance after sewing, Even if it is excellent in appearance quality, when it is actually worn and stretched, the polyurethane yarn of the core yarn is exposed to the outside, and the dark color clarity of the extended part such as the elbow and knee is insufficient, The effect of the coated yarn was also unsatisfactory.

  In addition, with regard to dust adhesion, the fabric containing polyurethane yarn is left standing, and over time, and when it is used as a garment, when it is attached / detached, the dust adhesion is noticeable in the case of a fabric with high darkness. The problem is that the appearance quality of the product is remarkably lowered.

  As a countermeasure, there is a method of applying anti-static processing in order to prevent the adhesion of dust, but there are problems such as cost increase. In other words, the effect of the high-order processing is insufficient to solve the above-mentioned purpose, and since it has a stretch function of high elongation, it has a problem that it is difficult to deal with clothing with high polyurethane content and high darkness. there were.

  Moreover, the example which uses the polyurethane thread colored by patent document 1 for the pantyhose waist | hip | lumbar part as a response | compatibility from the original thread with respect to the above-mentioned problem is disclosed. Patent Document 2 also discloses a method for producing a colored polyurethane yarn.

However, when these melt spinning methods are used, it is difficult to obtain a high-quality polyurethane yarn with a multi-thread obtained by converging a low-fineness yarn or a low-fineness single yarn. In particular, it was thin, had a high polyurethane blend ratio, and could not cope with imparting dark color clarity and appearance quality to a deeply dyed stretch fabric.
Japanese Patent Publication No. 60-44406 Japanese Patent Publication No. 8-30288

  An object of the present invention is to provide excellent dark-coloredness, appearance quality, antistatic properties, dust adhesion prevention property, and the like of the obtained stretch fabric and clothes when used for clothes and the like. It is to provide a polyurethane yarn and a method for producing the same. Specifically, an object of the present invention is to provide a polyurethane yarn having a moderate elongation and having a certain degree of mechanical setting, deep color and antistatic properties, and a method for producing the same.

In order to solve the above problems, the polyurethane yarn of the present invention employs the following solutions. That is, a polyurethane yarn produced by dry spinning, the main component of the polyurethane is a polyol with a diisocyanate, containing mosquitoes over carbon black and the monoamine, the content of carbon black is 0.1 wt% to 20 wt% A polyurethane yarn characterized in that the carbon black is ketjen black .

Moreover, in order to solve the said subject, the manufacturing method of the polyurethane thread | yarn of this invention employ | adopts the following solution means. That is, the main constituents added carbon black and the monoamine to the polyurethane solution is a polyol with a diisocyanate, a manufacturing method of a reportage polyurethane yarn to produce a polyurethane yarn by dry spinning the polyurethane solution, wherein the carbon black is Ketjen It is a chain black and contains the carbon black in the range of 0.1 wt% or more and 20 wt% or less .

  The clothes and the like using the polyurethane yarn of the present invention are excellent in deep color property, dark color vividness, dust adhesion prevention property, antistatic property and the like. Because of having these excellent properties, the polyurethane yarn of the present invention can be used alone or in combination with various fibers, for example, socks, stockings, circular knitting, tricot, swimsuit, ski pants, work clothes, smoke fire. Clothing, clothes, golf trousers, wet suits, bras, girdles, fastening materials for various textile products such as gloves and socks, fastening materials for preventing sanitary products such as paper diapers, fastening materials for waterproofing materials, imitation bait, artificial flowers, electricity It can be used for various applications such as insulating materials, wiping cloths, copy cleaners, and gaskets.

  First, the polyurethane used in the present invention will be described.

  The polyurethane used in the present invention is produced by dry spinning, and the main components are polyol and diisocyanate.

  That is, for example, polyurethane urea composed of polyol, diisocyanate and diamine may be used, and polyurethane composed of polyol, diisocyanate and diol may be used.

  Moreover, the polyurethane urea which uses the compound which has a hydroxyl group and an amino group in a molecule | numerator as a chain extender may be used.

  In addition, it is also preferable to use trifunctional or higher polyfunctional glycol or isocyanate or the like as long as the effects of the present invention are not hindered.

  Here, typical structural units constituting the polyurethane yarn of the present invention will be described.

  The polyol used in the present invention is preferably polyether glycol, polyester glycol, polycarbonate diol or the like.

  In particular, polyether glycol is preferably used from the viewpoint of imparting flexibility and elongation to the yarn. Examples of polyether glycols include polyethylene oxide, polyethylene glycol, polyethylene glycol derivatives, polypropylene glycol, polytetramethylene ether glycol (hereinafter abbreviated as PTMG), modified PTMG (which is a copolymer of THF and 3-MeTHF ( Hereinafter, 3M-PTMG is abbreviated), modified PTMG which is a copolymer of THF and 2,3-dimethyl THF, polyol having side chains on both sides disclosed in Japanese Patent Publication No. 2615131 and the like are preferably used. The These polyether glycols may be used alone or in combination of two or more.

