CN1396320A - Polyurethane spandex and its manufacturing method, cottons and silks and swimwear - Google Patents

Abstract

The present invention is related to polyurethane elastic fiber which is characterized by consisting from polyurethane urea and polyurethane and preparation thereof. The polyurethane elastic fiber of present invention can be used for the usage of swimming suit by way of such excellent anti-chlorine brittle function and thermoset property.

Description

Polyurethane elastic fiber, method for producing same, fabric and swimwear

technical field

The present invention relates to polyurethane elastic fiber, its production method, cloth and swimwear.

More specifically, it relates to a polyurethane elastic fiber excellent in chlorine resistance suitable for swimwear used in swimming pools and the like.

technical background

Polyurethane elastic fiber has a high degree of rubber elasticity and is widely used in stockings, underwear, sportswear, etc. due to its excellent mechanical properties such as tensile stress and recovery, and thermal properties.

However, when clothing products using polyurethane elastic fibers are soaked in chlorine bleach for a long time and washed repeatedly, there is a problem that the elastic function of polyurethane elastic fibers decreases.

That is, when swimwear using polyurethane elastic fibers is repeatedly soaked in sterilizing chlorine water with an active chlorine concentration of 0.5-3 ppm such as an aqueous pool, the elastic function of the polyurethane elastic fibers is significantly impaired, resulting in filament breakage.

In order to improve the chlorine resistance of polyurethane elastic fibers, polyester-based polyurethane elastic fibers using aliphatic polyester diol as a raw material have been disclosed, but the chlorine resistance is not sufficient. Moreover, due to the high biological activity of aliphatic polyester, it has the disadvantage that bacteria can easily invade polyester polyurethane elastic fibers, and there are also problems such as reduced elastic function of swimwear and easy occurrence of broken filaments during use or storage. Polyether-based polyurethane elastic fibers using polyether diol with minimal biological activity as a raw material have a low risk of embrittlement caused by bacteria, but there is still a problem that chlorine resistance is inferior to that of polyester-based polyurethane elastic fibers.

Polyether-based polyurethane elastic fibers lack thermal residual deformation characteristics. Therefore, various fiber cloths and silks containing polyurethane elastic fibers have the problem of thermal residual deformation.

That is, since polyurethane elastic fibers have very low thermal residual deformation efficiency, filaments made of polyurethane elastic fibers require a long time and high temperature for thermal residual deformation. In fiber cloth containing nylon fibers and polyurethane elastic fibers, when the thermal residual deformation temperature is high, there is a problem of causing unevenness of fibers. The breaking strength of this kind of silk is small, and it is also difficult to process the silk into fiber cloth. When wearing clothing made of this kind of silk, there is a concern that the clothing will be damaged. This concern is particularly pronounced in the case of filaments of small denier polyurethane elastic fibers used in women's socks and swimwear.

Contents of the invention

The object of the present invention is to provide a polyurethane elastic fiber suitable for swimwear having excellent chlorine resistance and thermal residual deformation characteristics and a method for stably producing the polyurethane elastic fiber in view of the above-mentioned problems in the prior art.

In order to solve the above-mentioned problems, the present invention adopts the following solutions.

That is, the polyurethane elastic fiber of the present invention is characterized by being formed of polyurethane urea and polyurethane.

In order to solve the above-mentioned problems, the method for producing polyurethane elastic fibers of the present invention adopts the following solutions.

That is, the method for producing polyurethane elastic fibers of the present invention is characterized in that a solution containing polyurethane urea and polyurethane as solutes is spun.

Embodiment of the invention

The present invention will be described in detail below.

The polyurethane elastic fiber of the present invention is formed of polyurethane urea and polyurethane.

The main constituents of the polyurethane urea in the present invention are preferably polyols, diisocyanates and diamines.

Polyols used in polyurethane urea are preferably polyether diols, polyester diols, polycarbonate diols, and the like.

When the polyurethane elastic fiber of the present invention is especially used in swimwear, from the perspective of preventing bacteria from causing embrittlement, as polyols, for example, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol (hereinafter referred to as PTMG) are preferably used. ), THF and 3-MeTHF copolymer denatured PTMG (hereinafter referred to as 3M-PTMG), THF and 2,3-dimethyl THF copolymer denatured PTMG, Japanese Patent No. 2615131, etc. Polyether diols such as side chain polyols. These polyether diols may be used alone or in combination of two or more, or by copolymerization.

As the polyurethane elastic fiber, when wear resistance and light resistance are especially required, it is preferable to use butylene adipate, polycaprolactone diol, and those having side chains disclosed in JP-A-61-26612, etc. Polyester-based diols such as polyester polyols and polycarbonate diols disclosed in JP-A-2-289516 and the like.

Such polyols may be used alone, or may be used after mixing or copolymerizing not less than two kinds. From the viewpoint of obtaining polyurethane elastic fibers excellent in elongation, strength, elastic recovery, and heat resistance, the number average molecular weight of the polyol used in the polyurethane urea of the present invention is preferably in the range of 1000 to 8000, more preferably 1800 ~6000 range.

