JPS58163727A - Production of polyurethane conjugate elastic yarn - Google Patents

Abstract

PURPOSE:Conjugate spinning is carried out using a thermoplastic polyurethane elastomer as the sheath component and another elastomer that is prepared by adding a specific polyisocyanate to the melted same polyurethane elastomer as the core component to produce the titled elastic yarn with high heat resistance and fusing resistance. CONSTITUTION:(A) A thermoplastic polyurethane elastomer such as a polyurethane obtained from diphenylmethane diisocyanate and polytetramethylene glycol is used as the sheath component, and (B) another polyurethane elastomer that is obtained by adding 5-30wt% of a polyisocyanate of 400 or more molecular weight, e.g., an addition product of diphenylmethane diisocyanate on both terminals of polytetramethylene glycol to the melted above thermoplastic polyurethane as the core component at a weight ratio of (5-50)A : (95-50)B to effect conjugate spinning and produce the objective conjugate yarn.

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to a method for producing a composite elastic yarn of a polycretaceous collection. Specifically, it has excellent heat resistance.

This invention relates to a method for producing a polyurethane composite elastic yarn having elastic recovery properties and anti-sticking properties.

There are three main methods for producing Frethane elastic yarns: dry spinning, eel spinning, and happy spinning. Among these, the melt spinning method is advantageous as an industrial manufacturing method because it does not require the use of #14, has a high spinning speed, and is compatible with equipment.

However, the polycrethane elastic yarn obtained by #I-spinning method is inferior in heat resistance because it uses nine-valued polycrystalline V-tane for spinnability, and the recovery from deformation caused by high temperature Ksi is difficult. It has a certain 111IlI point of 1st magnitude.

In order to solve this problem, the following methods have been proposed.

+1) Method of adding a polyfunctional compound during polymerization a)
Semi-uniform poly for direct spinning method than polymerization system! - is prepared by #1 brewing and extruded at a constant temperature or during hardening and milling μm mla after spinning
Among these methods, method 1) provides a sufficient amount of heat resistance to improve the heat resistance. - When the rolling temperature becomes high, it is necessary to increase the spinning temperature,
This has the disadvantage that spinning becomes unstable.

By the method q), the control of V%C#i haze reaction 6 is effective, and there is t@electricity of stagnation and false stability in the process from the polymerization system to the spinning system.

For (5) and (4), tkVc':) I/1 [is qv
Regarding heat resistance and recovery from quality cedar due to high I7A, [4441h method, but @1
The processing equipment is getting bigger.

It can be said that the industrial manufacturing method is disadvantageous due to the high cost.

Father, the polyurethane elastic system Fi1 is easy to attach (deweighting from the spinning pobin is 1), and this tendency is remarkable in the poly9 urethane elastic yarn which is superior by #l@spinning [remarkable 0] The polyurethane elastic yarn 74 Cment has an incyanate group inside the filament or on the Fi surface.
``It seems that chemical bonds such as lower anneal bonds occur and cause the glue in the filament to bend.

Use of this normal TwI (positive spinning i1) @, spinning draft up, internal addition of 4 rough 4 n, etc.
Countermeasures such as addition of 1 are taken iIk first.

Among these, the proper use of spinning jlI cutting is effective against sticking, white powder on guides and needles during threading, product contamination due to waxy material lying on the guide and needles, and shortening of cleaning synchronization between guides and needles.
Avoid negative effects such as knitting tension fluctuations! i-eru.

Father, the spinning draft up (Fi) once decreases, causing a decrease in operability in higher-order processes.

On the other hand, regarding the addition of internal additives such as /4 Rough 4 N,
The present inventors conducted research to eliminate the drawbacks of conventional filaments, such as inhibiting stable operation during tIIf spinning and inhibiting the characteristics of the urethane elastic material, and to obtain a polyurethane elastic yarn with excellent heat resistance, etc. As a result, the present invention t9! Get it done.

An object of the present invention is to provide a polyurethane composite elastic yarn having particularly excellent heat resistance and elastic recovery properties, and improved anti-wearing properties. Another object is to provide a method for manufacturing such elastic strips in an engineering, easy and inexpensive manner.