  Further, from the viewpoint of obtaining abrasion resistance and light resistance as a polyurethane yarn, butylene adipate, polycaprolactone diol, polyester glycol such as polyester polyol having a side chain disclosed in JP-A No. 61-26612 and the like, The polycarbonate diol disclosed in JP-B-2-289516 is preferably used.

  These polyols may be used alone, or may be used by mixing or copolymerizing two or more kinds. The molecular weight of the polyol used in the present invention is preferably from 1,000 to 8000, more preferably from 1800 to 6000, from the viewpoint of obtaining elongation, strength, heat resistance and the like when it is made into a yarn. By using a polyol having a molecular weight within this range, an elastic yarn excellent in elongation, strength, elastic recovery, and heat resistance can be obtained.

  Next, as the diisocyanate used in the present invention, aromatic diisocyanates such as diphenylmethane diisocyanate (hereinafter abbreviated as MDI), tolylene diisocyanate, 1,4-diisocyanate benzene, xylylene diisocyanate, 2,6-naphthalene diisocyanate, It is particularly suitable for synthesizing polyurethane having high heat resistance and high strength. Further, as the alicyclic diisocyanate, for example, methylene bis (cyclohexyl isocyanate) (hereinafter referred to as H12MDI), isophorone diisocyanate, methylcyclohexane 2,4-diisocyanate, methylcyclohexane 2,6-diisocyanate, cyclohexane 1,4-diisocyanate, hexa Hydroxylylene diisocyanate, hexahydrotolylene diisocyanate, octahydro 1,5-naphthalene diisocyanate and the like are preferable. Aliphatic diisocyanates can be used effectively especially when suppressing fading of polyurethane yarns. And these diisocyanates may be used independently and may use 2 or more types together.

  Next, as the chain extender in the present invention, it is preferable to use at least one of low molecular weight diamine and low molecular weight diol.

  In addition, you may have a hydroxyl group and amino groups in a molecule like ethanolamine. Preferred low molecular weight diamines include, for example, ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, hexamethylenediamine, p-phenylenediamine, p-xylylenediamine, m-xylylenediamine, p, p ′. -Methylenedianiline, 1,3-cyclohexyldiamine, hexahydrometaphenylenediamine, 2-methylpentamethylenediamine, bis (4-aminophenyl) phosphine oxide and the like. It is also preferred that one or more of these are used. Particularly preferred is ethylenediamine. By using ethylenediamine, it is possible to obtain a yarn excellent in elongation, elastic recovery, and heat resistance. A triamine compound capable of forming a crosslinked structure such as diethylenetriamine may be added to these chain extenders to such an extent that the effect is not lost.

  Typical low molecular weight diols include ethylene glycol, 1,3 propanediol, 1,4 butanediol, bishydroxyethoxybenzene, bishydroxyethylene terephthalate, 1-methyl-1,2-ethanediol, and the like. is there. It is also preferred that one or more of these are used. Particularly preferred are ethylene glycol, 1,3 propanediol, and 1,4 butanediol. When these are used, a diol-extended polyurethane has a high heat resistance and a high strength yarn can be obtained.

  Further, the molecular weight of the elastic yarn of the present invention is preferably in the range of 40000 to 150,000 as the number average molecular weight from the viewpoint of obtaining a fiber having durability and high strength.

  The molecular weight in the present invention is measured by GPC and converted by polystyrene.

  The polyurethane yarn of the present invention is particularly preferably made of a diol and a diisocyanate, and has a polyurethane yarn that has no practical problems including process passability and is excellent in heat setting properties. The melting point on the high temperature side is in the range of 200 ° C. or higher and 280 ° C. or lower. The melting point on the high temperature side in the present invention refers to the value of second run when the yarn is measured by DSC, and corresponds to the melting point of the so-called hard segment of polyurethane.

  And, at least one selected from the group consisting of PTMG having a molecular weight in the range of 1800 to 6000 as polyol, MDI as diisocyanate, ethylene glycol, diol, 1,3 propanediol and 1,4 butanediol is used. Polyurethane yarns that have been synthesized and have a melting point on the high temperature side in the range of 200 ° C. or higher and 280 ° C. or lower are particularly high in elongation, and as described above, there are practical problems including process passability. This is preferable because it is excellent in heat setting.

  From the viewpoint of setting the melting point on the high temperature side of the polyurethane yarn to 200 ° C. or higher and 280 ° C. or lower, it is preferable to conduct a test in advance and select the ratio of diisocyanate, polyol, and diol.