As the diisocyanate used in the polyurethane urea of the present invention, aromatic diisocyanate, aliphatic diisocyanate, alicyclic diisocyanate, araliphatic diisocyanate, and modified products of these diisocyanates (carbodiimide modified product, urethane denatured form, urodiketone denatured form, etc.), a mixture of not less than two of them, and the like.

Specific examples of the aforementioned aromatic diisocyanates are preferably 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-benzylidene diisocyanate, 2,6-benzylidene diisocyanate, Diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate (hereinafter referred to as MD1), 4,4'-diphenyl diisocyanate, 3,3 '-Dimethyl-4,4'-diphenyl diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate , 1,4'-diisocyanate benzene, xylylene diisocyanate, 2,6-naphthalene diisocyanate, etc.

Specific examples of the aforementioned aliphatic diisocyanate are preferably ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 2,2,4-trimethyl Hexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylhexanoate, bis(2-isocyanate ethyl) carbonate, 2-isocyanate ethyl-2, 6-hexyl diisocyanate, etc.

As specific examples of the above-mentioned alicyclic diisocyanates, dicyclohexylmethane-4,4'-diisocyanate, cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, bis(2-isocyanate ethyl )-4-cyclohexylene-1,2-dicarboxylate, 2,5-norbornanyl diisocyanate, 2,6-norbornanyl diisocyanate, methylene bis(cyclohexyl isocyanate) (hereinafter referred to as H ₁₂ MDI), Methylcyclohexane 2,4-diisocyanate, Methylcyclohexane 2,6-diisocyanate, Cyclohexane 1,4-diisocyanate, Hexahydroxylylene diisocyanate, Hexahydrobenzylidene Diisocyanate, octahydro-1,5-naphthalene diisocyanate, etc.

Specific examples of the aforementioned araliphatic diisocyanate are preferably m-xylylene diisocyanate, tere-xylylene diisocyanate, α, α, α', α'-tetramethylxylylene diisocyanate, and the like.

Among these, aromatic diisocyanate is preferable, and MDI is more preferable from the standpoint of improving the strength of the final product and obtaining excellent heat resistance and strength in various applications.

From the viewpoint of inhibiting yellowing of polyurethane silk, aliphatic diisocyanate is preferred.

Likewise, these diisocyanates may be used alone or in combination of two or more.

The chain extender used in the polyurethane urea of the present invention is preferably a low molecular weight diamine or the like. Examples of low molecular weight diamines include ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, hexamethylenediamine, 1,3-cyclohexyldiamine, hexahydrom-phenylenediamine, 2- Methylpentamethylenediamine, bis(4-aminophenyl)phosphine oxide, etc. It is preferable to use one kind or not less than two kinds selected from these low molecular weight diamines. Ethylenediamine is preferable from the standpoint of elongation and elastic recovery, and further from obtaining excellent heat resistance.

As the chain extender, one having a hydroxyl group and an amino group in the molecule such as ethanolamine is preferably used.

Of these chain extenders, it is preferable to use a triamine compound capable of forming a crosslinked structure, for example, diethylenetriamine which does not lose its effect.

In the present invention, the polyurethane preferably has polyols, diisocyanates and diols as its main constituents.

The polyols and diisocyanates used in polyurethane can be the same as those used in polyurethane urea, but they can also be different from those used in polyurethane urea.

Among them, polytetramethylene ether glycol having a number average molecular weight of 2,500 to 5,000 is preferable as the polyhydric alcohol.

In the present invention, the chain extender used in polyurethane is preferably a low-molecular-weight diol. As the low molecular weight diol, for example, ethylene glycol, 1,3-propanediol, 1,4-butanediol, dihydroxyethoxybenzene, dihydroxyethylene terephthalate and the like are preferable.

One kind or not less than two kinds selected from these low-molecular-weight diols may be used.

The polyurethane elastic fiber of the present invention is formed from the above-mentioned polyurethane urea and the above-mentioned polyurethane.

Polyurethane elastic fibers formed only of polyurethane urea have insufficient chlorine embrittlement resistance and are inferior in thermal residual deformation.

Polyurethane elastic fibers made of only polyurethane have poor recovery properties and tend to become unstable in spinning, and there is a problem that elastic fibers with uniform deniers cannot be obtained especially at coarse deniers.

In the present invention, from the viewpoint of obtaining polyurethane elastic fibers particularly good in chlorine water resistance, thermal residual deformation, mechanical residual deformation, strength, elongation, and stress relaxation, the content of polyurethane is preferably 3% by weight to 97% by weight. % range, more preferably in the range of 3% by weight to 90% by weight.

In particular, from the viewpoint of stably spinning elastic fibers of uniform fineness, it is preferably 3% by weight to 50% by weight, more preferably 10% by weight to 40% by weight.

The content of polyurethane is preferably appropriately determined according to the use of the polyurethane elastic fiber.

