JP2002348727A - Polyurethane elastic fiber for sanitary product and method of producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide polyurethane elastic fiber for sanitary products which has excellent elastic properties causing no fatigue even at low temperature with high apparent fineness, fitting properties, good wearing properties and excellent wearing feel and the like. SOLUTION: The objective polyurethane elastic fiber is made of poly- urethane-urea polymer prepared from polyol, diisocyanate and diamine as the main components wherein the polyol includes random copolymer of tetrahydrofuran and ethylene oxide and/or propylene oxide.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyurethane elastic fiber for sanitary, which has excellent elastic properties without settling even at a low temperature, and has both good stretchability and recoverability, which is suitable for sanitary products, and its production. About the method.

[0002]

2. Description of the Related Art Elastic fibers are widely used in sanitary applications such as disposable diapers and sanitary napkins due to their excellent elasticity.

As such elastic fibers, polyurethane elastic fibers are used, which are disclosed in JP-A-63-235320, JP-A-5-239177 and JP-A-2-1-1.
No. 9511 discloses a technique for spinning a copolymer of tetrahydrofuran and 3-methyltetrahydrofuran, and a polyurethane polymer comprising an organic diisocyanate and a diamine compound.

[0004]

However, in the prior art, when elastic fibers are used in a disposable diaper or the like, it is difficult to draft up, and the amount of elastic fibers used per product can be reduced. And the production cost could not be reduced.

[0005] Further, the production amount per unit time cannot be improved.

An object of the present invention is to provide a polyurethane elastic fiber for sanitary and a method for producing the same, which could not be obtained by the prior art.

[0007]

The polyurethane elastic fiber for sanitary of the present invention employs the following means in order to solve the above-mentioned problems.

That is, a polyurethane urea whose main constituent is a polyol, a diisocyanate and a diamine, wherein the polyol contains a random copolymer of tetrahydrofuran and ethylene oxide and / or propylene oxide. It is a polyurethane elastic fiber.

The method for producing a polyurethane elastic fiber for sanitary of the present invention employs the following means in order to solve the above-mentioned problems.

That is, a polyurethaneurea solution containing a polyurethaneurea as a solute containing a polyol, a diisocyanate and a diamine as a main component, containing a random copolymer of tetrahydrofuran and ethylene oxide and / or propylene oxide is spun. Is a method for producing a polyurethane elastic fiber for sanitary use.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the polyurethane elastic fiber for sanitary of the present invention will be described in more detail.

The sanitary polyurethane elastic fiber of the present invention is a polyurethane urea whose main constituent is a polyol, diisocyanate and diamine.

The method for synthesizing polyurethane urea is not particularly limited. In particular, polymerization is preferably performed in a solution from the viewpoint of efficiently performing the reaction. Note that trifunctional or higher polyfunctional glycols and isocyanates may be used as long as the effects of the present invention are not impaired.

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

[0015] The polyol used in the present invention has excellent cold resistance and high elongation, and from the viewpoint of obtaining a material having high recoverability, tetrahydrofuran (hereinafter referred to as T).
A so-called random copolymer in which HF) and ethylene oxide and / or propylene oxide are arranged irregularly is used.

In the present invention, when a block copolymer is used, the resulting polyurethane elastic fiber has remarkable water absorption, and thus has a problem that physical properties at the time of water absorption are reduced.

That is, the polyol used in the present invention is also expressed as a copoly (alkylene ether) glycol selected from poly (tetramethylene-co-ethylene ether) glycol and poly (tetramethylene-co-1,2-propylene ether) glycol. Can be done.

In the poly (tetramethylene-co-ethylene ether) glycol, the ethylene ether is contained in an amount of 15 to 37 mol% based on the total alkylene ether.
It is preferably contained, more preferably 20 to 35 mol%.

Further, poly (tetramethylene-co-1,2)
-Propylene ether) glycol;
Propylene ether is preferably contained in an amount of 15 to 30 mol% based on all alkylene ethers.