  Furthermore, the polyurethane used in the present invention has as an end-blocking agent dimethylamine, diisopropylamine, ethylmethylamine, diethylamine, methylpropylamine, isopropylmethylamine, diisopropylamine, butylmethylamine, isobutylmethylamine, isopentylmethyl. Monoamines such as amine, dibutylamine and diamylamine are used. It is also preferred that one or more end-capping agents are used in combination. In that case, monoisol such as ethanol, propanol, butanol, isopropanol, allyl alcohol, cyclopentanol, monoisocyanate such as phenyl isocyanate, etc. are used. It is also preferable.

  The polyurethane yarn of the present invention contains a pigment. In the present invention, there is a problem that a high deep color cannot be obtained unless a dye is contained.

  In the present invention, carbon black is used as the pigment. Phthalocyanine pigment, azo pigment, titanium oxide, zinc oxide, barium sulfate, iron oxide, cerium oxide, magnesium oxide, azo dye, indigoid dye, phthalocyanine dye may be used in combination, preferably carbon black and phthalocyanine series Compounds, more preferably carbon black and copper phthalocyanine. Any pigment other than carbon black used in the present invention may be used as long as it has a black hue as a polyurethane yarn by a combination thereof, and any hue may be used. For example, it is also preferable to use a complementary color. Depending on the particle size of the dye, especially the average primary particle size and specific surface area of the carbon black, the hue of the polyurethane yarn may shift in the red direction. Add phthalocyanine compounds, especially pigment blue and pigment green of copper phthalocyanine pigments. Thus, the polyurethane yarn can be made achromatic black. Furthermore, from the viewpoint of compensating for the hue, pigments other than carbon black can be used in combination of two or more.

  In the polyurethane yarn of the present invention, when containing carbon black, the effect of high deep color and antistatic properties is remarkable, and when it is combined with other fibers to form a stretch fabric such as a knitted fabric or a woven fabric, a remarkable dark and vivid color is obtained. Property and dust adhesion prevention property are preferable.

As the carbon black used in the present invention, a hydrocarbon or a crystallite aggregate formed by burning or thermally decomposing a hydrocarbon-containing compound shown in JIS K6200 in a state where the supply of air is insufficient is applied. can, an oil furnace process, gas furnace process, those produced by any method of channel method or a thermal method can be used, Ke Tchenbura' click and the like.

  In the present invention, the content of carbon black is preferably in the range of 0.1 wt% to 20 wt% from the viewpoint of obtaining good black uniformity and spinnability, and has good darkness and antistatic properties. From the viewpoint of obtaining, 0.5 wt% or more and 10 wt% or less is more preferable.

  In addition, it is also preferable that these contents are suitably determined by testing in advance according to the use.

  Further, the carbon black of the present invention has an average primary particle diameter of 20 nm to 100 nm as measured with an electron microscope from the viewpoint of speeding up dispersion in polyurethane and making the characteristics of the polyurethane yarn produced a target characteristic. Are preferred. Further, from the viewpoint of obtaining good darkness and antistatic properties, 30 nm to 80 nm is more preferable.

Furthermore, the carbon black of the present invention preferably has a specific surface area (BET adsorption method) of 20 m ² / g or more from the viewpoint of increasing the darkness of the polyurethane yarn. Furthermore, it is preferably 30 m ² / g or more.

  In addition, the carbon black used in the present invention prevents impurities from being mixed into the polyurethane yarn to be produced, and from the viewpoint of achieving the target characteristics, the carbon black is heated at 950 ° C. defined in Japanese Industrial Standard K6221 for 7 minutes. Those whose weight loss (volatile content) is in the range of 0.5 to 5% are preferred.

  In the polyurethane yarn of the present invention, a dye is added so that the L value is 35 or less. When the L value exceeds 35, when a stretch fabric such as a knitted fabric or a woven fabric is combined with other fibers, dark clearness cannot be obtained.

  The L value is the brightness in Hunter Lab color display, and the smaller the value, the lower the brightness, that is, the deeper the black color. From the viewpoint of black color development, it is important that the L value is 35 or less. L value becomes like this. Preferably it is 30 or less, More preferably, it is 27 or less.

  In the present invention, the polyurethane may contain various stabilizers. For example, hindered phenolic agents such as BHT and Sumitomo Chemical Co., Ltd. “Smulizer GA-80” manufactured by Sumitomo Chemical Co., Ltd., and various benzotriazole and benzophenone based agents such as “Tinuvin” manufactured by Ciba Geigy Co., Ltd. , Phosphorus drugs such as “Sumilyzer P-16” manufactured by Sumitomo Chemical Co., Ltd., various hindered amine drugs, inorganic substances such as minerals such as talc, metal soap such as fluorine or silicone resin powder, magnesium stearate, In addition, bactericides and deodorants containing silver, zinc and their compounds, lubricants such as silicone and mineral oil, various antistatic agents such as barium sulfate, cerium oxide, betaine and phosphate It is also preferred that these be reacted with a polymer. In order to further enhance the durability to light and various nitric oxides, for example, a nitric oxide supplement such as HN-150 manufactured by Nippon Hydrazine Co., Ltd., for example, “Sumilyzer GA manufactured by Sumitomo Chemical Co., Ltd.” It is also preferable to use a thermal oxidation stabilizer such as -80 ", for example, a light stabilizer such as" Sumisorb 300 # 622 "manufactured by Sumitomo Chemical Co., Ltd.

