JP6383570B2 - Polyurethane elastic fiber - Google Patents

Description

  TECHNICAL FIELD The present invention relates to a polyurethane elastic fiber having heat-bonding properties useful for preventing fraying of clothing products mainly containing polyurethane elastic fibers, and a knitted fabric or woven fabric using the elastic fibers.

Polyurethane elastic fibers are fibers having an excellent elastic function, and are used by knitting and knitting with various fibers from synthetic fibers such as nylon and polyester to regenerated fibers and natural fibers. Its use is very wide ranging from garments such as foundations, socks, pantyhose, swimwear, compression wear, etc., where demand has been rapidly increasing in recent years, to diapers, bandages, nets, tapes, and automobile interior materials.
Normally, fabrics using polyurethane elastic fibers are manufactured through manufacturing processes such as cutting, sewing, finishing, etc., but when cutting and sewing, depending on the design of the fabric, the cutting part is likely to fray easily. A problem arises in that the polyurethane elastic fibers come off from the knitted fabric structure of the fabric at a harder frayed edge and the stretchability of the fabric at that portion is lowered.
In addition, in products using polyurethane elastic fibers, such as pantyhose, when a part of the yarn in the fabric breaks during use, the structure collapses from that part. Happens. If a “run” occurs when worn, the appearance will be greatly impaired, and there will be problems from the viewpoint of the durability of products using polyurethane elastic fibers, such as being forced to change, and economical to the user.

  In order to cope with these problems, in Patent Document 1 below, a specific polyurethane compound is added to polyurethane urea, and the polyurethane elastic fiber has thermal bonding performance, so that heat treatment at the time of processing causes the cut portion of the fabric. It is disclosed to improve fraying. However, in the method described in Patent Document 1, sufficient heat bonding performance cannot be expressed unless a high temperature of 180 ° C. is applied. For example, in pantyhose, a general preset temperature is used. A sufficient fraying prevention function cannot be obtained at a processing temperature of 90 ° C. to 120 ° C. In the technique described in Patent Document 1, in order to obtain a sufficient fraying prevention function, it is necessary to increase the preset temperature at the time of processing, and a facility for applying a high preset temperature to the processor is required. Equipment burden increases. In addition, since the high temperature is applied, not only the energy cost is increased, but also the texture of the product is lowered.

  Patent Document 2 below discloses the use of polyurethane elastic fibers having a low melting point. However, the polyurethane elastic fiber obtained by the technique described in Patent Document 2 can prevent fraying even by heat treatment at a low temperature, but due to the low melting point, it is due to heat during knitting processing such as dyeing and setting. There is a large decrease in the physical properties of the yarn, and at a preset temperature of 170 ° C. or higher, which is the use condition of general polyurethane elastic fibers other than pantyhose, a heat resistance aspect such as a significant decrease in fabric recoverability and yarn breakage occurs. There was a problem.

JP 2007-177359 A JP 2006-307409 A

  In view of the problems of the prior art, the problem to be solved by the present invention is to provide a polyurethane elastic fiber having high recoverability, heat resistance, heat fusion even at a low processing temperature, and having a high fraying prevention function It is to be.

  As a result of intensive studies to solve the above problems, the present inventors have determined that a polyurethane compound having a specific molecular weight is used as a polyurethane elastic fiber as a polyurethane elastic fiber that exhibits a fraying prevention property of clothing products at a lower processing temperature than in the past. It has been found that the above-mentioned problems can be solved by adding to the coalescence, and the present invention has been made.

That is, the present invention is as follows.
[1] A polyurethane elastic fiber containing a polyurethane compound and a polyurethane urea polymer, wherein the polyurethane compound is obtained by reacting a high molecular weight polyol, a diisocyanate, and a low molecular weight diol, and has a molecular weight of 60,000 to 150,000. And the polyurethane elastic fiber, wherein among the diisocyanate-derived units constituting the polyurethane compound and the polyurethaneurea polymer, the aliphatic diisocyanate-derived unit is 5 mol% or more and 50 mol% or less .

  [2] The polyurethane elastic fiber according to [1], wherein the polyurethane compound is contained in an amount of 5% by weight to 50% by weight and the polyurethane urea polymer is contained in an amount of 50% by weight or more.

  [3] The polyurethane elastic fiber according to [1] or [2], wherein an outflow start temperature of the polyurethane compound by a flow tester is 80 ° C. or higher and 160 ° C. or lower.

[ 4 ] The aliphatic diisocyanate is 1,6-hexamethylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, And the polyurethane elastic fiber according to any one of the above [ 1 ] to [3], which is at least one selected from the group consisting of isophorone diisocyanate.

[ 5 ] The polyurethane elastic fiber according to any one of [1] to [ 4 ], wherein the heat-bonding peeling stress between polyurethane elastic fibers when wet-heat treatment at 98 ° C. is 0.1 cN / dt or more.

[ 6 ] The polyurethane elastic fiber according to any one of [1] to [ 5 ], wherein the heat-bonding peeling stress between polyurethane elastic fibers when subjected to a dry heat treatment at 180 ° C. is 0.2 cN / dt or more.

[ 7 ] The polyurethane elastic fiber according to any one of [1] to [ 6 ], wherein a deknitting stress at the time of wet heat treatment at 98 ° C. is 0.2 cN / dt or more.

[ 8 ] A fabric using at least a part of the polyurethane elastic fiber according to any one of [1] to [ 7 ].

