JPS6197471A - Production of polyurethane elastic fiber - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for producing polyurethane elastic fibers by a melt spinning method. More specifically, the present invention relates to a method for preventing bobbin threads from sticking by applying an oil agent to the fibers during melt-spinning of polyurethane elastic fibers. (Prior Art) Melt-spinning has traditionally been a method for obtaining polyurethane elastic fibers. , dry spinning method, wet spinning method, etc. are generally used.
However, in both methods, when the fibers are wound onto a bobbin during spinning, the fibers stick to each other, and when the bobbin is unwound, large tension or tension unevenness occurs, which causes problems in the subsequent process. This was the main cause of thread breakage. Many proposals have been made to date on methods for preventing this stalemate. For example, a method has long been proposed in which an aqueous or oil-based slurry of fine mineral solid particles such as talc, silica, and colloidal alumina is applied to fibers. Although these methods are certainly effective in preventing bobbin thread from sticking, it is difficult to maintain uniform dispersion of solid particles in water or oil, making it difficult to prevent thread from sticking uniformly. Disadvantages include large tension unevenness during unwinding, solid Wi particles falling into the yarn path in the subsequent process, large tension fluctuations, and abrasion of the contact area of the yarn due to solid fine particles. There is.

Avoiding mineral solid particles, metal salt powder of higher fatty acids is dispersed in water or oil based on mineral oil.
1-286, Japanese Patent Publication No. 40-5557), a method of dispersing and dissolving room temperature solid waxes such as higher aliphatic carboxylic acids, higher aliphatic alcohols, paraffin, and polyethylene in an oil agent mainly containing mineral oil (Japanese Patent Publication No. 48-1986) 272, Japanese Patent Publication No. 4G-9955, and Japanese Patent Publication No. 44-8907) have also been proposed. However, in these methods, the wear tlN of the thread contact area is eliminated due to the softness of the dispersed solids, but the dispersion and dissolution are still unstable, resulting in uneven adhesion to the threads and scum of the solids. It is difficult to completely avoid falling onto the thread path.

Polyalkylene oxide-modified silicone oil is the best known as a liquid at room temperature and has good anti-sticking properties (Japanese Patent Publication No. 45-40719, 1989-1989, 57 -128270). In particular, the higher the molecular weight of the added polyalkylene oxide, the greater the anti-sticking performance, but the viscosity increases, and the frictional resistance of the thread is so high that it cannot be used as it is, so base oil such as low viscosity mineral oil, silicone oil, etc. need to be dissolved in However, high-molecular polyalkylene oxide-modified silicone oils have extremely low solubility in these base oils, and even when using compatibilizers such as higher alcohols and their fatty acid esters, there is a limit to the amount of solubility. However, these compatibilizers often deteriorate the quality of polyurethane elastic yarns.

Furthermore, it must be pointed out that the sticking of the bobbin yarn during spinning of polyurethane elastic yarn is due to the rubbery t! f. It seems that this is not due to mere adhesion due to quality, but also due to chemical bonds. That is, after spinning, the reactive isocyanate end groups of the urethane polymer are present on the surface of the filament wound on the carrier bobbin for several days, and the allophanate bonds and other chemical bonds are formed at the interface where the filaments connect. It is thought that the filaments form between the two filaments, making their adhesion stronger. This phenomenon is particularly noticeable when polyurethane elastic fibers are produced by Rakunan spinning. As a method for preventing sticking caused by chemical bonding of isocyanate end groups, a method has been proposed in which mineral oil in which monoamines have already been dissolved is applied during spinning, and the isocyanate end groups are deactivated by the monoamines.
11i'146-16312), and oil agents containing appropriate diamines have also been proposed by the present inventors (Japanese Unexamined Patent Publication No. 182170/1982).
However, the effect of these 11 amines is limited to the deactivation of the reactive groups of the filament, and has no effect on the sticking caused by the adhesion of the rubbery substance of polyurethane, and as mentioned above, polyalkylene oxide-modified silicone also
Since there is a limit to anti-sticking properties, it is necessary to prevent sticking of bobbin systems, especially when the polymer viscosity is low during melt spinning and the filament is still soft at the moment it is wound onto the bobbin, or when the fiber denier is as thin as 20 deniers or less. was still insufficient in many cases.