  The composition of the polyurethane of the present invention is preferably such.

  The fineness and cross-sectional shape of the polyurethane yarn of the present invention are not particularly limited. For example, when the polyurethane yarn of the present invention is combined with other fibers to form a stretch fabric such as a knitted fabric or a woven fabric, the fineness of the polyurethane yarn is in the range of 10 to 110 decitex from the viewpoint of obtaining dark color clarity of the resulting stretch fabric. Is preferable, and the range of 15 to 55 dtex is more preferable.

  Further, the cross-sectional shape of the yarn may be circular or flat.

  Next, the manufacturing method of the polyurethane yarn of this invention is demonstrated in detail.

  In the present invention, it is preferable to prepare a polyurethane solution first. The method for producing the polyurethane solution and the method for producing the polyurethane as the solute of the solution may be either a melt polymerization method or a solution polymerization method, or may be another method. However, the solution polymerization method is more preferable. In the case of the solution polymerization method, there is little generation of foreign substances such as gel in the polyurethane, it is easy to spin, and it is easy to obtain a low-definition polyurethane yarn.

  Of course, in the case of solution polymerization, there is an advantage that the operation of making a solution can be omitted.

  The polyurethane particularly suitable for the present invention includes PTMG having a molecular weight of 1800 to 6000 as polyol, MDI as diisocyanate, ethylene glycol, diol, 1,3 propanediol and 1,4 butanediol as diol. And those having a melting point on the high temperature side of 200 ° C. or higher and 280 ° C. or lower.

  Such polyurethane can be obtained, for example, by synthesizing using the above-mentioned raw materials in DMAc, DMF, DMSO, NMP, or the like or a solvent containing these as a main component. For example, each raw material is charged and dissolved in such a solvent, and heated to an appropriate temperature to be reacted to form a polyurethane, a so-called one-shot method, or a polyol and a diisocyanate are first melt-reacted, and then the reaction product A method of dissolving polyurethane in a solvent and reacting with the above-mentioned diol to form polyurethane can be employed as a particularly suitable method.

  When a diol is used as a chain extender, a typical method for adjusting the high-temperature melting point of polyurethane to a range of 200 ° C. or higher and 280 ° C. or lower can be achieved by controlling the types and ratios of polyol, MDI, and diol. . When the molecular weight of the polyol is low, a polyurethane having a high melting point can be obtained by relatively increasing the proportion of MDI. Similarly, when the molecular weight of the diol is low, the proportion of polyol is relatively small. By doing so, a polyurethane having a high melting point at a high temperature can be obtained.

  When the molecular weight of the polyol is 1800 or more, it is preferable to proceed the polymerization at a ratio of (number of moles of MDI) / (number of moles of polyol) = 1.5 or more in order to make the melting point on the high temperature side 200 ° C. or more. .

  In synthesizing such polyurethane, it is also preferable to use one or a mixture of two or more catalysts such as amine catalysts and organometallic catalysts. Examples of the amine catalyst include N, N-dimethylcyclohexylamine, N, N-dimethylbenzylamine, triethylamine, N-methylmorpholine, N-ethylmorpholine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethyl-1,3-propanediamine, N, N, N ′, N′-tetramethylhexanediamine, bis-2-dimethylaminoethyl ether, N, N, N ′ , N ′, N′-pentamethyldiethylenetriamine, tetramethylguanidine, triethylenediamine, N, N′-dimethylpiperazine, N-methyl-N′-dimethylaminoethyl-piperazine, N- (2-dimethylaminoethyl) morpholine, 1-methylimidazole, 1,2-dimethylimidazole, N, N-dimethyla Noethanol, N, N, N′-trimethylaminoethylethanolamine, N-methyl-N ′-(2-hydroxyethyl) piperazine, 2,4,6-tris (dimethylaminomethyl) phenol, N, N-dimethyl Examples include aminohexanol and triethanolamine.

  Examples of organometallic catalysts include tin octoate, dibutyltin dilaurate, and lead dibutyl octoate.

  The concentration of the polyurethane solution thus obtained is usually preferably in the range of 30% by weight to 80% by weight.

  In the method for producing a polyurethane yarn of the present invention, a dye is added to the polyurethane solution so that the L value (lightness) of the polyurethane yarn is 35 or less.