The fineness, cross-sectional shape, etc. of the polyurethane elastic fiber of the present invention are not particularly limited. For example, the cross-sectional shape may be circular or flat.

The polyurethane elastic fiber of the present invention preferably contains various stabilizers, pigments and the like. For example, as photostabilizers, antioxidants, and the like, hindered phenol-based agents such as so-called BHT and Sumitomo Chemical Co., Ltd.'s "Sumilaiza-" GA-80, etc., benzotriphenylene-based agents such as "Chiubin" manufactured by Chiba Gaigi Co., Ltd. Azole-based and benzophenone-based reagents, phosphorus-based reagents such as Sumitomo Chemical Co., Ltd. "Sumilaiza-" P-16, various hindered amine-based reagents, inorganic pigments such as titanium oxide, zinc oxide, and carbon black, and fluorine-based resins Powder or silicone-based resin powder, metal soaps such as magnesium stearate, fungicides containing silver, zinc and their compounds, deodorants, polysiloxane, mineral oil and other lubricants, barium sulfate, oxidized Various antistatic agents such as cerium, betaine, and phosphoric acid are also preferably reacted with polymers.

In particular, from the perspective of further improving the durability against chlorine water for sterilization, light, and various nitrogen oxides, for example, it is best to use metal oxides selected from Mg, Zn, and Al such as zinc oxide, magnesium oxide, and aluminum oxide. compounds, composite oxides, hydroxides; solid solutions consisting of two or more selected from the group of metal oxides, composite oxides, and hydroxides selected from Mg, Zn, and Al, and Hydrotalcite-based compounds; anti-chlorine degradation agents such as mineral mixtures such as Mg ₂ Ca(CO ₃ ) ₄ (Fentaito) and hydromagnesite (brucite), for example, HN-150 produced by Nippon Hidradine Co., Ltd. Nitrogen supplements, for example, thermal oxidation stabilizers such as "Sumilaiza-" GA-80 manufactured by Sumitomo Chemical Industries, Ltd., for example, light stabilizers such as "Sumiso-bu"300#622 manufactured by Sumitomo Chemical Industries, Ltd., etc.

In particular, when the polyurethane elastic fiber of the present invention is used for swimwear, it is more preferable to use a chlorine deterioration inhibitor.

In the present invention, as this anti-chlorine deterioration agent, it is preferable to use at least one metal compound selected from the following 1) to 3):

1) Any of metal oxides, composite oxides, and hydroxides selected from Mg, Zn, and Al,

2) Among oxides, composite oxides, and hydroxides of metals selected from Mg, Zn, and Al, a solid solution consisting of two or more of the selected metals,

3) Hydrotalcite-like compounds.

That is, it is preferable to use only at least one type selected from group 1), at least one type selected from group 2), at least one type selected from group 3, and those selected from group 1) and group 2 respectively. ) at least one species from group 1), at least one species from groups 1) and 3), at least one species from groups 2) and 3), at least one species from groups 1), 2) and 3) Select at least one kind from the group.

As such an anti-chlorine deterioration agent, preferred are, for example, magnesium oxide, magnesium hydroxide, zinc oxide, zinc hydroxide, aluminum oxide, aluminum hydroxide, compounds containing divalent metal M (M represents at least one selected from Zn and Mg) 1 type) and aluminum, a composite oxide with a molar ratio of divalent metal to aluminum of 1 to 5, a composite oxide of MgO and ZnO, 2ZnO, ZnAl ₂ O ₄ 3ZnO, ZnAl ₂ O ₄ 4ZnO, ZnAl ₂ O ₄ 5ZnO, composite oxides represented by ZnAl ₂ O ₄ , hydrotalcites represented by Mg ₆ Al ₂ (OH) ₁₆ CO ₃ 4H ₂ O and Mg _4.5 Al ₂ (OH) ₁₃ CO ₃ 3.5H ₂ O compound, MgO/ZnO solid solution, ZnO/AlO solid solution, MgO/ZnO/AlO solid solution, Mg ₂ Ca(CO ₃ ) ₄ (Fentaito) and Mg ₄ (CO ₃ ) ₄ Mg(OH) ₃ 4H ₂ O (water Magnesite) mixture, etc. The most preferred are zinc oxide, hydromagnesite compounds, MgO/ZnO solid solution and a mixture of Mg ₂ Ca(CO ₃ ) ₄ and hydromagnesite.

In order to obtain a sufficient anti-chlorine degradation effect without adversely affecting the physical properties of the fiber, the amount of the anti-chlorine degradation agent added is preferably 0.1% to 10% by weight, more preferably 1% to 5% by weight, relative to the fiber mass.

The anti-chlorine deterioration agent used in the present invention is preferably a fine powder with an average particle diameter not greater than 1 μm in view of spinning stability.

For the purpose of improving the dispersibility of the anti-chlorine deterioration agent into the yarn and stabilizing the spinning, for example, it is preferable to use organic substances such as fatty acids, fatty acid esters, polyol-based organic substances, silane-based coupling agents, and titanate-based coupling agents. or their mixture for surface treatment.