The sheath is made of a heat-resistant polyurethane elastic material, and the i! Polyurethane elastomer with molecular weight 4
The core is a polyurethane elastic body made of 5 to 50 weights of a polyisocyanate compound of 00 or more,
It is characterized by composite melt-spinning at a weight ratio of /95 to 5015G.

Heat q! applied to the present invention! The type II polyurethane elastomer contains a known medium-sized polyurethane polymer.
, polyols having a molecular weight of 500 to 6ooo, such as dihydroxy polyether, dihydroxy polyester, dipidroxy polylactone, di. Hydroxy polyester amide, dipidroxy polycarbonate, block polymers thereof, etc., and an organic diisocyanate having a molecular weight of 500 or less, P'-diphenylmethane diisocyanate, tolylene diinocyanate, and hydrogenated P.

Obtained by reaction of P'-diphenylmethane diisocyanate, tetranotylene diisocyanate, hexamethylene diisocyanate, 1,5-7-ethylene diisocyanate, etc. with chain exfoliation, for example, water, J-drazine, diamine, glycol, etc. It is a polymer.

Among these polymers, the best one is polytetramethylene glycol as the polyol.

Danta is polycaprolactone, 11! Poly using Adipate! − is. Further, as the organic diincyanate, rtf, P%P''-diphenylmethane diisocyanate is preferable.As the chain length, glycol is particularly preferable, and 2%P'-bishydroxyethoxybenzene and 1.4-butanediol are particularly preferable. be.

In the present invention, heat q! ! Polymers synthesized without the use of branched polyurethanes or bridge-shaped polyurethanes are used, but of course polymers containing branched or *@-cured to the extent that the spinning temperature does not become excessively high may also be used. can.

In addition, among the combinations of the above-mentioned polymer components, the thermoplastic polyurethane elastomer used as the core component and the thermoplastic polyurethane elastomer used as the sheath component are selected from among the combinations of the above-mentioned polymer components, such as a citrus polymer or a different type of polyurethane. - can be used in combination with 迩Vat.

The polyisocyanate compound with a molecular weight of 400 or more used in the present invention is a compound having at least two incyanate groups in the molecule. An organic diisocyanate with a molecular weight of 500 F or more with twice the molar density is diluted to form a compound. Of course, a compound having three or more hydroxyl groups can also be used as the polyol. Also, as a polyisocyanate compound,
As the organic diisocyanate dimer R, carbodiimide-modified polyinsyanate can also be suitably used.

Because of the number of incyanate groups that can be combined in one molecule of the polyincyanate compound, 2 to 4 are preferable, and diincyanate compound 2 is particularly preferable. If there are too many incyanate groups, the viscosity of the polyincyanate compound becomes high, making it difficult to handle.

Fi, molecules 1i as suitable polyisocyanate compounds
500 to 2,500 polyols, such as polyethers, polyesters, polyesteramides, and polycarbonates, and at least one type of polyol selected from fresh polyols, with organic diisocyanate compounds having a molecular weight of 500% or less added to both ends. . Particularly suitable polyols include polytetramethylene glycol, polycaprolactone t#i polybutylene adipate, and organic silyl cyanates include P,P'-diphenylmethane diincyanate. In addition, the polyincyanate compound has a molecular weight of aoOGt-h, 800%
~5000 is preferred.

In producing the composite elastic yarn of Mokil@Beak, a known core-sheath composite spinneret is used, and the polyurethane yarn composite elastic yarn is obtained by melt-proofing.

In core-sheath composite spinning, the core component becomes the fiber axis of the composite elastic yarn! Even if the core-shaped composite elastic yarn is eccentric from the center of the straight cross section, the core component and the delicate axis Km of the composite elastic system
It may be a concentric M'E@-shaped composite fiber in which the center of the straight cross section is the same, but - the center! ! ! Core composite fibers are preferred. The reason for this is that the -6 side of the &I/IC sheath component in the eccentric core-axial composite elastic yarn becomes extremely thin, making it impossible to obtain a sufficient core-axial composite fiber. A certain Sakaki Kaishi ◆The coming characteristics of polyurethane elastic yarn are wisdom (to appear).