Further, the polyol used in the present invention may be composed of only a random copolymer, may be a copolymer copolymerized with another polyol, or may be a copolymer mixed with another polyol. It may be.

As other polyols, excellent cold resistance,
Poly (1,4-tetramethylene glycol) (hereinafter abbreviated as PTMG), Patent No. 261513, from the viewpoint of obtaining a material having high extensibility and high recoverability.
No. 1, diol containing a neopentyl group in the main chain, polycarbonate diol disclosed in JP-A-2-289616, etc., JP-A-5-9851
No. 1, the ester-based diols disclosed in
It is preferable to use 4-butanediol, 1,6-hexanediol, polycaprolactonediol, polyethylene ether glycol, polypropylene ether glycol, a copolymerized polyol of neopentylene oxide and tetrahydrofuran, or the like. And such another polyol may be one kind, or may be two or more kinds.

In the present invention, the molar fraction of ethylene oxide and / or propylene oxide units is 5
It is preferably in the range of 90%.

The weight average molecular weight of the polyol used in the present invention is preferably in the range of 1,000 or more and 6,000 or less from the viewpoint of elongation, strength, heat resistance and the like when formed into yarn.

More preferably, the range is from 1300 to 4,500. By using a polyol having a molecular weight in this range, an elastic yarn having well-balanced mechanical properties can be obtained.

Next, the diisocyanate used in the present invention is
For example, 5-isocyanate-1- (isocyanatomethyl) -1,3,3-trimethylcyclohexane, 1-
Isocyanate-4-[(4-isocyanatophenyl) methyl] benzene, 1-isocyanate-2-
[(4-Isocyanate-phenyl) methyl] benzene, 1,1′-methylenebis (4-isocyanatocyclohexane), 4-methyl-1,3-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate (hereinafter abbreviated as MDI) ), 2,4-tolylene diisocyanate (hereinafter abbreviated as TDI), 1,4-
Aromatic diisocyanates such as diisocyanate benzene, xylylene diisocyanate, and 2,6-naphthalenedi isocyanate are particularly preferable for synthesizing polyurethane having high heat resistance and strength.

Further, as the alicyclic diisocyanate, for example, methylene bis (cyclohexyl isocyanate)
(Hereinafter abbreviated as H ₁₂ MDI), isophorone diisocyanate, methylcyclohexane 2,4-diisocyanate, methylcyclohexane 2,6-diisocyanate,
Preferred are cyclohexane 1,4-diisocyanate, hexahydroxylylene diisocyanate, hexahydrotolylene diisocyanate, octahydro 1,5-naphthalenediisocyanate, and the like. Aliphatic diisocyanates are preferably used particularly for suppressing yellowing of polyurethane yarns.

These diisocyanates may be used alone or in combination of two or more.

The molar ratio of such diisocyanates is:
From the viewpoint of the strength characteristics of the obtained polyurethane elastic fiber,
It is preferable that the diisocyanate is in the range of 1.2 or more and 2.3 or less with respect to the polyol 1.

Next, a diamine is used as the chain extender used in the present invention.

As the diamine, it is preferable to use at least one of diamines having a hydroxyl group and an amino group in the molecule, such as low molecular weight diamine and ethanolamine.

Examples of the low molecular weight diamine include hydrazine, ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, and 2-methyl-1,5-diamine.
Pentanediamine, 1,2-diaminobutane, 1,3-
Diaminobutane, 1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane, 2,2-dimethyl-1,3-diaminopropane, 1,3-diamino-2,
2-dimethylbutane, 2,4-diamino-1-methylcyclohexane, 1,3-pentanediamine, 1,3-cyclohexanediamine, bis (4-aminophenyl) phosphine oxide, hexamethylenediamine, 1,3
-It is preferable to use cyclohexyldiamine, hexahydrometaphenylenediamine, 2-methylpentamethylenediamine, bis (4-aminophenyl) phosphine oxide and the like. In particular, ethylenediamine is preferably used from the viewpoint of obtaining a material having excellent elongation and elastic recovery. It is also preferable to add a triamine compound capable of forming a crosslinked structure, such as diethylenetriamine, to these chain extenders to such an extent that the effect is not lost.