(Problems to be Solved by the Invention) The present invention solves problems in producing polyurethane elastic fibers by a melt spinning method, such as sticking of bobbin threads, sticking, scum falling into the thread path, and resulting thread breakage. This is an attempt to solve such problems.

(Means for Solving the Problems) In order to solve the above problems, the present invention provides a method for producing elastic polyurethane fibers using mineral oil and/or
Or polydiorganosiloxane mixed with amino-modified silicone, with a viscosity of 100 centistokes (80 centistokes)
°C) The following blended oil is applied to polyurethane elastic i# fiber and then rolled up.

The mineral oil referred to here has a viscosity of 100% as a whole blended oil.
You can choose any value as long as it is below centistokes (hereinafter referred to as C8) (80℃), but usually 4 to 25 centistokes.
A material with a low viscosity of about C8 is desirable from the viewpoint of ease of melting with other oil components and reduction of fiber friction. Polydiorganosiloxane is most desirable because polydimethylsiloxane is a commonly used product, but some of the methyl groups may be substituted with other monovalent organic groups such as alkyl groups and phenyl groups. As with mineral oil, the viscosity can be any value as long as the viscosity of the entire oil is 100C8 (80℃) or less and 2 tons, but usually a low viscosity type of 5 to 20C811 degrees is the same as mineral oil. Desirable for a reason. However, since higher viscosity silicone oils are generally more effective at mold release, using a high viscosity type in only a portion can also be expected to have some anti-sticking properties. The mixing ratio of mineral oil and polydiorganosiloxane (including each alone) depends on the amino group content, viscosity, blending ratio, etc. of the amino-modified silicone blended in the mixture of the two. That is, some amino-modified silicones may be difficult to dissolve in mineral oil or polydiorganosiloxane depending on the conditions, resulting in some separation and cloudiness. Uneven adhesion due to poor solubility of amino-modified silicone,
This tends to cause problems such as scum falling into the thread path. The present invention requires that the amino-modified silicone be completely dissolved in the mineral oil, polydiorganosiloxane, or mixture thereof. Adding a portion of a compatibilizer such as alcohol or ester to the blended oil in order to completely dissolve the amino-modified silicone is outside the scope of the present invention and does not exceed 1%. Since this often leads to deterioration of the thread quality of polyurethane fibers and a decrease in anti-stick properties, it is desirable to keep the amount of oil to 10% or less of the total blended oil. It is most desirable to completely dissolve the amino-modified silicone using only the following ingredients:

The amino-modified silicone used in the present invention generally refers to polydimethylsiloxane with an amino group added to its molecular chain, but it is of course also effective to substitute the methyl group with another alkyl group or allyl group. Depending on the position of addition of the amino group, there are side chain types and single terminal types, and the amino group itself includes monoamines, diamines, etc., but all types are effective.

Regarding viscosity and amino group content, any oil can exhibit anti-sticking properties to a greater or lesser extent, and the viscosity of the entire blended oil only needs to be less than 100°C (80°C), and generally prevents bobbin thread from sticking. The higher the amino group content of the amino-modified silicone, the better the prevention performance is, and when there is an extreme difference in viscosity, the higher the viscosity, the better.

However, in 'melt spinning', the fibers after spinning are extremely soft, and the viscosity of the blended oil applied at that time is 100cs1a.
If it is h, the oiling roller, guide nozzle, or other yarn contacting parts will be highly abrasive due to the viscosity of the oil, and loose filaments or yarn breakage will easily occur, which is not preferable. Most preferably, the viscosity of the blended oil is 2008 or less.