  As such a dye, the aforementioned carbon black or the like is preferably used. Any method can be adopted as a method of adding the dye to the polyurethane solution.

  When the dye is added to the polyurethane solution, it can be used in the form of powder, slurry or paste. The timing of addition is a method of adding at the time of polyurethane polymerization, a masterbatch containing a dye is prepared in advance, a method of blending the masterbatch into a base polymer solution at the time of spinning, or a liquid containing a dye is prepared and blended at the time of spinning. The dye can be added by a general deposition method such as a method. As a typical method for mixing, various means such as a method using a static mixer, a method using stirring, a method using a homomixer, and a method using a twin screw extruder can be adopted. Here, it is preferable to add the pigment | dye to add as a masterbatch of a solution from a viewpoint of performing uniform addition to a polyurethane solution.

  The addition of the dye to the polyurethane solution may cause a phenomenon in which the solution viscosity of the mixed solution after the addition becomes higher than expected compared to the solution viscosity of the polyurethane before the addition. From the viewpoint of preventing this phenomenon, dimethyl Monoamines such as amine, diisopropylamine, ethylmethylamine, diethylamine, methylpropylamine, isopropylmethylamine, diisopropylamine, butylmethylamine, isobutylmethylamine, isopentylmethylamine, dibutylamine, diamylamine and the like are used as end-capping agents. It is also preferable to further mix and use end-capping agents such as monools such as ethanol, propanol, butanol, isopropanol, allyl alcohol, cyclopentanol, and monoisocyanates such as phenyl isocyanate.

  When the dye is added to the polyurethane solution, it may be added at the same time as, for example, the agent such as a light-resistant agent and an antioxidant.

  In the present invention, a polyurethane yarn is produced by dry spinning a polyurethane solution.

  Since the setting property and stress relaxation of the polyurethane yarn of the present invention are particularly susceptible to the speed ratio between the godet roller and the winder, it is preferably determined as appropriate according to the intended use of the yarn.

  That is, from the viewpoint of obtaining a polyurethane yarn having desired setting properties and stress relaxation, it is preferable that the speed ratio of the godet roller and the winder is wound in a range of 1.15 to 1.65. And when obtaining the polyurethane yarn which has especially high setting property and low stress relaxation, the speed ratio of a godet roller and a winder has the more preferable range of 1.15 or more and 1.4 or less, and 1.15 or more and 1. A range of 35 or less is more preferable.

  On the other hand, when obtaining a polyurethane yarn having low setability and high stress relaxation, the speed ratio of the godet roller and the winder is preferably wound in the range of 1.25 or more and 1.65 or less, and 1.35 or more. The range of 1.65 or less is more preferable.

  Further, the spinning speed is preferably 450 m / min or more from the viewpoint of improving the strength of the obtained polyurethane yarn.

  When the polyurethane yarn of the present invention is combined with other fibers to form stretch fabrics such as knitted fabrics and woven fabrics, it is used for ladies and men's use, school uniforms, Japanese clothing, linings, etc., but particularly suitable for black formal use. .

  The invention is explained in more detail by means of examples.

  The strength, elongation, setting property, stress relaxation, deep color property, dark color sharpness, dust adhesion prevention property and antistatic property in the present invention will be described.

[Strength, elongation, setability, stress relaxation]
The setability, stress relaxation, strength, and elongation were measured by tensile testing polyurethane yarn using an Instron 4502 type tensile tester.

  300% elongation of a 5 cm (L1) sample was repeated 5 times at a tensile speed of 50 cm / min. The stress at this time was defined as (G1). The sample length was then held for 30 seconds. The stress after holding for 30 seconds was defined as (G2). Next, the length of the sample when the elongation of the sample was recovered and the stress became zero was defined as (L2). Furthermore, it extended until the sample cut | disconnected 6th time. The stress at the time of rupture was defined as (G3), and the sample length at the time of rupture was defined as (L3). Hereinafter, the above characteristics are calculated by the following formula.

Strength = (G3)
Stress relaxation = 100 × {((G1) − (G2)) / (G1)}
Set property = 100 × {((L2) − (L1)) / (L1)}
Elongation = 100 × {((L3) − (L1)) / (L1)}
[Heat setting]
The heat setting property was measured by the following method.

The sample yarn was free treated with 100 ° C. steam for 10 minutes, then free treated with 100 ° C. boiling water for 2 hours and dried at room temperature for one day. Next, the sample yarn (length = (L5)) was stretched 100% (length = 2 × (L5)). This length was treated with 115 ° C. steam for 1 minute. Further, a dry heat treatment at 130 ° C. was performed at the same length, and the same length was further left at room temperature for one day. Next, the elongation state of the sample yarn was removed, and the length (L6) was measured.
The heat setting property is calculated by the following formula.