  By using the polyurethane elastic fiber of the present invention for fabrics and apparel products, the fraying is suppressed because adhesion occurs between the polyurethane elastic fibers or between the polyurethane elastic fibers and the other yarn at a lower processing temperature than before. You can get clothing products. Not only can the energy cost at the time of processing be kept low, but also it is possible to avoid a decrease in texture and deterioration of the counterpart material due to heat treatment at high temperatures. Also. The polyurethane elastic fiber of the present invention has not only a low processing temperature but also a heat resistance sufficient to maintain a sufficient elastic performance even at a high processing temperature. It is possible to provide a product in combination with any partner yarn commonly used in textile products in which the fiber is used.

It is a figure explaining the thermobonding peeling stress measuring method of polyurethane elastic fibers. It is a figure explaining the thermal-bonding peeling stress measuring method in the knitted fabric which consists of a polyurethane elastic fiber covered with the nylon thread | yarn.

Hereinafter, embodiments of the present invention will be described in detail.
The polyurethane elastic fiber of the present invention contains or consists essentially of a polyurethane compound and a polyurethane urea polymer. However, the inclusion of other additives is not excluded.

  The polyurethane urea polymer used in this embodiment can be obtained by reacting, for example, a polymer polyol, diisocyanate, a bifunctional amine, and a terminal stopper having a monofunctional active hydrogen atom.

  As the polymer polyol, various diols composed of a substantially linear homo- or copolymer, for example, polyester diol, polyether diol, polyester amide diol, polyacryl diol, polythioester diol, polythioether diol, polycarbonate diol or A mixture thereof or a copolymer thereof may be used. Polyalkylene ether glycol is preferable, for example, polyoxyethylene glycol, polyoxypropylene glycol, polytetramethylene ether glycol, polyoxypentamethylene glycol, copolymer polyether composed of tetramethylene group and 2,2-dimethylpropylene group A copolymer polyether glycol composed of glycol, tetramethylene group and 3-methyltetramethylene group, or a mixture thereof. Among them, polytetramethylene ether glycol, which shows an excellent elastic function, and a copolymer polyether glycol composed of a tetramethylene group and a 2,2-dimethylpropylene group are preferable, and the number average molecular weight is preferably 500 to 5,000. . A more preferred number average molecular weight is 1,000 to 3,000.

  Examples of the diisocyanate include aliphatic, alicyclic and aromatic diisocyanates. For example, 4,4′-diphenylmethane diisocyanate (MDI), 2,4′-diphenylmethane diisocyanate, 2,4- and 2,6-tolylene diisocyanate, m- and p-xylylene diisocyanate, α, α, α ′ , Α′-tetramethyl-xylylene diisocyanate, 4,4′-diphenyl ether diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) Cyclohexane, 3- (α-isocyanatoethyl) phenyl isocyanate, 1,6-hexamethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate or a mixture thereof or a combination thereof. Examples include polymers.

  With respect to the method for producing the polyurethane urea polymer of the present embodiment, a known polyurethane reaction technique such as a prepolymer method or a one-shot method can be used. For example, polyalkylene ether glycol and diisocyanate are reacted under diisocyanate-excess conditions to synthesize a urethane prepolymer having an isocyanate group at the terminal, and then this urethane prepolymer is subjected to a chain extension reaction with a bifunctional amine to produce polyurethane. Urea can be obtained.

Regarding the operation of the polyurethane reaction, an amide polar solvent such as dimethylformamide, dimethyl sulfoxide, dimethylacetamide or the like can be used during the synthesis of the urethane prepolymer or the reaction between the urethane prepolymer and the active hydrogen-containing compound. Preferred is dimethylacetamide.
Moreover, when synthesizing a polyurethane urea polymer, a known metal catalyst or amine catalyst may be used alone or in combination of two or more. Examples of the metal catalyst include organotin catalysts such as zinc, titanium, and bismuth in addition to organotin catalysts such as dibutyltin dilaurate and stannous octoate. Examples of the amine-based catalyst include triethylenediamine, N, N, N ′, N′-tetramethylhexamethylenediamine, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, N-methyl-N ′-( 2-dimethylaminoethyl) piperazine, N-methylmorpholine, N-ethylmorpholine, triethylamine, N, N-dimethylaminoethanol, 1,8-diaza-bicyclo [5,4,0] undecene-7 (DBU), Organic acid salt etc. are mentioned.

  The polyurethane compound used in this embodiment can be obtained by reacting a polymer polyol, diisocyanate, and a low molecular diol. Moreover, you may make the terminal stopper which has a monofunctional active hydrogen atom react.

  As the high-molecular polyol, various diols consisting of substantially linear homo- or copolymers, for example, polyester diol, polyether diol, polyester amide diol, polyacryl diol, polythioester diol, polythioether diol, or these diols Examples thereof include a mixture or a copolymer thereof. Polyether diol includes polyoxyethylene glycol, polyoxypropylene glycol, polytetramethylene ether glycol, polyoxypentamethylene glycol, copolymer polyether glycol consisting of tetramethylene group and 2,2-dimethylpropylene group, tetramethylene group And a copolymerized polyether glycol consisting of 3-methyltetramethylene groups or a mixture thereof. Polyester diols include adipate polyester diols by condensation dehydration reaction of dibasic acids such as adipic acid and phthalic acid and glycols such as ethylene glycol and 1,4-butanediol, and polycaprolactone by ring-opening polymerization of ε-caprolactone. Diol, polycarbonate diol and the like. The polymer polyol preferably has a number average molecular weight of 500 to 2,500. More preferably, it is 600-2,200.

  Examples of the diisocyanate include aliphatic, alicyclic and aromatic diisocyanates. For example, 4,4′-diphenylmethane diisocyanate (MDI), 2,4′-diphenylmethane diisocyanate, 2,4- and 2,6-tolylene diisocyanate, m- and p-xylylene diisocyanate, α, α, α ′ , Α′-tetramethyl-xylylene diisocyanate, 4,4′-diphenyl ether diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) Cyclohexane, 3- (α-isocyanatoethyl) phenyl isocyanate, 1,6-hexamethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate or a mixture thereof or a combination thereof. Examples include polymers.