Even a very small amount of amino group content in amino-modified silicone is effective in preventing adhesion, but in order to ensure this effect, the ratio (compounding ratio) of amino-modified silicone to the total blended oil must be 9.1% by weight. As mentioned above, it is desirable that the amino equivalent (Note 1) of the amino fl'E silicone be 10.000 or less. -The higher the blending ratio of amino-modified silicone and the lower the amino equivalent, the more difficult it becomes to dissolve the amino-modified silicone in mineral oil and polydiorganosiloxane. It is desirable that the amount is less than 800% by weight and the amino equivalent is 800 or more.

The oil agent used in the present invention is composed of mineral oil, polydiorganosiloxane, and amino-modified silicone, but anti-sticking ingredients other than JT, such as conventional mineral-based talc, silica, colloidal amine, etc. Further blending of solid fine particles, metal salt powder of higher fatty acids, high gauze aliphatic carboxylic acids, higher aliphatic alcohols, paraffin, room temperature solid wax such as polyethylene, high molecular weight polyalkylene oxide modified silicone oil or amines, etc. Unless they are reactive with the amount of amino acids, adding them will increase the anti-sticking effect accordingly.

However, because the effects of amino-modified silicone are so great, it is not really necessary to add such additional ingredients, and on the contrary, it may cause problems such as wear of the thread guide, falling off of scum, and uneven adhesion. However, although the present invention relates to a melt spinning method for polyurethane elastic fibers, the effectiveness of applying the oil agent of the present invention to other spinning methods is not recommended. In the present invention, the amino group content is quantitatively expressed in terms of amino equivalent (1), and the relationship is such that the smaller the amino equivalent, the larger the amino group content.

Measuring method for amino equivalent: Take about 12 samples in a flask and stir. Add 25 rnf of isopropyl alcohol, stir thoroughly, dissolve in a bath, and neutralize with IN hydrochloric acid using an indicator bromophenol blue. Amino Hyakuho is calculated using the following formula.

The compounded oil in the present invention is a base oil in which amino-modified silicone is sufficiently dissolved and dispersed in mineral oil, polydiorganosiloxane, or a mixture thereof.Of course, the mineral oil and polydiorganosiloxane themselves also have some ability to prevent bobbin thread sticking. However, most of the anti-sticking properties are in the amino-modified silicone, and mineral oil and polydiorganosiloxane are used to fully demonstrate the effects of the amino-modified silicone (it does not swirl even when straining.The amino-modified silicone is It is not clear what kind of action exerts the sticking prevention t!1 =, but according to the present inventors' estimation, the amino groups of the amino-modified silicone are still attached to the polyurethane immediately after melt-spinning; It is thought that the silicone molecular chains l connected to the amino groups strongly bonded to the isocyanate groups remaining on the surface, or strongly adsorbed to the fiber surface even without bonding, and strongly covered the fiber surface. Silicone originally has good mold releasability, but in the past, silicone was not sufficiently bonded or adsorbed to the fiber surface, so it did not perform its original function.
It is presumed that the original function was fully exhibited thanks to the amino groups present in the silicone molecular chain.

(Example) The present invention will be illustrated below with reference to Examples.

Example[.

Polytetramethylene glycol 6 with molecule 511,200
9.4 parts of L4 bis(β-hydroxyethoxy)benzene, 24.4 parts of 4.4'-diphenylmethane diisocyanate.
The mixture was melted at 6° C., extruded through a nozzle using a screw extruder, and wound around a bobbin at a spinning speed of 500 m/min to obtain a 20-denier monofilament. Immediately before winding, an oil having the following composition was applied to the filament in an amount of about 10% by weight using a guide nozzle.

The blending ratio of each oil agent is a weight ratio. The viscosity of all the blended oils was 1 nocs or less.

The spinning results for each oil agent are shown in Table 1.