Heat setting property = 100 × {((L6) − (L5)) / (L5)}
[Deep color]
In the test piece preparation method, a sample yarn was wound around a 5 × 5 cm sample plate closely with a minimum load so that the influence of the color of the sample plate did not appear, and used as a sample. The front surface of the sample and the standard white surface of common use (JIS Z 8722 4.3.4) were covered with a uniform flat and transparent glass plate having a thickness of about 1 mm.

  The L value (brightness) was measured using a multi-light source spectrocolorimeter MSC-IS-2DH (manufactured by Suga Test Instruments). The L value is the brightness in Hunter Lab color display, and the smaller the value, the lower the brightness, that is, the deeper the black color.

[Dark color clarity, dust adhesion prevention]
A woven stretch fabric was produced by the following method, and the darkness vividness was evaluated.

  First, a sample polyurethane yarn was processed to obtain a covering yarn. A cationic dyeable polyester 168DTEX-48FIL was used as a blended partner yarn, and a covering yarn for a weft was obtained by processing a yarn using a covering machine under the conditions of twist number = 450 t / m and draft = 3.0. Similarly, a covering yarn for warp yarn was obtained by processing cationic dyeable polyester 168dTEX-48FIL using a covering machine under the condition of twist number 700 T / M draft = 3.5.

  Next, warping and weaving were performed. 5100 warp yarns (1100 rough winding warp) were glued and warped, and woven with a 2/1 twill structure using a rapier loom.

  Next, a dyeing process was performed. The raw machine obtained by weaving is scoured according to conventional methods, intermediate set (185 ° C), weight reduction, dyeing (cationic dye, 120 ° C), drying, finish treatment, finishing set (180 ° C, fabric speed 20 m / min, Set zone 24m) was carried out.

  And the dark color vividness and dust adhesion prevention property of the obtained fabric were evaluated.

  Dark color sharpness was determined in five stages, paying attention to the texture of the fabric (exposed polyurethane). The fabric is stretched under a load of 1.8 kg / 2 in. Grade 5-No peeling at all, Grade 4-Slightly peeled but almost unnoticeable, Grade 3-Grade 2-Slightly peeled -Grade 1 worried about eye opening-It was assumed that there was much eye opening and the urethane was exposed and the quality was low.

  The dust adhesion prevention property was determined in three stages. Evaluation was made by paying attention to the degree of dust adhesion after leaving a 1 m long × 70 cm wide fabric on an equilateral triangular table with an inclination of 60 degrees for one week in an atmosphere of 23 ° C. × 40% RH. Grade 3-No dust adhesion, Grade 2-Slight dust adhesion, Grade 1-Dust adhesion.

[Antistatic]
The above-mentioned woven stretch fabric was used as a sample, and the frictional voltage was measured by the following method as an index indicating antistatic properties.

  A friction static voltage was measured by using a rotary static tester manufactured by Koa Trading Co., Ltd. p. The charged voltage (friction charged voltage) after rotating for 1 minute at m was measured.

[Reference Example 1]
A polyurethane DMAC solution (35% by weight) composed of PTMG, MDI and ethylene glycol having a molecular weight of 2900 was polymerized to obtain a polymer solution A1. Next, carbon black manufactured by Asahi Carbon Co., Ltd. (average primary particle size 44 nm, specific surface area 40 m ² / g) and DMAc were added to A1, and a carbon black master batch dispersion was prepared. Horizontal mill WILLY A. Using DYNO-MIL KDL manufactured by BACHOFE, filled with 85% zirconia beads, a uniform fine dispersion was prepared at a flow rate of 20 g / min, and B1 (7% by weight of solid carbon black, 28% solid polyurethane % By weight, total 35% by weight). Further, polyurethanes formed by the reaction of t-butyldiethanolamine and methylene-bis- (4-cyclohexyl isocyanate) described in U.S. Pat. No. 3,555,115, and p described in U.S. Pat. No. 3,553,290. -A DMAc solution (35% by weight) of a mixture of a condensation polymer of cresol and divinylbenzene in a ratio of 2 to 1 was prepared as an antioxidant solution C1 (35% by weight). Polymer solutions A1, B1, and C1 were uniformly mixed at 95.5 wt%, 2.5 wt%, and 2.0 wt% to obtain Solution D1. This is dry-spun at a speed ratio of 540 m / min with a speed ratio of 1.4 between the godet roller and the winder, so that 200 g of polyurethane yarn having a content of 20 decitex, monofilament and carbon black of 0.5% by weight is wound. Got the body.