  Examples of the low molecular diol used as the chain extender include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 2,2-dimethyl-1,3-propanediol, 1,4-butanediol, 1,3-butanediol, hexamethylene glycol, diethylene glycol, 1,10-decanediol, 1,3-dimethylolcyclohexane, 1,4-dimethylolcyclohexane can be used. Ethylene glycol, 1,3-propanediol, and 1,4-butanediol are preferable.

  Examples of the terminal terminator having a monofunctional active hydrogen atom include methanol, ethanol, 2-propanol, 2-methyl-2-propanol, 1-butanol, 2-ethyl-1-hexanol, and 3-methyl-1-. Monoalcohols such as butanol, monoalkylamines such as isopropylamine, n-butylamine, t-butylamine, 2-ethylhexylamine, diethylamine, dimethylamine, di-n-butylamine, di-t-butylamine, diisobutylamine, di And dialkylamines such as -2-ethylhexylamine and diisopropylamine. These may be used alone or in combination.

  Regarding the method for producing the polyurethane compound of the present embodiment, a known polyurethane reaction technique such as a prepolymer method or a one-shot method can be used. For example, a high-molecular polyol and diisocyanate are reacted under an excess of diisocyanate to synthesize a urethane prepolymer having an isocyanate group at the end, and then this urethane prepolymer is subjected to a chain extension reaction with a low-molecular diol to produce a polyurethane compound. Can be obtained.

Regarding the operation of the polyurethane reaction, an amide polar solvent such as dimethylformamide, dimethyl sulfoxide, dimethylacetamide or the like can be used during the synthesis of the urethane prepolymer or the reaction between the urethane prepolymer and the low molecular diol. Preferred is dimethylacetamide.
Moreover, when synthesizing a polyurethane urea polymer, a known metal catalyst or amine catalyst may be used alone or in combination of two or more. Examples of the metal catalyst include organotin catalysts such as zinc, titanium, and bismuth in addition to organotin catalysts such as dibutyltin dilaurate and stannous octoate. Examples of the amine-based catalyst include triethylenediamine, N, N, N ′, N′-tetramethylhexamethylenediamine, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, N-methyl-N ′-( 2-dimethylaminoethyl) piperazine, N-methylmorpholine, N-ethylmorpholine, triethylamine, N, N-dimethylaminoethanol, 1,8-diaza-bicyclo [5,4,0] undecene-7 (DBU) And organic acid salts thereof.

  The polyurethane compound used in the present embodiment has a molecular weight of 60,000 to 150,000. The molecular weight described here refers to a molecular weight in terms of polystyrene measured by GPC described later. When the molecular weight of the polyurethane compound is less than 60000, the strength of the polyurethane elastic fiber is lowered, and the heat resistance against heat at the time of dyeing and setting is greatly lowered. Further, when the molecular weight of the polyurethane compound exceeds 150,000, sufficient heat bonding performance cannot be obtained. The molecular weight of a preferred polyurethane compound having both the strength / heat resistance of the polyurethane elastic fiber and the thermal adhesive peel stress is from 80000 to 130,000, more preferably from 90000 to 120,000.

  The polyurethane elastic fiber of the present embodiment contains or consists of a polyurethane compound and a polyurethane urea polymer, but the proportion of the polyurethane compound in the polyurethane elastic fiber is preferably 5% by weight or more and 50% by weight or less. . If the ratio of the polyurethane compound is less than 5% by weight, sufficient heat-sealing performance cannot be expressed by heat during processing. If it exceeds 50% by weight, the strength and heat resistance of the polyurethane elastic fiber are greatly increased. It will drop to. The content of a preferable polyurethane compound having both the strength and heat resistance of the polyurethane elastic fiber and the thermal adhesive peeling stress is more preferably 10% by weight or more and 40% by weight or less.

  The polyurethane compound contained in the polyurethane elastic fiber of the present embodiment preferably has an outflow start temperature by a flow tester described later in the range of 80 ° C. or higher and 160 ° C. or lower. If the polyurethane compound outflow start temperature is lower than 80 ° C, yarn breakage may occur due to heat during processing, and spinning may become unstable when producing polyurethane elastic fibers. Does not exhibit thermal bonding performance. The flow temperature of the polyurethane compound having both the strength / heat resistance of the polyurethane elastic fiber and the thermal adhesive peel stress is more preferably 90 ° C. or higher and 150 ° C. or lower.

In the polyurethane elastic fiber of the present embodiment, 5 mol% or more and 50 mol% or less of all the diisocyanate-derived units constituting the polyurethane compound and the polyurethane urea polymer in the polyurethane elastic fiber are aliphatic diisocyanates. preferable. If the content of the aliphatic isocyanate-derived unit is less than 5 mol%, the heat bonding performance becomes insufficient, and if it exceeds 50 mol%, problems such as a decrease in strength of the polyurethane elastic fiber and thread breakage after heat treatment may occur. is there.
The aliphatic diisocyanate described here may have a chain structure or a cyclic structure.

  Specific examples of the aliphatic diisocyanate having a chain structure include ethylene diisocyanate, tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, Examples include 2,6-diisocyanatomethyl caproate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate.