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

[0033] The polyurethane elastic fiber for sanitary of the present invention preferably has a residual strain at -5 ° C of 90% or less, more preferably 50% or less, and even more preferably 26% or less.

The polyurethane elastic fibers for sanitary use of the present invention include so-called BHT and "Sumilyzer" GA-80 manufactured by Sumitomo Chemical Co., Ltd. as ultraviolet absorbers, antioxidants and gas-resistant stabilizers. Hindered phenolic drugs, various "tinuvins" and other benzotriazole drugs, manufactured by Sumitomo Chemical Co., Ltd.
Phosphorus drugs such as Sumilizer "P-16", hindered amine drugs such as various "tinuvins", inorganic pigments such as titanium oxide, zinc oxide and carbon black, and metals such as magnesium stearate Soaps, fungicides containing silver, zinc and their compounds, deodorants, lubricants such as silicones and mineral oils, barium sulfate, cerium oxide, betaine, phosphoric acid and other antistatic agents It is also preferable that the composition contains an agent or the like and is reacted with a polymer.

In order to further enhance the durability against light and various types of nitric oxide, a nitric oxide supplement such as HN-150 manufactured by Nippon Hydrazine Co., Ltd.
For example, "Sumilyzer" GA- manufactured by Sumitomo Chemical Co., Ltd.
80, it is preferable to use a light stabilizer such as "Sumisorb" 300 # 622 manufactured by Sumitomo Chemical Co., Ltd.

Next, the method for producing the polyurethane elastic fiber for sanitary of the present invention will be described in detail.

In the present invention, it is preferable to prepare a polyurethaneurea solution first.

In the present invention, any method may be used for producing polyurethaneurea, which is a solute of polyurethaneurea solution, and for producing polyurethaneurea solution.

That is, either the melt polymerization method or the solution polymerization method may be used. However, more preferred is the solution polymerization method. In the case of the solution polymerization method, the generation of foreign substances such as gel in polyurethane urea is small. Also, needless to say, solution polymerization is preferable from the viewpoint of production efficiency because labor for preparing a solution is omitted.

In the present invention, a polyurethaneurea containing a polyol, a diisocyanate and a diamine as main components containing a random copolymer of tetrahydrofuran and ethylene oxide and / or propylene oxide is used.

Among these, the weight average molecular weight of the polyol is particularly in the range of 1,000 or more and 6000 or less, and the diamine as a chain extender includes hydrazine, ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 2-methyl -1,5-pentanediamine, 1,2
-Diaminobutane, 1,3-diaminobutane, 1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane, 2,2-dimethyl-1,3-diaminopropane, 1,3-diamino-2, 2-dimethylbutane, 2,
4-diamino-1-methylcyclohexane, 1,3-pentanediamine, 1,3-cyclohexanediamine, bis (4-aminophenyl) phosphine oxide, hexamethylenediamine, 1,3-cyclohexyldiamine, hexahydrometaphenylenediamine, 2-methylpentamethylenediamine, bis (4-aminophenyl)
It is at least one selected from the group consisting of phosphine oxides, and the diisocyanate is preferably a polyurethaneurea synthesized in a solution using MDI as a main raw material.

Such polyurethane urea is, for example, D
It can be obtained by synthesizing the above-mentioned raw materials in MAC, DMF, DMSO, NMP or the like or a solvent containing these as main components.

For example, a so-called one-shot method in which each raw material is charged and dissolved in such a solvent and heated to an appropriate temperature to react to obtain a polyurethane urea,
A method in which a polyol and MDI are first subjected to a melt reaction, and thereafter, the reactant is dissolved in a solvent and reacted with the above-described diamine to obtain a polyurethaneurea can be employed as a particularly preferable method.