Preferably, the polyurethane elastic fiber of the present invention is spun together with other natural fibers, chemical fibers, synthetic fibers, and semi-synthetic fibers to form fabrics, dyed and finished, sewn, and made into products such as swimwear. In order to weave knitted goods made of polyurethane elastic fibers and other fibers, various interweaving methods can be used. This knitwear can be warp-knitted or weft-knitted. When used for swimwear, it is best to be warp-knitted in terms of its function.

It can be knitted using a tricot machine or a raschel machine. The weaving weave can adopt any kind of weaving such as half weaving, reverse half weaving, double bar warp and satin weave, double bar warp weave and flat weave.

In terms of quality and style, the surface of knitwear is best made of other natural fibers, chemical fibers, synthetic fibers, and semi-synthetic fibers.

In the present invention, swimwear can be produced by sewing after dyeing by a usual method.

The swimwear of the present invention, in addition to being good in fit and quality, has little deterioration caused by chlorine water such as swimming pools, and has improved durability.

The method for producing the polyurethane elastic fiber of the present invention will be described below.

In the present invention, it is preferable to initially prepare a solution using polyurethane urea and polyurethane as solutes.

In the present invention, any method may be used for the production of polyurethane urea and polyurethane as the solute of the solution.

That is, either a melt polymerization method or a solution polymerization method may be used. However, more preferred is the solution polymerization method. In the solution polymerization method, polyurethane urea and polyurethane rarely produce foreign matter such as gel, and it is easy to obtain low-denier polyurethane elastic fibers. In addition, considering the labor saving and production efficiency of forming a solution, it is of course also preferable to adopt the solution polymerization method.

As the polyurethane urea used in the present invention, polyols with a molecular weight of 1000 to 8000, MDI, ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, hexamethylenediamine, 1,3- At least one diamine selected from cyclohexyldiamine and 2-methylpentamethylenediamine is synthesized, and the high-temperature side melting point is preferably 250°C to 300°C.

For the synthesis of polyurethane urea, for example, the best method is to first melt the polyol and MDI, then dissolve the reactant in DMAc, DMF, DMSO, NMP, etc. or a solvent based on them, and then mix with the above-mentioned diamine react to form a polyurethane urea solution.

Adjusting the melting point of polyurethane urea on the high temperature side to 250-300°C can be achieved by controlling the types and ratios of polyols, MDI, and diamines. When the molecular weight of the polyol is very high, the ratio of MDI can be increased relatively, and polyurethane urea with high melting point at high temperature can be obtained. When the molecular weight of the polyol is 1000 or more, the addition ratio ( (The number of moles of NCO groups based on diisocyanate)/(The number of moles of hydroxyl groups based on polyol)) is preferably not less than 1.3.

When synthesizing such a polyurethane urea, it is preferable to use a mixture of one or not less than two kinds of amine catalysts and organometallic catalysts. As amine-based catalysts, there are, for example, N,N-dimethylcyclohexylamine, N,N-dimethylbenzylamine, triethylamine, N-methylmorpholine, N,N-ethylmorpholine, N, N, N', N'-tetramethylethylenediamine, N, N, N', N'-tetramethyl-1,3-propanediamine, N, N, N', N'-tetramethyl Methylhexamethylenediamine, di-2-dimethylaminoethylether, N,N,N',N',N'-pentamethyldiethylenetriamine, tetramethylguanidine, triethylenediamine, N,N '-Dimethylpiperazine, N-methyl-N'-dimethylaminoethylpiperazine, N-(2-dimethylaminoethyl)morpholine, 1-methylimidazole, 1,2- Dimethylimidazole, N,N-dimethylaminoethanol, N,N,N'-triethylaminoethylethanolamine, N-methyl-N'-(2-hydroxyethyl)piperazine, 2, 4,6-tris(dimethylaminoethyl)phenol, N,N-dimethylaminohexanol, triethanolamine, etc.

As the organometallic catalyst, tin octoate, dibutyltin dilaurate, lead dibutyl octoate, and the like are preferable.

In the present invention, the concentration of the polyurethaneurea solution is usually preferably in the range of 30% by weight to 80% by weight.

Polyurethane used in the present invention is synthesized using at least one diol selected from polyols with a molecular weight of 1,000 to 8,000, MDI, ethylene glycol, 1,3-propanediol, and 1,4-butanediol , and the addition ratio as the ratio of the number of moles of NCO groups based on diisocyanate to the number of moles of hydroxyl groups based on polyol is preferably not less than 1.3.

More preferably, polytetramethylene ether glycol having a number average molecular weight of 2,500 to 5,000 is used, and the addition ratio as a ratio of the number of moles of NCO groups based on diisocyanate to the number of moles of hydroxyl groups based on polyol is 3.0 to 4.5 .