Specific examples of the aliphatic diisocyanate having a cyclic structure include 4,4′-dicyclohexylmethane diisocyanate (H ₁₂ MDI), 1,3-bis (isocyanatomethyl) cyclohexane (1,3-H ₆ XDI), 1,4. -Bis (isocyanatomethyl) cyclohexane (1,4-H ₆ XDI), isophorone diisocyanate (IPDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, bis (2-isocyanatoethyl) -4-cyclohexylene-1,2 -Dicarboxylate, 2,5-norbornane diisocyanate, 2,6-norbornane diisocyanate, methylcyclohexane-2,4-diisocyanate, methylcyclohexane-2,6-diisocyanate, cyclohexane-1,4-diis Examples include isocyanate, hexahydroxylylene diisocyanate, hexahydrotolylene diisocyanate, and octahydro-1,5-naphthalene diisocyanate.

The polyurethane elastic fiber of this embodiment includes 1,6-HDI, IPDI, H ₁₂ MDI, 1,3-H ₆ XDI, and 1,4-H among the aliphatic diisocyanates having the above-mentioned chain and cyclic structures. More preferably, it is at least one selected from the group consisting of ₆ XDI. These may be used alone or in combination of two or more.
As described above, the unit derived from the aliphatic diisocyanate constituting the polymer in the polyurethane elastic fiber of the present invention may be contained in either one of the polyurethane compound and the polyurethane urea polymer. Although it may be contained in both, it is preferred that the polyurethane elastic fiber is contained only in the polyurethane compound from the viewpoint of heat resistance and stretch recovery of the polyurethane elastic fiber.

  In the polyurethane elastic fiber of this embodiment, it is preferable that the peeling stress at the time of heat-processing and heat-bonding polyurethane elastic fibers is more than a specific performance, respectively. For example, when processing of pantyhose is assumed, it is preferable that the peeling stress is 0.1 cN / dt or more when the polyurethane fiber is thermally bonded to each other by a wet heat of 98 ° C. by an evaluation method described later. If this thermal bond peeling stress is 0.1 cN / dt or more, a sufficient run-preventing function can be exhibited in a product using the polyurethane elastic fiber of the present embodiment, for example, pantyhose. From the viewpoint of developing a run prevention function, the thermal adhesive peeling stress is more preferably 0.2 cN / dt or more, and further preferably 0.3 cN / dt or more.

  Further, when the produced circular knitted fabric is treated at a preset wet heat of 98 ° C. by the evaluation method described later, it is preferable that the knitting stress when the polyurethane elastic fiber is pulled out from the knitted fabric is 0.2 cN / dt or more. . When the knitting stress of the knitted fabric is 0.2 cN / dt or more, a sufficient fraying prevention function is exhibited in various garments. From the viewpoint of exhibiting a fraying prevention function, the knitted fabric unknitting stress is more preferably 0.3 cN / dt or more, and further preferably 0.4 cN / dt or more.

  When a fabric for general clothing is assumed, it is preferable that the peeling stress of the yarn when the polyurethane fibers are thermally bonded to each other at 180 ° C. dry heat is 0.2 cN / dt or more by an evaluation method described later. If this thermal bond peeling stress is 0.2 cN / dt or more, the fabric using the polyurethane elastic fiber of this embodiment can exhibit a sufficient fraying prevention function. From the viewpoint of developing a fraying prevention function, the thermal adhesive peeling stress is more preferably 0.2 cN / dt or more, and further preferably 0.3 cN / dt or more.

  The polyurethane elastic fiber of this embodiment is obtained by spinning a polyurethane spinning stock solution obtained by dissolving a polyurethane composition comprising a polyurethane compound having a molecular weight of 60000 to 150,000 and a polyurethaneurea polymer in an amide polar solvent, It is obtained by processing. The spinning method may be any known spinning method, but dry spinning is preferable from the viewpoint of the strength of the polyurethane elastic fiber. Examples of the amide polar solvent include dimethylformamide, dimethyl sulfoxide, and dimethylacetamide.

As a method of mixing the polyurethane compound and the polyurethane urea polymer, any method may be used. A method of mixing after dissolving in a solvent, a method of combining polyurethane yarn and a polyurethane compound after spinning from separate nozzles during spinning, a method of combining yarns, a method of localizing a polyurethane compound on the fiber surface and taking a sheath core structure Any of these may be used. However, from the viewpoint of production processability, it is preferable to spin a spinning stock solution in which a polyurethane compound and a polyurethane urea polymer are uniformly mixed.
In order to mix uniformly in the polyurethane spinning dope, a method of mixing a polyurethane compound and / or polyurethane urea polymer synthesized in an amide polar solvent, a polyurethane compound polymerized without solvent was dissolved in an amide polar solvent. Examples thereof include a method of later adding to a polyurethane urea solution, a method of adding a melted polyurethane polymer to the polyurethane urea solution, and a method of dissolving a powdered or pelleted polyurethane compound in an amide polar solvent of the polyurethane composition.

  The polyurethane elastic fiber of the present embodiment includes known additives usually used for polyurethane elastic fibers, such as ultraviolet absorbers, antioxidants, light stabilizers, gas anti-coloring agents, chlorine-resistant agents, colorants, Matting agents, lubricants, fillers and the like may be added.

  The polyurethane elastic fiber of this embodiment preferably contains 1.0% by weight or more and 6.0% or less of dimethyl silicone. By containing 1.0% by weight or more of dimethylsilicone, when using polyurethaneurea elastic fiber, the yarn from the package has good detackiness and suppresses degradation of detacking over time. be able to. In addition, when the content of dimethyl silicone is 6.0% by weight or less, it is possible to prevent the yarn from collapsing from the package.

  The polyurethane elastic fiber of this embodiment can contain dimethyl silicone, mineral oil, or the like as an oil agent, and may contain modified silicones such as polyester-modified silicone, polyether-modified silicone, and amino-modified silicone. In addition, oils include mineral fine particles such as talc and colloidal alumina, higher fatty acid metal salt powders such as magnesium stearate and calcium stearate, higher aliphatic carboxylic acids, higher aliphatic alcohols, paraffin, polyethylene and other solid waxes at room temperature. Etc. may be used alone or in any combination as required.