In the synthesis of the polyurethane urea, an amine catalyst or an organometallic catalyst may be used alone or in combination of two or more. Typical examples thereof include amine catalysts such as N, N-
Dimethylcyclohexylamine, N, N-dimethylbenzylamine, triethylamine, N-methylmorpholine, N-ethylmorpholine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethyl -1,3-propanediamine, N, N, N ',
N'-tetramethylhexanediamine, bis-2-dimethylaminoethyl ether, N, N, N ', N', N '
-Pentamethyldiethylenetriamine, tetramethylguanidine, triethylenediamine, N, N'-dimethylpiperazine, N-methyl-N'-dimethylaminoethyl-piperazine, N- (2-dimethylaminoethyl) morpholine, 1-methylimidazole, , 2-dimethylimidazole, N, N-dimethylaminoethanol, N,
N, N'-trimethylaminoethylethanolamine,
N-methyl-N '-(2-hydroxyethyl) piperazine, 2,4,6-tris (dimethylaminomethyl) phenol, N, N-dimethylaminohexanol, triethanolamine and the like can be preferably used. As the organometallic catalyst, tin octoate, dibutyl tin dilaurate, lead dibutyl octoate and the like can be preferably used.

Further, in the present invention, it is preferable to use a chain terminator in order to control the molecular weight of the polyurethane and the viscosity of the polyurethane spinning solution.

As such a chain terminator, n-butanol,
Diethylamine, cyclohexylamine, n-hexylamine and the like are preferred.

It is preferable that the chain terminating agent is usually used as a mixture with a chain extender.

Also, small amounts of trifunctional substances such as diethylenetriamine and glycerol can be used to control polymer viscosity.

The concentration of the polyurethaneurea solution thus obtained is not particularly limited, but is usually preferably in the range of 30% by weight to 80% by weight.

In the present invention, it is preferable to add the various additives described above to the polyurethane urea solution. As a method of adding the additive to the polyurethane urea solution, any method can be adopted. As a typical method, it is preferable to adopt a method using a static mixer, a method using stirring, or the like.

Here, the additives are preferably added in the form of a solution. If it is a solution, it can be uniformly added to the polyurethaneurea solution.

In the present invention, a polyurethane urea solution is spun to obtain a polyurethane elastic fiber. The spinning method may be any of a wet method, a dry method, and a melting method.

From the viewpoint of increasing the spinning speed, spinning is preferably performed by a dry method. In dry spinning, at least two gas supply units are provided, and a gas suction unit is used to form a fiber by discharging a polyurethane solution from a spinneret to a spinning cylinder provided between the gas supply units. The temperature of the gas supplied from the gas supply unit provided at the lower part of the spinning cylinder is set
The temperature is preferably set to 0 ° C. or lower from the viewpoint of eliminating yarn unevenness.

During spinning, the speed ratio between the godet roller and the winder is preferably determined according to the purpose of use of the yarn.

In the present invention, winding is preferably performed with the speed ratio between the godet roller and the winder set to 1.1 or more and 1.8 or less.

The spinning speed is 300 m / min or more and 800
It is preferably at most m / min.

[0057]

EXAMPLES The present invention will be described in more detail with reference to Examples. However, the present invention is not limited by these examples.

The method of quantifying stress relaxation, strength, elongation, residual strain and heat resistance in the present invention will be described. [Stress relaxation, strength, elongation, residual strain] Stress relaxation, strength,
For elongation and residual strain, use polyurethane yarn with Instron 45.
It was obtained by performing a tensile test using a 02 type tensile tester.

The stress relaxation, strength and elongation were measured at 22 ° C., and the residual strain was measured at −5 ° C.

These are defined below.

A 5 cm (L1) sample was subjected to 300% elongation at a tensile speed of 50 cm / min five times. The stress at this time was defined as (G1).

Next, the length was held for 30 seconds. The stress after holding for 30 seconds was defined as (G2).

When the stress is set to 0, the sample length is set to (L
2).

Further, the polyurethane yarn was stretched until the polyurethane yarn was cut.