  Table 1 shows the breaking elongation, breaking strength, setability, stress relaxation, and deep color of the obtained yarn. The L value was 25, indicating a good deep color. Further, the breaking strength was the same as or higher than that of Comparative Example 1 in which the base polymer was the same and the content of carbon black was the same, but the L value (brightness) was 36 or more. Next, Table 2 shows the dark color vividness, dust adhesion preventing property and antistatic property of the obtained stretch fabric. The base polymer is the same, and the carbon black content is the same, but the L value (brightness) is 36 or higher compared to the dark color sharpness grade 2 and dust adhesion prevention grade 1 of Comparative Example 1. A stretch fabric having a dark color sharpness of 4th grade, dust adhesion preventing grade of 3rd grade and excellent antistatic property was obtained.

[Reference Example 2]
Carbon black (average primary particle size 22 nm, specific surface area 114 m ² / g), copper phthalocyanine pigment (CI Pigment Green 7), and DMAc are added to A1, and carbon black master. A batch dispersion was prepared. Adjustment was performed in the same manner as in Reference Example 1. This was designated as B2 (solid content of carbon black 7% by weight, solid content of copper phthalocyanine pigment 1% by weight, solid content of polyurethane 27% by weight, total 35% by weight). Polymer solutions A1, B2, and C1 were uniformly mixed at 78 wt%, 20 wt%, and 2 wt% to obtain solution D2. This was dry-spun at a speed ratio of 1.40 between the godet roller and the winder at a speed of 540 m / min, so that the content of 20 dtex, monofilament, carbon black was 10% by weight, and the content of copper phthalocyanine pigment was 1. 200 g of a 4% by weight polyurethane yarn wound body was obtained.

  Table 1 shows the breaking elongation, breaking strength, setability, stress relaxation, and deep color of the obtained yarn. The L value was 18, indicating good deep color. The machine set was also moderate. Next, Table 2 shows the dark color vividness, dust adhesion preventing property and antistatic property of the obtained stretch fabric. Compared with the dark color sharpness grade 2 and dust adhesion prevention grade 1 of Comparative Example 1 having the same base polymer and an L value (lightness) of 36 or more, the dark color sharpness of Reference Example 1 is grade 5 and dust adhesion prevention Was a third grade, and a stretch fabric with excellent antistatic properties was obtained.

[Example 1]
Polyurethane urea DMAc solution (35% by weight) composed of PTMG having a molecular weight of 1800, MDI, ethylenediamine and diethylamine as a terminal blocking agent was polymerized to obtain a solution A2. Next, Lion black carbon black (Ketjen Black EC, average primary particle size of 40 nm, specific surface area of 1270 m ² / g) and DMAc were added to A2 to prepare a carbon black master batch dispersion. This was designated as B3 (7% by weight of carbon black in solid content, 28% by weight of polyurethane in solid content, total 35% by weight). Adjustment was performed in the same manner as in Reference Example 1. A2, B3, and C1 were uniformly mixed at 88 wt%, 10 wt%, and 2 wt% to obtain a solution D3. By spinning the solution D3 at a speed of 600 m / min with a speed ratio of the godet roller and the winder of 1.20, a 20-dtex multifilament and a carbon black content of 2.0% by weight 500 g wound thread body was obtained.

  Table 1 shows the breaking elongation, breaking strength, setability, stress relaxation, and deep color of the obtained yarn. The L value was 23, indicating a good deep color. Next, Table 2 shows the dark color vividness, dust adhesion preventing property and antistatic property of the obtained stretch fabric. The base polymer is the same, and the carbon black type is the same, but the dark color of Reference Example 1 is higher than that of Comparative Example 2 which has an L value (brightness) of 36 or more, as compared with the dark color sharpness first grade and dust adhesion prevention first grade. A stretch fabric having a sharpness of 5th grade, a dust adhesion preventing property of 3rd grade and excellent antistatic properties was obtained.

[Example 2]
Polyurethane urea DMAC solution (35% by weight) composed of PTMG, MDI having a molecular weight of 1800, ethylenediamine having a molar ratio of 80/20, 1,3-cyclohexyldiamine and diethylamine as a terminal blocking agent was polymerized to obtain a solution A3. A3, B3, and C1 were uniformly mixed at 78 wt%, 20 wt%, and 2 wt% to obtain Solution D3. By spinning the solution D3 at a speed of 600 m / min with a speed ratio of the godet roller and the winder of 1.30, 20 dtex multifilament and polyurethane yarn having a carbon black content of 4.0% by weight 500 g wound thread body was obtained.

  Table 1 shows the breaking elongation, breaking strength, setability, stress relaxation, and deep color of the obtained yarn. The L value was 21, indicating good deep color. Next, Table 2 shows the dark color vividness, dust adhesion preventing property and antistatic property of the obtained stretch fabric. Compared with the first example of dark color sharpness grade 1 and dust adhesion prevention grade 1 of Comparative Example 3 having the same base polymer and an L value (brightness) of 36 or more, the dark color clarity of reference example 1 is grade 5 and dust adhesion prevention property. Was a third grade, and a stretch fabric with excellent antistatic properties was obtained.