The synthesis of this polyurethane preferably adopts the following method, for example, various raw materials are dropped into DMAc, DMF, DMSO, NMP etc. and in the solvent that mainly consists of them, make it dissolve, heat to appropriate temperature, make it react, The so-called one-step method of obtaining a polyurethane solution; firstly, after the polyol and MDI are melt-reacted, the reactant is dissolved in the above-mentioned solvent, and then reacted with the above-mentioned diol to obtain a polyurethane solution.

When synthesizing such polyurethane, it is preferable to use a mixture of one or not less than two kinds of amine catalysts and organometallic catalysts. As the amine catalyst, there are, for example, N,N-dimethylcyclohexylamine, N,N-dimethylbenzylamine, triethylamine, N-methylmorpholine, N,N-ethylmorpholine, N , N, N', N'-tetramethylethylenediamine, N, N, N', N'-tetramethyl-1,3-propanediamine, N, N, N', N'-tetramethyl Hexamethylenediamine, Di-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-dimethylaminoethanol, N,N,N'-triethylaminoethylethanolamine, N-methyl-N'-(2-hydroxyethyl)piperazine, 2, 4,6-tris(dimethylaminoethyl)phenol, N,N-dimethylaminohexanol, triethanolamine, etc.

As the organometallic catalyst, tin octoate, dibutyltin dilaurate, lead dibutyl octoate, and the like are preferable.

In the present invention, the concentration of the polyurethane solution is usually preferably 30% by weight to 80% by weight, preferably the same as that of the polyurethaneurea solution.

In the present invention, a method of adding a polyurethane urea solution to a polyurethane urea solution may be used, or a method of adding a polyurethane urea solution to a polyurethane solution may be used.

In the present invention, it is preferable to employ a method of adding a small amount of solution to a large amount of solution in order to uniformly mix the solutions with each other.

In the present invention, polyurethane is preferably contained in an amount of 3% by weight to 97% by weight, more preferably in an amount of 3% by weight to 50% by weight, and most preferably in an amount of 10% by weight to 40% by weight.

At this time, it is best to add the polyurethane solution to the polyurethaneurea solution.

As a method of adding the polyurethane solution to the polyurethaneurea solution, any method can be used, and a method using a static mixer, a method using stirring, and the like are preferable.

Here, it is preferable to add the polyurethane solution added at the same time as the chlorine deterioration inhibitor, spinning light stabilizer, antioxidant and other reagents and pigments.

In the present invention, a solution containing polyurethane urea and polyurethane as solutes is spun, and the spinning method is preferably dry spinning or wet spinning.

Dry spinning is not particularly limited, and any method can be used.

The residual deformability and stress relaxation of the polyurethane elastic fiber of the present invention are easily affected by the speed ratio of the guide roll and the winder, and therefore should be appropriately determined according to the application.

In the present invention, it is desirable that the speed ratio of the guide roller and the winder is 1.15 to 1.65 for winding. In particular, when producing polyurethane elastic fibers with high residual deformation and low stress relaxation, it is more preferable to wind the above-mentioned speed ratio at 1.15 to 1.40, and it is most preferable to wind it at 1.15 to 1.35.

On the other hand, when producing polyurethane elastic fibers with low residual deformation and high stress relaxation, it is more preferable to wind the above-mentioned speed ratio at 1.25 to 1.65, more preferably at 1.35 to 1.65.

The spinning speed is preferably not lower than 450 m/min from the viewpoint of increasing the strength of the polyurethane elastic fiber during production.

Example

The present invention will be described in more detail below using examples.

Firstly, methods for measuring strength, stress relaxation, residual deformation, elongation, chlorine embrittlement resistance, and thermal residual deformation in the present invention will be described.

[Strength, stress relaxation, residual deformation, elongation]

The strength, stress relaxation, residual deformability, and elongation can be measured by performing a tensile test on the sample wire using a tensile testing machine of Universal Precision Tensile Testing Machine Model 4502.

These can be defined as follows. A sample of 5 cm (L1) was stretched to a length of 300% at a tensile speed of 50 cm/min and repeated 5 times, and the stress at this time was recorded as (G1).

The stretched length of 300% was held for 30 seconds, and the stress after holding for 30 seconds was designated as (G2). The length of the sample wire at which the stretched length is recovered and the stress becomes 0 is expressed as (L2). Furthermore, the sample wire was stretched until the sixth time to break. The stress at the time of breaking is represented as (G3), and the length of the sample wire at the time of breaking is represented as (L3).

Hereinafter, the above-mentioned characteristics are obtained by the following formula.