  The polyurethane elastic fiber of the present embodiment can be combined with other fiber materials to obtain a fabric such as a knitted fabric or a woven fabric. These can be, for example, various stretch foundations such as girdles, bras, intent products, underwear, and clothing products such as tights, pantyhose, body suits, spats, swimwear, sportswear, outerwear, stretch linings, and the like. The fabric using the polyurethane elastic fiber according to the present embodiment is highly frayed by heat-bonding the polyurethane elastic fiber in the fabric with the polyurethane elastic fiber or the partner yarn through a thermal processing process such as presetting, dyeing, and final setting. Expresses the prevention function. The fiber material used for the fabric using the polyurethane elastic fiber of the present embodiment is not particularly limited. For example, polyamide fiber such as nylon 6 or nylon 66, polyester fiber such as polyethylene terephthalate or polytrimethylene terephthalate, copper ammonia regeneration Examples include natural fibers such as rayon, viscose rayon, acetate rayon, cotton, silk, wool, and hemp.

EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these.
First, an analysis method for polyurethane compounds and various evaluation methods for evaluating the performance of polyurethane elastic fibers will be described.

(1) Molecular Weight Measurement of Polyurethane Compound A polyurethane compound is dissolved in a dimethylacetamide solution containing LiBr 0.02 mol / L so that the solid content concentration is 0.25% by weight to obtain a measurement sample.
The produced sample is measured by the GPC-101 manufactured by Shodex under the following conditions. In addition, the molecular weight of a polyurethane compound refers to the number average molecular weight calculated from a calibration curve obtained from the peak top molecular weight of all polystyrene standard samples (SM-105) manufactured by Shodex.
Column: (sample side) → KD-G → KD-806M → KD-806M → KD-802.5 → KD-801 × 3 → RI-71S (detector) (all the above are manufactured by Shodex)
Column oven temperature: 60 ° C
Flow rate: 1.0 ml / min
Eluent: Dimethylacetamide solution containing LiBr at a concentration of 0.02 mol / L

(2) Outflow start temperature measurement of polyurethane compound The polyurethane compound is measured using a flow tester CFT-500D type (manufactured by Shimadzu Corporation). When the polyurethane compound is in the form of particles such as pellets, when the maximum outer diameter exceeds 2 mm, it is measured after being reduced to 2 mm or less. In addition, when the polyurethane compound is dissolved in a solvent such as dimethylacetamide, the solution is cast on a glass plate so that the thickness after drying is about 100 μm and dried in a drying cabinet at 50 ° C. for 12 hours or more. After being filmed, it is cut out on a strip of 5 mm width, further cut into 1 mm intervals, and thinned to about 1 mm × 5 mm × 100 μm for measurement.
The amount of sample required for one measurement is 1.5 g, the die (nozzle) is 0.5 mm in diameter and 1.0 mm in thickness, 5 kg extrusion load is applied, and preheating is performed at an initial setting temperature of 80 ° C. A curve of the stroke length (mm) and temperature when the temperature is raised to 250 ° C. at a rate of 3 ° C./min after 240 seconds is obtained. As the temperature rises, the polymer inside the toner is heated and begins to flow out of the die. The temperature at this time is defined as the outflow start temperature.

(3) Thermal adhesive peel stress (Polyurethane elastic fibers at 98 ° C wet heat)
Two test yarns sampled at a width of 5 cm (both ends are fixed by being sandwiched between double-sided tapes) are entangled at the center as shown in FIG. In a state where the raw yarn is stretched to 100%, it is treated with steam at 98 ° C. for 20 minutes. After the treatment, the sample is removed from the metal frame, the entanglement is released, and the two are brought into contact with each other only at the fused portion. The test yarn ends are overlapped.
Using a tensile tester (Orientec Co., Ltd. UTM-III-100 type (trade name)), both ends of each test yarn are held and set together with the upper and lower chucks of the tester. The maximum stress P (cN) at which the tensile bonded portion is peeled off at 50 cm / min is measured and divided by the fineness (dt) of the polyurethane elastic fiber sample.

(4) Thermal adhesive peel stress (polyurethane elastic fibers at 180 ° C dry heat)
Two test yarns sampled with a width of 5 cm (both ends are fixed with a double-sided tape) are entangled at the center as shown in FIG. 1, and fixed to the mold with an interval of 1 cm. Washing with hot water is performed at 90 ° C. for 10 minutes in a state where the raw yarn is stretched to 100%, and then treated at 180 ° C. for 1 minute with dry heat. After the treatment, the sample is removed from the metal frame, the entanglement is released, and the two are brought into contact with each other only at the fused portion. The test yarn ends are overlapped.
Using a tensile tester (Orientec Co., Ltd. UTM-III-100 type (trade name)), both ends of each test yarn are held and set together with the upper and lower chucks of the tester. The maximum stress P (cN) at which the tensile bonded portion is peeled off at 50 cm / min is measured and divided by the fineness (dt) of the polyurethane elastic fiber sample.