The stress at break was (G3) and the sample length at break was (L3).

The above characteristics were obtained by the following equations.

Strength = (G3) Stress relaxation (%) = 100 × ((G1) − (G2)) / (G1) Residual strain (%) = 100 × ((L2) − (L1)) / (L1) Elongation (%) = 100 × ((L3) − (L1)) / (L1) [Heat resistance] The yarn was stretched by 100% and placed in an atmosphere of dry air at 180 ° C. for 1 minute. After the treatment, the yarn is left free in an atmosphere of 21 ° C. and 65% RH after leaving it in a free state, and then the stress at 200% elongation is measured using an Instron 4502 type tensile tester, and compared with the stress before the treatment. Thus, the stress retention was determined. Example 1 A polyol which is a random copolymer having a ratio of THF to ethylene oxide of 7: 3 and a molecular weight of 1951 (“Tetraxinol AS” manufactured by Sanyo Chemical Industries, Ltd.) −
200S ″) After reacting 2900 g and 595.8 g of MDI without solvent, dissolve in 6602 g of dimethylacetamide, and add 53.7 g of ethylenediamine and 5.45 g of diethylamine to obtain a 35% by weight polyurethaneurea solution. A sample solution was prepared by adding an appropriate amount of an antioxidant, a gas-resistant stabilizer and titanium oxide to the polyurethane urea solution, and the obtained solution was dry-spun at a speed of 500 m / min to obtain 470 dtex. A 56 filament yarn was obtained.

Table 1 shows the elongation, strength, stress relaxation, residual strain measured at −5 ° C., and heat resistance of the yarn.

[0069]

[Table 1]

Example 2 2820 g of a polyol (“Tetroxynol AS-200S” manufactured by Sanyo Chemical Industries, Ltd.), which is a random copolymer having a ratio of THF to ethylene oxide of 7: 3 and a molecular weight of 1951, and MDI579 .
After reacting 35 g under solvent-free conditions, it was dissolved in 6439 g of dimethylacetamide, and ethylenediamine 4
1.8 g, Dytek® A amine 2 manufactured by DuPont
The addition of 0.16 g and 5.30 g of diethylamine gave a 35 weight percent polyurethaneurea solution. An antioxidant to this polyurethane urea solution,
A sample solution was prepared by adding appropriate amounts of a gas-resistant stabilizer and titanium oxide. The resulting solution was dry-spun at a speed of 500 m / min to obtain a yarn of 470 dtex and 56 filaments.

Table 1 shows the results of elongation, strength, stress relaxation, residual strain measured at -5 ° C., and heat resistance of this yarn.

Example 3 3000 g of a polyol, which is a random copolymer having a ratio of THF to propylene oxide of 8 to 2 and a molecular weight of 2,000, and 618.75 g of MDI
Was reacted under no solvent conditions, and dissolved in 6736 g of dimethylacetamide.
And 3.56 g of diethylamine to give a 35% by weight polyurethaneurea solution.
A sample solution was prepared by adding an appropriate amount of an antioxidant, a gas-resistant stabilizer and titanium oxide to this polyurethane urea solution. The resulting solution was dry-spun at a speed of 500 m / min to obtain a yarn of 470 dtex and 56 filaments.

Table 1 shows the results of elongation, strength, stress relaxation, residual strain measured at -5 ° C., and heat resistance of this yarn.

Example 4 3000 g of a polyol ("Tetoxynol AS-300S" manufactured by Sanyo Chemical Industries, Ltd.), which is a random copolymer having a ratio of THF to ethylene oxide of 7: 3 and a molecular weight of 3556, and MDI411 .
After reacting 28 g under solvent-free conditions, it was dissolved in 6435 g of dimethylacetamide, and ethylenediamine 4
A 35% by weight polyurethaneurea solution was obtained by adding 8.2 g and 5.33 g of diethylamine. A sample solution was prepared by adding an appropriate amount of an antioxidant, a gas-resistant stabilizer and titanium oxide to this polyurethane urea solution. The obtained solution is dry-spun at a speed of 500 m / min to obtain 470 dtex,
A 56 filament yarn was obtained.