Note 2) The unwinding coefficient bobbin is fed out at a speed of 50 m/min.
This refers to the draft rate of the thread at the minimum winding speed at which the thread is fed out without being wound around the bobbin when the winding speed is changed and the thread is unwound.

The smaller the unraveling coefficient is, the greater the effect of preventing thread sticking is.

All oils A-H use low viscosity mineral oil or low viscosity silicone oil as the base oil, so the blended oil viscosity is 10.
0C3 or less, loose filament during spinning, yarn 1
There was no 7If'L. Comparative Example G is an oil agent in which fine solid particles of magnesium stearate are dispersed, and although it has an excellent anti-sticking effect, the dispersion in the oil agent is unstable, resulting in thread-like hescum and falling off. Comparative Example F was an oil containing a polyalkylene oxide-modified silicone and a diamine, and although there was no scum falling into the yarn path, the anti-sticking effect was slightly inferior. Oil agent H was an oil agent containing only mineral oil and polydimethylsiloxane, and its anti-sticking effect was extremely weak. Oils A-E are oils according to the present invention, and although the mixing ratio of mineral oil and polydimethylsiloxane and the type and amount of amino-modified silicone are different, they are all better than Oils H, which is made only of base oil. It showed better anti-sticking performance than oils F and G, which were conventionally said to have the best anti-sticking properties, and showed good operability with fewer thread breaks in subsequent processes.

Example 2 The table below shows the results obtained by changing the viscosity of the blended oil under the same spinning conditions as in Example 1. The oil agent is a mixture of 95 parts of mineral oil and polydimethylsiloxane with an amino acid content of 9000 and a viscosity of 9003.
The viscosity was adjusted by changing the viscosity of the mixture of mineral oil and polydimethylsiloxane.

Table 2 Table 2. As shown in Figure 2, when the viscosity of the blended oil was 1 oocs or less, the anti-sticking properties were good, and no thread breakage or loose filaments were observed during spinning, but when the viscosity of the blended oil exceeded 100 cs, the spinning At times, the above-mentioned troubles occurred frequently, and it was difficult to obtain a bobbin made of perfect urethane elastic yarn.

(Effects of the Invention) As described above, according to the polyurethane elastic fiber production of the present invention, there is extremely little bobbin system sticking, thread breakage during spinning,
There is no occurrence of loose filaments, scum falling off, etc., and bobbin thread with less thread breakage can be obtained in subsequent processes.

procedural amendment old December 22, 1982 Mr. Manabu Shiga, Commissioner of the Patent Office, is qualified.

1. Indication of the case Patent Application No. 214900 filed in 1982 2. Name of the invention Process for producing polyurethane elastic fibers 8. Person making the amendment Relationship to the case Patent applicant address 17-4 Sumida 5-chome, Sumida-ku, Tokyo 534 Patent Department 5, Kaburobo Co., Ltd., 1-5-90 Tomobuchi-cho, Bejima-ku, Osaka City, “Claims” and “Detailed Description of the Invention” of the specification subject to amendment
Column 6, Contents of amendment (1) The statement in the scope of claims of the specification is amended as shown in the attached sheet.

(2) The description in the detailed description of the invention section of the specification should be divided into the following categories:
Paper Patent Claims When producing polyurethane elastic fibers by a melt spinning method, a blended oil with a viscosity of 100 centistokes (30°C) or less, which is made by blending amino-modified silicone with mineral oil and/or polydiolganosiloxane, A method for producing polyurethane elastic fibers, which comprises applying the polyurethane elastic fibers and then winding them up.

Claims (1)

[Claims] When producing polyurethane elastic fibers by the melt spinning method, a blended oil with a viscosity of 100 centistokes (30°C) or less, which is made by blending amino-modified silicone with mineral oil and/or polyzirganosiloxane, is applied to the polyurethane elastic fibers. A method for producing polyurethane elastic fibers characterized by post-rolling.