5 to 50% by weight is suitable. Particularly preferably, in the method of the present invention, the polyincyanate compound crosslinked fiber #6 in the polyurethane elastomer as a core component is used. Compared to the case of spinning, since the surface layer is acupunctured by the @ component, there is less activity of incyanate groups due to moisture in the air on the surface of the 74 lament or due to the spinning deflection after winding, resulting in a lower C anti-6 rate. #Always high ◎ [If it exceeds 50%, the 1 positive electric power setting at the time of spinning is rough, the spinnability is poor, and some problems such as partial positive electric power sticking. On the other hand, if the amount of the polyincyanate compound added is less than 5% by weight, the polyurethane composite elastic yarn will have insufficient heat resistance and elastic recovery, and will not be sloppy.

In addition, in the production of polyurethane-based composite elastic yarn, [fgtm@lk of the anti-6-spun polyurethane elastomer with a core component is the part where the Kamecho polyOV tan elastomer is melt-extruded, and the polyisocyanate compound t11ii is added and mixed. partial and composite spinning spatulas)? It is preferable to carry out the spinning process using a spinning device that is equipped with a spinning machine.

In addition, in the part where the polynoncyanate compound is added and mixed with molten thermoplastic polyurethane Km, 1g1
Although it is possible to use a kneading device with #'i stationary kneading elements, it is more convenient to use a mixing device with #'i static kneading elements. As a mixing IHII having a static mixing element, a known Fi can be used. The shape and element conditions of the static hybrid element will differ depending on the conditions used, but the polyurethane elastomer and polyincyanate compound must be sufficiently mixed before being discharged from the spinneret. It is important to make the selection accordingly. Melt spinning of sheath component F! A well-known Kijo extruded iso can be used. The poly9 urethane elastomer obtained in this way was prepared using a core-sheath composite spinneret.

When the weight ratio of the core component of the composite system of Mokuyamei is less than 509b, it has the advantage of being excellent in heat resistance and elastic recovery properties, which are the characteristics of the core component, which is a polyurethane resistant material. will be kept alive. When the weight ratio of the core component is more than 95%, the amount of the sheath component discharged is small, and the number of young fruits to prevent sticking is reduced, and the low modulus and high tolerance characteristics of the sheath component are impaired.

Furthermore, the core-sheath type composite spinning Ks? C: By bringing the viscosity of both the core component and the sheath component of the polycrethane elastic body close to each other, a composite elastic yarn with good thermal stability can be obtained.

In addition, the thermoplastic polycrethane elastic material that is the sheath component is resistant to corrosion.
,! Antioxidants, lubricants, titanium oxide, etc. matte%1t
By including the polyurethane-based composite elastic yarn, the primary properties of the polyurethane-based composite elastic yarn are not impaired.

When the desired composite yarn is obtained, 7 can be obtained.

Hereinafter, the explanation will be given with reference to examples.

Example 1 Dehydrated polytetramethane gellicol 550 G11 with a hydroxyl value of 112 (all parts hereinafter refer to parts by weight) and t4bis(β-tFoxyethoxy)benzene (1
1) Charge 245 parts of 41:B) into a kneader with a t-jump, and dissolve thoroughly while stirring. Keep at a temperature of 85C, and add 1255 parts of this 6 (t% P-diphenylmethane diincyanate (lid DI)). The poly9V tongue obtained by 6 was extruded and turned into pellets K.
BT shape, Jimel? - Obtain a polyurethane elastomer having a relative viscosity of 2.29 at 1 g/100 mm measured in Lumamide at 25°C.

On the other hand, polytetramethylene glycol y-* with a basic acid value of 152
5150 all and MDI500alt 60 at 80℃
Warp for a minute to obtain a polyincyanate compound. The molecular weight of this polyincyanate compound was #11564, which was calculated from the incyanate group content of 616% incyanate group.

The obtained thermal polycrethane elastomer was used as a core component. Incidentally, when the L component is melted, the polyincyanate compound is supplied.**The extruder tJt1%/1 is equipped with a cross wire device having a solder and a static kneading element.

A core-sheath composite spinneret was used to spin the core-sheath fiber.

Composite spinning nozzle [Using nozzle [L5m1,101]
5 The spinneret was spun at a temperature of 22'0° C. and a winding speed of 50 Os+a/-, taking into account the core and -component ratio, to obtain a composite fiber of 60 denier and 574 strands. The results are shown in Table 1. The heat set rate and unwinding coefficient in Table 1 are the electric values determined after the spun urethane yarn was soaked at room temperature for 7 days.