(5) Knit fabric disassembly stress After covering the polyurethane elastic fiber of this embodiment with nylon 66 yarn 13dT / 7f with 1600T / m and covering draft 2.3, the yarn is round-knitted with 24 gauge / 2.54cm. A single-neck round knitted fabric is produced with a knitting tension of 1 g load. The prepared circular knitted fabric is pre-set with 98 ° C. steam for 20 minutes, boiled with 100 ° C. water for 30 minutes, and finally set with 120 ° C. steam for 20 seconds. Cut the heat-treated knitted fabric along the stitches and set the knitted fabric on the upper chuck as shown in Fig. 2 using a tensile tester (UTM-III-100 (trade name) manufactured by Orientec Co., Ltd.). The end of the polyurethane elastic fiber pulled out from the end of the knitted fabric is set on the lower chuck, pulled at a speed of 50 cm / min, and the stress T (cN) when the polyurethane elastic fiber is extracted from one end of the knitted fabric is measured. Divide by the fineness (dt) of the elastic fiber sample.

(6) Run evaluation The treated knitted fabric prepared in the previous section was put on a foot shape with a diameter of 33 cm at the knee, the knee thread was cut into two and a half stitches, and then the flexion and extension movement was performed 50 times to obtain the length of the run. (Cm) was measured. The case where no run was performed was “◯”, the case where the run was less than 1 cm was “Δ”, and the case where the run was 1 cm or more was “x”.

[ Reference Example 1]
The polytetramethylene ether glycol having a number average molecular weight of 2000 is reacted with 1.6 times molar equivalent of 4,4′-diphenylmethane diisocyanate under stirring in a dry nitrogen atmosphere at 80 ° C. for 3 hours. A capped polyurethane prepolymer was obtained. After cooling to room temperature, dimethylacetamide was added and dissolved to obtain a polyurethane prepolymer solution.
On the other hand, a solution of ethylenediamine and diethylamine dissolved in dry dimethylacetamide is prepared and added to the prepolymer solution at room temperature to obtain a polyurethane urea solution having a polyurethane solid content concentration of 30 wt% and a viscosity of 450 Pa · s (30 ° C.). PA1 was obtained.

  Separately, polytetramethylene ether glycol having a number average molecular weight of 2000 and 2.5 times molar equivalent of 4,4′-diphenylmethane diisocyanate were reacted under stirring in a dry nitrogen atmosphere at 80 ° C. for 3 hours. After the polyurethane prepolymer was capped with an isocyanate at the end, 1,4-butanediol was added to the prepolymer at room temperature to obtain a polyurethane having a molecular weight of 110,000 in terms of polystyrene and an outflow start temperature of 154 ° C. Dimethylacetamide was added thereto to obtain a polyurethane solution PU1 having a solid content concentration of 30% by weight.

  The obtained polyurethane urea solution and polyurethane solution were mixed at a weight ratio of PA1: PU1 = 80: 20, and 4,4′-butylidenebis (3-methyl-6-t) was added to the solid content of the polyurethane urea and polyurethane. -Butylphenol) is mixed with 1% by weight and 0.5% by weight of 2- (2′-hydroxy-3′-t-butyl-5′-methylphenyl) -5-chlorobenzotriazole is mixed with the polyurethane solution. The solution was defoamed under reduced pressure at room temperature to obtain a spinning dope.

  This spinning dope is dry-spun at a spinning speed of 800 m / min and a hot air temperature of 310 ° C. Before the resulting polyurethane elastic fiber is wound on a package, 80% by weight of polydimethylsiloxane and 18% by weight of mineral oil are used as finishing agents. Then, an oil agent composed of 2% by weight of magnesium stearate was applied to the polyurethane elastic fiber in an amount of 4% by weight, and the polyurethane elastic fiber of 22 dtex / 2 filament was obtained by winding it on a paper tube.

[Example 2]
Instead of the polyurethane solution PU1 of Reference Example 1, polytetramethylene ether glycol having a number average molecular weight of 2000 and 2.5-fold molar equivalent of 1,6-hexamethylene diisocyanate (HDI) were added in a dry nitrogen atmosphere at 80 times. After reacting for 3 hours at a temperature under stirring to make a polyurethane prepolymer end-capped with an isocyanate, 1,4-butanediol was added to the prepolymer at room temperature to obtain a molecular weight of 65000 and an outflow start temperature of 133. A polyurethane at 0 ° C. was obtained. Dimethylacetamide was added thereto to obtain a polyurethane solution PU2 having a solid concentration of 30% by weight.
The obtained polyurethane solution was mixed at PA1: PU2 = 80: 20, and a polyurethane elastic fiber having 22 dtex / 2 filaments was obtained in the same manner as in Reference Example 1.

[ Reference Example 3]
Instead of PU1 of Reference Example 1, PU2 of Example 2 was mixed at a weight ratio of PA1: PU2 = 40: 60, and a polyurethane elastic fiber having 22 dtex / 2 filaments was obtained in the same manner as Reference Example 1.

[Example 4]
Instead of the polyurethane solution PU1 of Reference Example 1, polytetramethylene ether glycol having a number average molecular weight of 2,000 and 2.5 times molar equivalent of 4,4′-dicyclomethane diisocyanate (H12MDI) were added under a dry nitrogen atmosphere. The mixture was reacted at 80 ° C. with stirring for 3 hours to obtain a polyurethane prepolymer whose end was capped with an isocyanate, and then 1,4-butanediol was added to the prepolymer at room temperature, and the molecular weight was 100,000. A polyurethane having a temperature of 118 ° C. was obtained. Dimethylacetamide was added thereto to obtain a polyurethane solution PU3 having a solid content concentration of 30% by weight.
The obtained polyurethane solution was mixed at PA1: PU2 = 80: 20, and a polyurethane elastic fiber having 22 dtex / 2 filaments was obtained in the same manner as in Reference Example 1.