Intensity = (G3)

Stress relaxation=100×((G1)-(G2))/(G1)

Residual deformability=100×((L2)-(L1))/(L1)

Elongation=100×((L3)-(L1))/(L1)

[Chlorine embrittlement resistance]

Polyurethane elastic yarn:

Dilute the sodium hypochlorite solution with ion-exchanged water to form an available chlorine concentration of 3ppm, and then a urea concentration of 3ppm, and add chlorine water adjusted to pH 7.2 with sulfuric acid buffer solution into a constant temperature tank whose temperature is adjusted to 28°C. A weight of 5 g was applied to the sample wire, and the sample wire was immersed in a constant temperature bath, and the time until the sample wire was broken was evaluated.

knitwear:

The knitted fabric stretched by 50% in the transverse direction was dipped in the same chlorine water constant temperature bath as the polyurethane elastic yarn described above, and the time until the polyurethane elastic yarn of the knitted fabric was seen to be broken was evaluated.

[Hot Residual Deformability]

In a free state, the sample wire (length=L5) was stretched by 100% (length=2×(L5)), and treated at 180° C. for 1 minute at this length. Furthermore, at this length, it was left to stand at room temperature for 1 day. Release the stretched state of the sample wire, and measure its length (L6).

Thermal residual deformation=100×((L6)-(L5))/(L5)

[Example 1]

Tetramethylene ether diol and MDI with a molecular weight of 1800 are packed into a container so that the CR value is 1.58, react at 90° C., and dissolve the obtained reactant in N, N-dimethylacetamide (DMAc), Next, a DMAc solution containing ethylenediamine and diethylamine was added to the solution in which the above-mentioned reactant was dissolved to obtain a polyurethaneurea solution (solution A1) having a solid content in the polymer of 35% by weight.

In addition, tetramethylene ether diol and MDI with a molecular weight of 2900 were put into a container to make the CR value 3.5, and reacted at 90°C, then dissolved in DMAc, and then added ethyl alcohol to the solution in which the above reactant was dissolved. A DMAc solution of diol and butanol was used to obtain a polyurethane solution (solution B1) having a solid content in the polymer of 35% by weight.

Next, 450 g of solution B1 was added to 1800 g of solution A1, and stirred for 2 hours to obtain solution C1. Next, zinc oxide (fine zinc oxide, manufactured by Honso Chemical Co., Ltd.) was added to the solution C1 so that the polyurethane elastic fiber contained 3% by weight of zinc oxide, and stirred for 2 hours to prepare a solution D1. The speed ratio of the guide roller and the winder was set at 1.20, and the solution D1 was dry-spun at a speed of 540 m/min, and polyurethane elastic fibers (44 dtex, 4 filaments) were wound.

There is no trouble such as yarn breakage during spinning, and stable spinning is possible. The obtained polyurethane elastic fiber contains 19% by weight of polyurethane, has excellent resistance to chlorine embrittlement, and has excellent thermal residual deformation. The results are shown in Table 1 together.

[Example 2]

970 g of solution B1 was added to 1800 g of solution A1, and stirred for 2 hours to prepare solution C2. Next, zinc oxide (fine zinc oxide, manufactured by Honso Chemical Co., Ltd.) was added to the solution C2 so that the polyurethane elastic fiber contained 3% by weight of zinc oxide, and stirred for 2 hours to prepare a solution D2. The speed ratio of the guide roller and the winder was set to 1.20, and the solution D2 was dry-spun at a speed of 540 m/min, and the polyurethane elastic fiber (44 dtex, 4 filaments) was wound.

There is no trouble such as yarn breakage during spinning, and stable spinning is possible. The obtained polyurethane elastic fiber contains 34% by weight of polyurethane, has very good resistance to chlorine embrittlement, and has excellent thermal residual deformation. The results are shown in Table 1 together.

[Example 3]

Put tetramethylene ether diol and MDI with a molecular weight of 2100 into a container, make the CR value 2.1, react at 90°C, then dissolve in DMAc, and then add DMAc containing ethylene glycol and butanol to the above solution solution to obtain a polyurethane solution (solution B2) having a solid content in the polymer of 35% by weight.

Next, 1200 g of solution B2 was added to 1800 g of solution A1, and stirred for 2 hours to obtain solution C3. Next, zinc oxide (fine zinc oxide, manufactured by Honso Chemical Co., Ltd.) was added to the solution C3 so that the polyurethane elastic fiber contained 3% by weight of zinc oxide, and stirred for 2 hours to prepare a solution D3. The speed ratio of the guide roller and the winder was set to 1.20, and the solution D3 was dry-spun at a speed of 540 m/min, and the polyurethane elastic fiber (44 dtex, 4 filaments) was wound.

There is no trouble such as yarn breakage during spinning, and stable spinning is possible. The obtained polyurethane elastic fiber contains 39% by weight of polyurethane, has excellent resistance to chlorine embrittlement, and has extremely excellent thermal residual deformation. The results are shown in Table 1 together.

[Example 4]

1200 g of solution B1 was added to 800 g of solution A1, and stirred for 2 hours to obtain solution C4. Next, zinc oxide (fine zinc oxide, manufactured by Honso Chemical Co., Ltd.) was added to the solution C4 so that the polyurethane elastic fiber contained 3% by weight of zinc oxide, and stirred for 2 hours to prepare a solution D4. The speed ratio of the guide roller and the winder was set to 1.20, and the solution D4 was dry-spun at a speed of 540 m/min, and the polyurethane elastic fiber (44 dtex, 4 filaments) was wound.