Table 1 shows the elongation, strength, stress relaxation, residual strain measured at −5 ° C., and heat resistance of the yarn.

Example 5 3000 g of a polyol (“Tetroxynol AS-300S” manufactured by Sanyo Chemical Industries, Ltd.), which is a random copolymer having a ratio of THF to ethylene oxide of 7: 3 and a molecular weight of 3556, and MDI411 .
After reacting 28 g under solvent-free conditions, it was dissolved in 6442 g of dimethylacetamide, and ethylenediamine 4
3.3 g, Dytek® A amine manufactured by DuPont
The addition of 29 g and 4.88 g of diethylamine gave a 35 weight percent polyurethaneurea solution. A sample solution was prepared by adding an appropriate amount of an antioxidant, a gas-resistant stabilizer and titanium oxide to this polyurethane urea solution. The resulting solution was dry-spun at a speed of 500 m / min to obtain 470 dtex, 5
A 6-filament yarn was obtained.

Table 1 shows the results of elongation, strength, stress relaxation, residual strain measured at −5 ° C., and heat resistance of this yarn.

Comparative Example 1 PTMG2 having a molecular weight of 2,000
After 900 g and 594.50 g of MDI were reacted under no solvent conditions, the resultant was dissolved in 6608 g of dimethylacetamide, and 55.8 g of ethylenediamine and 7.89 g of diethylamine were added to obtain a 35% by weight polyurethaneurea solution. A sample solution was prepared by adding an appropriate amount of an antioxidant, a gas-resistant stabilizer and titanium oxide to this polyurethane urea solution. The resulting solution was dry-spun at a speed of 500 m / min to obtain a yarn of 470 dtex and 56 filaments.
Table 1 also shows the elongation, strength, stress relaxation, and residual strain and heat resistance of the yarn measured at -5 ° C.

[0079]

According to the present invention, the elastic properties are not impaired even at a low temperature, have excellent low-temperature properties without settling, have good stretchability and recoverability, and have good heat resistance. A polyurethane elastic fiber for sanitary can be obtained. When the polyurethane elastic fiber for sanitary of the present invention is used in the manufacture of sanitary products such as disposable diapers and sanitary napkins, it is possible to reduce the production cost and increase the production amount per unit time, fit, appearance quality, A product excellent in wearability, feeling of wear, and the like can be obtained at a production cost.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Takayoshi Shiraishi 1-2-1, Sonoyama, Otsu, Shiga Prefecture Toray Dupont Co., Ltd. Shiga Plant F-term (reference) 4L035 AA04 BB02 BB11 EE01 EE08 EE20 GG04 HH01 HH10 KK05 MH02 MH09 MH12 MH13

Claims (6)

[Claims] 1. Polyurethane urea whose main constituent is a polyol, diisocyanate and diamine,
A polyurethane elastic fiber for sanitary use, characterized in that the polyol contains a random copolymer of tetrahydrofuran and ethylene oxide and / or propylene oxide. 2. The polyurethane elastic fiber for sanitary according to claim 1, wherein the molar fraction of ethylene oxide and / or propylene oxide units is in the range of 5 to 90%. 3. The polyol has a molecular weight of 1,000 or more and 60 or more.
The polyurethane elastic fiber for sanitary according to claim 1 or 2, wherein the elastic fiber is in the range of 00 or less. 4. The sanitary polyurethane elastic fiber according to claim 1, wherein the residual strain at -5 ° C. is 90% or less. 5. A method of spinning a polyurethaneurea solution containing a polyurethaneurea as a solute containing a polyol, a diisocyanate and a diamine as a main component, containing a random copolymer of tetrahydrofuran and ethylene oxide and / or propylene oxide. For producing polyurethane elastic fibers for sanitary use. 6. The method according to claim 5, wherein the spinning method is a dry spinning method.