[Example 5]
Instead of the polyurethane solution PU1 in Reference Example 1, polytetramethylene ether glycol having a number average molecular weight of 2000 and 4,4'-molar equivalent of 4,4'-dicyclomethane diisocyanate (H12MDI) were added in a dry nitrogen atmosphere. After reacting under stirring at 3 ° C. for 3 hours to obtain a polyurethane prepolymer having an end capped with an isocyanate, 1,4-butanediol was added to the prepolymer at room temperature to obtain a molecular weight of 135,000 and an outflow start temperature of 184. A polyurethane at 0 ° C. was obtained. Dimethylacetamide was added thereto to obtain a polyurethane solution PU4 having a solid content concentration of 30% by weight.
The obtained polyurethane solution was mixed at PA1: PU4 = 80: 20, and a polyurethane elastic fiber having 22 dtex / 2 filaments was obtained in the same manner as in Reference Example 1.

[Example 6]
Instead of the polyurethane solution PU1 of Reference Example 1, polytetramethylene ether glycol having a number average molecular weight of 2000 and 2.5-fold molar equivalent of isophorone diisocyanate (IPDI) at 80 ° C. for 3 hours under a dry nitrogen atmosphere, After reacting with stirring to obtain a polyurethane prepolymer whose ends are capped with isocyanate, 1,4-butanediol is added to the prepolymer at room temperature to obtain a polyurethane having a molecular weight of 120,000 and an outflow start temperature of 145 ° C. It was. Dimethylacetamide was added thereto to obtain a polyurethane solution PU5 having a solid content concentration of 30% by weight.
The obtained polyurethane solution was mixed at PA1: PU5 = 70: 30, and a polyurethane elastic fiber having 22 dtex / 2 filaments was obtained in the same manner as in Reference Example 1.

[Example 7]
Polytetramethylene ether glycol having a number average molecular weight of 2000 and a mixed diisocyanate (MDI: 1,3-bis (isocyanatomethyl) cyclohexane (1,3-H6XDI) = 7: 3 (mole) with respect to 1.6 times the molar equivalent of the polytetramethylene ether glycol Ratio)) was allowed to react under stirring in a dry nitrogen atmosphere at 80 ° C. for 3 hours to obtain a polyurethane prepolymer whose ends were capped with an isocyanate. After cooling to room temperature, dimethylacetamide was added and dissolved to obtain a polyurethane prepolymer solution.
On the other hand, a solution of ethylenediamine and diethylamine dissolved in dry dimethylacetamide is prepared and added to the prepolymer solution at room temperature to obtain a polyurethane urea solution having a polyurethane solid content concentration of 30% by weight and a viscosity of 430 Pa · s (30 ° C.). PA2 was obtained.
The obtained polyurethane urea solution PA2 and PU1 of Reference Example 1 were mixed at PA2: PU1 = 80: 20 (weight ratio) to obtain polyurethane elastic fibers of 22 dtex / 2 filaments in the same manner as Reference Example 1.

[Example 8]
In Example 5, instead of polyurethane solution PU1, PU3 used in Reference Example 3 was mixed at PA2: PU3 = 80: 20 (weight ratio), and in the same manner as Reference Example 1, 22 dtex / 2 filament polyurethane Elastic fibers were obtained.

[Comparative Example 1]
The polytetramethylene ether glycol having a number average molecular weight of 2000 is reacted with 1.6 times molar equivalent of 4,4′-diphenylmethane diisocyanate under stirring in a dry nitrogen atmosphere at 80 ° C. for 3 hours. A capped polyurethane prepolymer was obtained. After cooling to room temperature, dimethylacetamide was added and dissolved to obtain a polyurethane prepolymer solution.
On the other hand, a solution of ethylenediamine and diethylamine dissolved in dry dimethylacetamide is prepared and added to the prepolymer solution at room temperature to obtain a polyurethane urea solution having a polyurethane solid content concentration of 30 wt% and a viscosity of 450 Pa · s (30 ° C.). PA1 was obtained.
4,4′-butylidenebis (3-methyl-6-tert-butylphenol) is 1% by weight, 2- (2′-hydroxy-3′-tert-butyl) based on the solid content in the obtained polyurethaneurea solution PA1. 0.5% by weight of -5′-methylphenyl) -5-chlorobenzotriazole was mixed with a polyurethane solution to obtain a uniform solution, and then defoamed under reduced pressure at room temperature to obtain a spinning dope.
This spinning dope is dry-spun at a spinning speed of 800 m / min and a hot air temperature of 310 ° C. Before the resulting polyurethane elastic fiber is wound on a package, 80% by weight of polydimethylsiloxane and 18% by weight of mineral oil are used as finishing agents. Then, an oil agent composed of 2% by weight of magnesium stearate was applied to the polyurethane elastic fiber in an amount of 4% by weight, and the polyurethane elastic fiber of 22 dtex / 2 filament was obtained by winding it on a paper tube.

[Comparative Example 2]
A polytetramethylene ether glycol having a number average molecular weight of 2000 and 2.5 times molar equivalent of 4,4′-diphenylmethane diisocyanate were reacted under stirring in a dry nitrogen atmosphere at 80 ° C. for 3 hours. After forming an isocyanate-capped polyurethane prepolymer, 1,4-butanediol was added to the prepolymer at room temperature to obtain a polyurethane having a molecular weight of 110000 and an outflow start temperature of 154 ° C. in terms of polystyrene. Dimethylacetamide was added thereto to obtain a polyurethane solution PU1 having a solid content concentration of 30% by weight.
4,4′-Butylidenebis (3-methyl-6-t-butylphenol) is 1% by weight, 2- (2′-hydroxy-3′-t-butyl-) based on the solid content in the obtained polyurethane solution PU1. After mixing 0.5% by weight of 5′-methylphenyl) -5-chlorobenzotriazole with the polyurethane solution to obtain a uniform solution, the solution was degassed under reduced pressure at room temperature to obtain a spinning dope.
This spinning dope is dry-spun at a spinning speed of 800 m / min and a hot air temperature of 310 ° C. Before the resulting polyurethane elastic fiber is wound on a package, 80% by weight of polydimethylsiloxane and 18% by weight of mineral oil are used as finishing agents. Then, an oil agent composed of 2% by weight of magnesium stearate was applied to the polyurethane elastic fiber in an amount of 4% by weight, and the polyurethane elastic fiber of 22 dtex / 2 filament was obtained by winding it on a paper tube.

