JP2003049368A - Oil agent for elastic fiber - Google Patents

Abstract

(57) [Summary] [PROBLEMS] To prevent elastic fibers from sticking to each other on a spinning bobbin when manufacturing an elastic fiber (in particular, by a melt spinning method).
In the subsequent processing step, the unwinding balance between the inner layer and the outer layer of the cheese is improved, the yarn slides moderately, the spinning bobbin and other yarns are prevented from falling and breaking, and sediment falling off on guides and the like during yarn running. (Scum) An oil agent for elastic fibers that can suppress the occurrence, stabilize the operation in the spinning process and the subsequent processing process by appropriately adjusting the metal friction with the knitting needle used in the product processing process and preventing yarn breakage. To provide. The present invention provides an oil agent for elastic fibers containing an amino-modified polyorganosiloxane resin represented by the general formula (1). Embedded image

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an oil agent for elastic fibers, and more particularly to an oil agent for elastic fibers containing an amino-modified polyorganosiloxane resin having a specific structure. Furthermore, the present invention relates to a method for producing elastic fibers (particularly polyurethane) using the oil agent.

[0002]

2. Description of the Related Art Conventionally, various proposals have been made regarding an oil agent for elastic fibers. A method of applying to a fiber an oil agent slurry in which solid fine particles, a metal salt powder of a higher fatty acid, etc. are dispersed in a base oil (Japanese Patent Publication No. 41-289 and Japanese Patent Publication No. 40-55).
57), a method of dispersing a room temperature solid wax in an oil agent mainly composed of mineral oil (Japanese Patent Publication No. 43-272 and Japanese Patent Publication No. 43-995).
5, JP-B-44-8907), a method of using a room temperature liquid substance as an anti-sticking component (JP-B-45-40719, JP-A-48-19893, JP-A-57-128276),
There is a method of dissolving cyclic aluminum siloxane in dimethylsiloxane (Japanese Patent Publication No. 39-24858). However, these methods cannot be said to be sufficient for preventing the fibers from sticking to each other on the spinning bobbin.

A method using a specific silicone resin is disclosed in JP-A-9-78460. Although this oil agent has a high anti-sticking effect, it has a high friction against metal and has a problem that thread breakage occurs in the knitting process.

Further, in order to reduce friction and deactivate the active isocyanate existing on the yarn surface, a method of containing a low molecular weight monoamine or diamine in an oil agent (Japanese Patent Publication No. 46-1).
6312, JP-A-58-132170). Further, a method of applying an oil agent containing an amino-modified silicone to urethane elastic fiber and then winding it up is disclosed in JP-B-6.
3-8233. The yarn wound up with these oil agents has a small yarn / yarn friction and has a large twill collapse when the yarn is taken out from the bobbin.

As a method of preventing twill collapse, Japanese Patent No. 2788097 has proposed a method of using amino-modified silicone and cyclic polyorganosiloxane in combination. However, in this method, unwinding generally becomes better as the amino equivalent of the amino-modified silicone is smaller, but when the amino equivalent is made smaller, spinning scum occurs in melt spinning in which NCO groups remain, and there is a problem in operation. .

As described above, many proposals for oil agents have been made. However, considering not only the prevention of sticking but also the operational stability in spinning and subsequent processing steps, a satisfactory oil agent has not been provided.

[0007]

Therefore, the present invention prevents the sticking of fibers to each other on a spun bobbin when producing elastic fibers (particularly by the melt spinning method), and the cheese is used in the subsequent processing step. Improves the unwinding balance between the inner and outer layers of the yarn, keeps the yarn slippery properly, prevents the spinning bobbin from falling and collapsing, and suppresses the generation of falling deposits (scum) on the guides etc. during running of the yarn. The object is to provide an oil agent for elastic fibers that can stably perform operations in the spinning step and subsequent processing steps by making metal friction with a knitting needle used in a product processing step appropriate and preventing yarn breakage. To do.

[0008]

Means for Solving the Problems As a result of repeated studies to solve the above problems, the present inventors have attached an oily agent for elastic fibers containing a specific amino-modified polyorganosiloxane resin to fibers in a spinning process. It was found that the above problems can be solved by doing so.

That is, the present invention is as follows. (1) An oil agent for elastic fibers, comprising an amino-modified polyorganosiloxane resin represented by the general formula (1).