Although the spinning was quite stable, about one breakage occurred in an average of 24 hours. The obtained polyurethane elastic fiber contains 58% by weight of polyurethane, has excellent resistance to chlorine embrittlement, and has excellent thermal residual deformation. The results are shown in Table 1 together.

[Example 5]

1600 g of solution B1 was added to 400 g of solution A1, and stirred for 2 hours to obtain solution C5. Next, zinc oxide (fine zinc oxide, manufactured by Honso Chemical Co., Ltd.) was added to the solution C5 so that the polyurethane elastic fiber contained 3% by weight of zinc oxide, and stirred for 2 hours to prepare a solution D5. The speed ratio of the guide roller and the winder was set at 1.20, and the solution D5 was dry-spun at a speed of 540 m/min, and polyurethane elastic fibers (44 dtex, 4 filaments) were wound.

Spinning was quite stable, but the yarn breakage occurred about once every 24 hours. The obtained polyurethane elastic fiber contained 78% by weight of polyurethane, had excellent resistance to chlorine embrittlement, and had excellent thermal residual deformation, and the results are shown in Table 1 together.

[Example 6]

Except that hydrotalcite (Mg ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O) powder was used instead of zinc oxide, other methods were the same as in Example 2 to obtain polyurethane elastic filaments. The obtained polyurethane elastic fiber has excellent chlorine embrittlement resistance and excellent thermal residual deformation. The results are shown in Table 1 together.

[Example 7]

Except that MgO/ZnO solid solution powder was used instead of zinc oxide, other methods were the same as in Example 2 to obtain polyurethane elastic filaments. The obtained polyurethane elastic fiber has excellent chlorine embrittlement resistance and excellent thermal residual deformation. The results are shown in Table 1 together.

[Example 8]

Polyurethane elastic yarns were obtained in the same manner as in Example 2, except that a 50:50 mixture of Mg ₂ Ca(CO ₃ ) ₄ (Fentaito) and hydromagnesite (manufactured by Microfine Minerals Ltd., UK) was used instead of zinc oxide. The obtained polyurethane elastic fiber has excellent resistance to chlorine embrittlement and excellent heat residual deformation, and the results are shown in Table 1.

[Example 9]

The polyurethane elastic fibers obtained in Example 2 and polyhexamethylene adipamide are melt-spun, and the obtained polyamide fibers (50 denier/17 filaments) are used to make tricot warps in two modes of warp knitting. Knitted fabric, this tricot fabric is dyed and finished and sewn into swimwear.

Chlorine embrittlement resistance of dyed tricot fabric with excellent performance of 122 hours, quality style is also very good.

The obtained swimwear was tested by wearing it in an actual swimming pool, and as a result, it was excellent in durability for 113 hours (average of wearing 4 times) until the polyurethane elastic yarns were broken.

[Comparative example 1]

Zinc oxide (fine zinc oxide, manufactured by Honso Chemical Co., Ltd.) was added to 1800 g of solution A1 to make polyurethane elastic fibers contain 3% by weight of zinc oxide, and stirred for 2 hours to prepare solution E1. The speed of the machine was taken as 1.20, and the solution E1 was dry-spun at a speed of 540 m/min, and the polyurethane elastic fiber (44 dtex, 4 filaments) was wound. The obtained polyurethane elastic fiber does not contain polyurethane, has low chlorine embrittlement resistance, and low thermal residual deformation. The results are shown in Table 1.

[Comparative example 2]

Zinc oxide (fine zinc oxide, manufactured by Honso Chemical Co., Ltd.) was added to 1800 g of solution B1 so that the polyurethane elastic fiber contained 3% by weight of zinc oxide, and stirred for 2 hours to prepare solution E2. The speed ratio between the guide roller and the winder was set at 1.20, and solution E2 was dry-spun at a speed of 540 m/min, and polyurethane elastic fibers (44 dtex, 4 filaments) were wound. When spinning with solution E2, the spinnability was poor and broken filaments were constantly generated.

The obtained polyurethane elastic fiber does not contain polyurethane urea. Although the chlorine embrittlement resistance is high and the thermal residual deformation is low, the recovery property is very poor (stress relaxation and residual deformation are large). The results are shown in Table 1.

[Comparative example 3]

Using the polyurethane elastic fiber of Comparative Example 1, tricot fabrics and swimwear were produced in the same manner as in Example 9. The chlorine embrittlement resistance of the dyed tricot fabric is very short, only 86 hours, and the swimwear wearing test shows that the polyurethane elastic yarn breaks at 79 hours.