[Comparative Example 3]
Instead of the polyurethane solution PU1 of Reference Example 1, a polytetramethylene ether glycol having a number average molecular weight of 2,000 and 2.5 times molar equivalent of MDI were reacted under stirring in a dry nitrogen atmosphere at 80 ° C. for 3 hours. Then, after making a polyurethane prepolymer whose ends were capped with isocyanate, 1,4-butanediol was added to the prepolymer at room temperature to obtain a polyurethane having a molecular weight of 160000 and an outflow start temperature of 177 ° C. Dimethylacetamide was added thereto to obtain a polyurethane solution PU6 having a solid content concentration of 30% by weight.
The obtained polyurethane solution was mixed at PA1: PU6 = 80: 20, and a polyurethane elastic fiber having 22 dtex / 2 filaments was obtained in the same manner as in Reference Example 1.

[Comparative Example 4]
Instead of PU1 in Reference Example 1, polytetramethylene ether glycol having a number average molecular weight of 2000 and 2.5 times molar equivalent of 1,6-hexamethylene diisocyanate were added at 80 ° C. for 3 hours under a dry nitrogen atmosphere. After reacting with stirring to obtain a polyurethane prepolymer whose ends are capped with isocyanate, 1,4-butanediol is added to the prepolymer at room temperature to obtain a polyurethane having a molecular weight of 30000 and an outflow start temperature of 118 ° C. It was. Dimethylacetamide was added thereto to obtain a polyurethane solution PU7 having a solid content concentration of 30% by weight.
Instead of PU1 of Reference Example 1, PU6 was mixed at a weight ratio of PA1: PU7 = 80: 20, and a polyurethane elastic fiber of 22 dtex / 2 filaments was obtained in the same manner as Reference Example 1.

[Comparative Example 5]
Instead of the polyurethane solution PU1 of Reference Example 1, polytetramethylene ether glycol having a number average molecular weight of 2,000 and 2.5 times molar equivalent of 4,4′-dicyclomethane diisocyanate (H12MDI) were added under a dry nitrogen atmosphere. The mixture was reacted at 80 ° C. with stirring for 3 hours to obtain a polyurethane prepolymer having an end capped with an isocyanate, and then 1,4-butanediol was added to the prepolymer at room temperature, and the molecular weight was 160000. A polyurethane having a temperature of 155 ° C. was obtained. Dimethylacetamide was added thereto to obtain a polyurethane solution PU8 having a solid content concentration of 30% by weight.
The obtained polyurethane solution was mixed at PA1: PU8 = 80: 20, and a polyurethane elastic fiber having 22 dtex / 2 filaments was obtained in the same manner as in Reference Example 1.
Table 1 below shows the composition and performance of each of the above Reference Examples, Examples and Comparative Examples.

  By using the polyurethane elastic fiber according to the present embodiment, fraying is suppressed, a fabric excellent in processability with few restrictions on conditions can be obtained, and fraying prevention performance is exhibited even at a processing temperature lower than before. Therefore, it can be used even by a processor who has not previously had equipment for high temperature application. Furthermore, by using fabrics that do not require edge trimming due to heat during processing, various stretch foundations such as girdles, bras, intimate products, underwear, tights, pantyhose, and the like can be provided with excellent wear feeling. The polyurethane elastic fiber of this embodiment is a waistband, body suit, spats, swimwear, stretch sportswear, stretch outerwear, medical wear, stretch lining, and other garments, diapers, belts, etc. It can be suitably used for non-clothing applications.

Claims (8)

A polyurethane elastic fiber containing a polyurethane compound and a polyurethane urea polymer, said polyurethane compound is obtained by reacting a high molecular weight polyol, a diisocyanate, and a low molecular weight diol, molecular weight Ri der 60000 150,000 or less, and The polyurethane elastic fiber, wherein among the diisocyanate-derived units constituting the polyurethane compound and the polyurethaneurea polymer, the aliphatic diisocyanate-derived unit is 5 mol% or more and 50 mol% or less .   The polyurethane elastic fiber according to claim 1, wherein the polyurethane compound contains 5 wt% or more and 50 wt% or less and the polyurethaneurea polymer contains 50 wt% or more.   The polyurethane elastic fiber according to claim 1 or 2, wherein an outflow start temperature of the polyurethane compound by a flow tester is 80 ° C or higher and 160 ° C or lower. The aliphatic diisocyanate is 1,6-hexamethylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, and isophorone diisocyanate. The polyurethane elastic fiber according to any one of claims 1 to 3 , which is at least one selected from the group consisting of: The polyurethane elastic fiber according to any one of claims 1 to 4 , wherein a heat-bonding peeling stress between polyurethane elastic fibers when wet-heat treatment at 98 ° C is 0.1 cN / dt or more. The polyurethane elastic fiber according to any one of claims 1 to 5 , wherein a heat-bonding peeling stress between polyurethane elastic fibers when subjected to a dry heat treatment at 180 ° C is 0.2 cN / dt or more. The polyurethane elastic fiber according to any one of claims 1 to 6 , wherein a deknitting stress when wet-heat treatment at 98 ° C is 0.2 cN / dt or more. Fabrics used in at least a portion of the polyurethane elastic fiber according to any one of claims 1-7.

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