The 150C heat setting rate is the setting rate when a $00s-long cretan yarn is dried at ISO and treated for 10 minutes. Also, #Shupoyuan was taken over by Pobinfu and V
This is the ratio of the surface speed of the pobbin and the surface speed of the take-up roller when unwinding the tongue yarn at a speed of 50 l/min. In addition, at the time of mepin ma, an oil cloth mainly made of mineral oil and modified silicone was attached to the urethane thread. Koji & Y Comparative Example 1-2 was prepared by using a core/sheath/sheath composite mouth jar, combining a thermoplastic polyurethane elastomer with a polyincyanate compound and adding T, and then spinning it into an α3-normal mouth jar.

From Table 111, the single spun yarn of Comparative Example 1-2 has high strength, high creep, and elongation recovery rate values, and those with low 150 cm set rate values have high unwinding coefficients and large stickiness.

The heat setting rate when no polyisocyanate compound is added is 81%.

Examples 1-1 to 1-5 have a high degree of stiffness, long frtllL with excellent elastic recovery properties and heat resistance, and also have improved high modulus and adhesion properties, which are disadvantages of single spinning. . Compare this to @1-IKs? Vsτ has a low core component weight ratio of 56g6, and has poor elastic recovery and heat resistance.

Example 4 #12 Dehydrated dihydroxypolyε-caprolag with a hydroxyl value of 56 625011 As B Hg 8579 parts, M
DI117111tMi - [1
61-tj was pelletized to obtain a polyurethane elastomer having a relative viscosity of 2.05.

In addition, dehydrated polybutylene adipe with a hydroxyl value of 56>s
sog@,t,aguthanedioh272fl-MDX1
22Bt8 was subjected to inversion 6 in the same manner as in Example 1 and pelletized to obtain a polyurethane elastic body having a relative viscosity of t60.

In addition, dihydroxy poly ε-Kab 09 with a hydroxyl value of 112
F ton 100011 and MD X 50 G 5111
The mixture was warped at 80° C. to obtain a circular polyinsyanate compound. The inocyanate group content of this polyisocyanate compound was 57%, and the molecular weight calculated from the incyanate group content was 1,508.

-Polygnalene alibate polyurethane as a component
yBvss A poly-ε-caprolactone polyurethane and a polyisocyanate compound are used as core components.

Spinning was carried out in the same manner as in Example 1.

After leaving the obtained composite elastic yarn for several days, the yarn quality was 150.
The cm set point and unwinding coefficient t#11 were determined.

Shown in 1t112 wheat.

m one piece - In the reference &h example 1, uniformly high strength and high degree,
It also has 500% stress, excellent heat resistance, and less adhesion.
Cane.

*1h14&.

- Watered dihydroxypolyε-cabrolactone with hydroxyl value 56 & 250 parts, BH11571 parts, wx+z117
211B,)! J methylolp oaq! II'
The reaction was carried out in the same manner as in the t1@-dormitory example, and a polyurethane elastomer having a relative viscosity of 2.58 was pelletized and used for the present day.

Also, dehydrated dihydroxypolyε-caprotictone with a hydroxyl value of 56 & 250 parts, 1111!167'9 parts, MD
1117111t was reacted with Example 1 in an unfavorable manner and pelletized to obtain a polyurethane elastomer having a circumferential viscosity of 2.05, which was used as a sheath component.

Further, dihydroxypolyε-cabrolactone 1000 #91 having an acid value of 112 and MDI500al were reacted at 80°C to obtain @a3&polyisocyanate compound. Incyanate group content F of this polyincyanate compound
i5.57%, Incyanate Foundation "The molecular weight extracted from the eel was 150'8. This polyincyanate compound was used as the core component.

Thereafter, one round of spinning was carried out in the same manner as in Example 1.

Leave the resulting composite elastic yarn for 7 days! Substrate after washing, 160
°C heat set rate and unwinding coefficient were measured. This result is the fifth
Shown in 1.

Table 6

Claims (1)

[Claims] The core is a thermoplastic polyurethane elastomer, and the core is a polyurethane elastomer made by combining a melted MOA flexible polyurethane elastomer with a polyincyanate compound having a molecular weight of 400 or more. 5/95-5015
1. A method for producing a polyurethane-based composite elastic system, which comprises performing composite melt-spinning at a weight ratio of 0.00.