[Comparative Example 1]
Polymer solution A1 and additive solution C1 are mixed, and the same carbon black (average primary particle diameter is 22 nm, specific surface area is 114 m ² / g) and additional DMAc, which are the same as those used in Reference Example 2, are used. In addition, after primary mixing with a stirring blade, a uniform solution E1 was obtained using a 45 mm diameter twin screw extruder manufactured by Kurimoto Steel Works. The solution E1 was dry-spun at a speed ratio of 540 m / min with a speed ratio of the godet roller and the winder of 1.40 to obtain a yarn having a content of 18 dtex, monofilament, and carbon black of 0.5% by weight. .

  Table 1 shows the breaking elongation, breaking strength, setability, stress relaxation, and deep color of the obtained yarn. The L value was 48. The dark color sharpness was second grade, and when a polyurethane yarn having a high L value was used as the fabric, the eyes were worried, and the dark color sharpness in this case was an unsatisfactory result.

[Comparative Example 2]
Polymer solution A2 and additive solution C1 were mixed, and carbon black (Ketjen Black EC, average primary particle diameter of 40 nm, specific surface area of 1270 m ² / g) manufactured by Lion Corporation and additional DMAc were added thereto. After the primary mixing, a uniform solution E2 was obtained using a 45 mm diameter twin screw extruder manufactured by Kurimoto Steel Works. The solution E2 was dry-spun at a speed of 600 m / min with a speed ratio of the godet roller and the winder of 1.20, so that 20 decitex multifilament and carbon black content of 0.05% by weight 500 g wound thread body was obtained.

  Table 1 shows the breaking elongation, breaking strength, setability, stress relaxation, and deep color of the obtained yarn. The L value was 39. When the polyurethane yarn having a high L value was used as a fabric, the dark color sharpness was first grade, and the urethane was exposed with a lot of eyes, resulting in an unsatisfactory result.

[Comparative Example 3]
Polymer solution A3 and additive solution C1 were mixed, and carbon black (average primary particle diameter of 140 nm or more, specific surface area of 20 m ² / g) and additional DMAc were added to this, and primary stirring was performed with a stirring blade. After mixing, a uniform solution E3 was prepared using a 45 mm diameter biaxial extruder manufactured by Kurimoto Steel Works. By spinning the solution E3 at a speed of 600 m / min with a speed ratio of the godet roller and the winder of 1.30, a 500 g spool of 20 dtex multifilament and carbon black content of 0.05% by weight Got.

  Table 1 shows the breaking elongation, breaking strength, setability, stress relaxation, and deep color of the obtained yarn. The L value was 43. When the polyurethane yarn having a high L value was used as a fabric, the dark color sharpness was first grade, and the urethane was exposed with a lot of eyes, resulting in an unsatisfactory result.

Claims (11)

A polyurethane yarn produced by dry spinning, port main constituent of polyurethane is a polyol with a diisocyanate, containing mosquitoes over carbon black and the monoamine, in the content of carbon black is less than 20 wt% 0.1 wt% A polyurethane yarn characterized in that carbon black is ketjen black .   The polyurethane yarn according to claim 1, further comprising a condensation polymer of p-cresol and divinylbenzene.   Furthermore, the polyurethane thread | yarn of Claim 1 or 2 containing the polyurethane produced | generated by reaction of t-butyl diethanolamine and a methylene-bis- (4-cyclohexyl isocyanate). Polyurethane yarn according to any one of claims 1 to 3, average primary particle size before Symbol carbon black is characterized by a 20 nm to 100 nm. The polyurethane yarn according to any one of claims 1 to 4 , wherein the carbon black has a specific surface area of 20 m ² / g or more. The polyurethane yarn according to any one of claims 1 to 5 , wherein the fineness is 10 to 110 dtex. Carbon black and the monoamine to the polyurethane solution which is a main component is a polyol and a diisocyanate addition, the polyurethane solution A manufacturing method of a reportage polyurethane yarn to produce a polyurethane yarn by dry spinning, the carbon black is Ketjen Black And a method for producing a polyurethane yarn, wherein the carbon black is contained in the range of 0.1 wt% to 20 wt% . The method for producing a polyurethane yarn according to claim 7 , wherein a condensation polymer of p-cresol and divinylbenzene is added to the polyurethane solution. The polyurethane yarn according to claim 7 or 8 , wherein a polyurethane produced by a reaction of t-butyldiethanolamine and methylene-bis- (4-cyclohexyl isocyanate) is added to the polyurethane solution. Method. The method for producing a polyurethane yarn according to any one of claims 7 to 9 , wherein the carbon black has an average primary particle size of 20 nm to 100 nm. Method for producing a polyurethane yarn according to any one of claims 7 to 10, a specific surface area of the carbon black is characterized in that it is 20 m 2 / ^g or more.