Table 1 A B A/B (weight ratio) metal compound Strength (cN) Stress relaxation (%) Residual deformability (%) Elongation(%) Chlorine embrittlement resistance (time) Thermal residual deformation (%) Example 1 A1 B1 4/1 Zinc oxide 42 29 twenty one 455 133 61 Example 2 A1 B1 180/97 Zinc oxide 47 30 20 458 138 65 Example 3 A1 B2 3/2 Zinc oxide 41 30 twenty two 461 126 70 Example 4 A1 B1 2/3 Zinc oxide 44 30 twenty three 470 140 71 Example 5 A1 B1 1/4 Zinc oxide 41 31 twenty four 465 157 71 Example 6 A1 B1 180/97 Hydrotalcite 45 30 twenty one 455 134 66 Example 7 A1 B1 180/97 MgO/ZnO 44 31 twenty two 460 135 65 Example 8 A1 B1 180/97 Mg ₂ Ca(CO ₃ ) ₄ /hydromagnesite 46 30 20 451 130 63 Comparative example 1 A1 - ∞ Zinc oxide 41 28 twenty one 479 117 55 Comparative example 2 - B1 0 Zinc oxide 38 33 30 472 173 75 A: Polyurethane urea solution B: Polyurethane solution

Invention effect

According to the present invention, there can be provided a polyurethane elastic fiber which has excellent chlorine embrittlement resistance and thermal residual deformation properties and is suitable for swimwear.

By using the polyurethane elastic fiber of the present invention, it is possible to provide knitwear and swimwear which are excellent in fit and quality and style, are less deteriorated by chlorine water in swimming pools and the like, and are excellent in durability.

Claims (18)

1. A polyurethane elastic fiber, characterized in that it is formed of polyurethane urea and polyurethane. 2. The polyurethane elastic fiber according to claim 1, characterized in that it contains polyurethane in an amount of 3% to 97% by weight. 3. The polyurethane elastic fiber according to claim 1, characterized in that the polyurethane can be obtained from diol, polyol with a molecular weight of 1000-8000 and diphenylmethane diisocyanate. 4. The polyurethane elastic fiber according to claim 1, wherein in the polyurethane, the addition ratio which is the ratio of the number of moles of NCO groups based on diisocyanate to the number of moles of hydroxyl groups based on polyol is 1.3 or more. 5. The polyurethane elastic fiber according to claim 1, characterized in that: polyurethane is made of at least one diol selected from ethylene glycol, 1,3-propylene glycol, and 1,4-butanediol, with a molecular weight of 2500 ～5000 polytetramethylene ether glycol and diphenylmethane diisocyanate are synthesized, and the addition ratio as the ratio of the number of moles of NCO groups based on diisocyanate to the number of moles of hydroxyl groups based on polyol is 3.0～ 4.5. 6. The polyurethane elastic fiber according to claim 1, characterized in that it contains at least one metal compound selected from the following 1) to 3), wherein, 1) Any one of metal oxides, composite oxides, and hydroxides selected from Mg, Zn, and Al; 2) A solid solution composed of two or more selected metal oxides, composite oxides, and hydroxides selected from Mg, Zn, and Al; 3) Hydrotalcite-like compounds. 7. The polyurethane fiber according to claim 6, characterized in that it contains said metal compound in an amount of 0.1% by weight to 10% by weight. 8. The polyurethane elastic fiber according to claim 1, characterized in that it contains a mixture of Mg ₂ Ca(CO ₃ ) ₄ and hydromagnesite. 9. The polyurethane elastic fiber according to claim 8, characterized in that it contains the above-mentioned mixture in an amount of 0.1% to 10% by weight. 10. A fabric characterized by comprising the polyurethane elastic fiber as claimed in claim 1. 11. A swimwear characterized in that it is made of the fabric as claimed in claim 10. 12. A method for producing polyurethane elastic fiber, which is characterized by: spinning a solution containing polyurethane urea and polyurethane as solutes. 13. The method for producing polyurethane elastic fibers according to claim 12, wherein the polyurethane solution is added to the polyurethaneurea solution, followed by spinning. 14. The method for producing polyurethane elastic fiber according to claim 12, characterized in that the spinning method is a dry method. 15. The method for producing polyurethane elastic fiber according to claim 12, characterized in that it contains 3% to 97% by weight of polyurethane. 16. The method for producing polyurethane elastic fibers according to claim 12, wherein the polyurethane is formed by synthesizing diol, polyol with a molecular weight of 1000-8000, and diphenylmethane diisocyanate in a solution. 17. The method for producing polyurethane elastic fiber according to claim 12 or 16, characterized in that: in the polyurethane, the addition ratio which is the ratio of the number of moles of NCO groups based on diisocyanate to the number of moles of hydroxyl groups based on polyol is 1.3 or greater than 1.3. 18. The method for producing polyurethane elastic fibers according to claim 12, wherein the polyurethane is composed of at least one diol selected from ethylene glycol, 1,3-propanediol, and 1,4-butanediol, with a molecular weight of 2,500 to 5,000 polytetramethylene ether glycol and diphenylmethane diisocyanate are synthesized, and the addition ratio as the ratio of the number of moles of NCO groups based on diisocyanate to the number of moles of hydroxyl groups based on polyol is 3.0 ~4.5.