[0010]

[Chemical 2] (Here, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , and R ₆ are each independently an alkyl group having 1 to 5 carbon atoms, and the molar ratio of a, b, and c is a / b / c. = 80 to 127/160 / 1.0 to 2.4, and d is 0.
Or 1, and the amino modified polyorganosiloxane resin has an amino equivalent of 3,400 to 42,000 and a number average molecular weight of 6,800 to 42,000. (2) The content of the amino-modified polyorganosiloxane resin is 0.1 to 20% by mass with respect to the total oil agent (1), the oil agent for elastic fiber (3), the elastic fiber is polyurethane (1) Alternatively, the oil agent for elastic fiber according to (2). (4) In the elastic fiber spinning step, the elastic fiber oil agent according to (1) or (2) is applied to the thread before it is wound up after spinning, and the method for producing the elastic fiber. . (5) The method for producing an elastic fiber according to (4), wherein the elastic fiber is polyurethane.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.

The elastic fiber oil agent of the present invention contains the amino-modified polyorganosiloxane resin represented by the above general formula (1).

Here, in the formula, O _1/2 represents an oxygen molecule shared with an adjacent structural unit in the polymer. Further, O _4/2 represents that there are four O _1/2 and O _2/2 represents that there are two O _1/2 . That is, the structural unit in which O _1/2 is described is a monofunctional structural unit having 3 organic groups,
_The structural unit in which _4/2 is described is a tetrafunctional structural unit having no organic group, that is, leaving all bonding hands,
The structural unit in which O _2/2 is described is a bifunctional structural unit having two organic groups.

In the general formula (1), R ₁ , R ₂ , R ₃ , R ₄ and R
₅ and R ₆ are each independently an alkyl group having 1 to 5 carbon atoms, and the molar ratio of a, b and c is a / b / c = 80 to 127/160 / 1.0 to
2.4, d is 0 or 1, and the amino equivalent of the amino-modified polyorganosiloxane resin is 3,400.
The number average molecular weight is 6,800 to 42,000.

Here, when the molar ratio of a is 80 or less, scum occurs, and when it is 127 or more, the prevention of sticking becomes insufficient. When the molar ratio of c is 1 or less, friction against metal becomes high, and 2.4
The above causes scum. When the amino equivalent is less than 3,400, spinning scum occurs, and when it exceeds 42,000, the prevention of sticking becomes insufficient. If the molecular weight is less than 6,800, scum occurs, and if it exceeds 42,000, the prevention of sticking becomes insufficient.

The above-mentioned amino equivalent is defined (or measured) as follows.

(Amino equivalent) = 1 / (amino group concentration) =
(Sample weight) / (Amino group mole number)

Therefore, the amino equivalent is calculated from the above relational expression. The following method can be used as a general measurement method.

1 g of an oil sample is weighed in a flask, 25 ml of isopropyl alcohol is added, and the mixture is stirred well to dissolve.
Neutralization titration is carried out with 0.1 mol / L hydrochloric acid using the indicator bromphenol blue. The amino equivalent weight is calculated by the following formula.

(Amino equivalent) = (Sample weight) × 10 ⁴ /
{(Hydrochloric acid factor) × (hydrochloric acid titration)} Mineral oil and / or dimethylsiloxane can be mentioned as the base oil of the oil agent containing the amino-modified polyorganosiloxane resin of the present invention.

Further, in the oil agent for elastic fiber of the present invention, if necessary, as an anti-sticking component, for example, mineral solid fine particles such as talc, silica, colloidal alumina, or metal powder salt of higher fatty acid, or polyether. Silicone, epoxy-modified silicone, amino-modified silicone having a linear structure, modified silicone such as silicone resin, and alcohols, fatty acid esters and the like can be appropriately mixed as a binder. Further, components usually used in spinning oils such as antistatic agents, antioxidants, and ultraviolet absorbers can be added.

The content of the amino-modified polyorganosiloxane resin of the present invention is 0.1 to 20% by mass, more preferably 1 to 10% by mass, based on the total oil. If the content is too large, the viscosity of the oil agent increases, the resistance to the yarn during spinning increases, and the spinning stability decreases. When the content is low, the active NCO group remains on the surface of the yarn, and therefore the yarn /
The chemical reaction between the yarns causes the yarns to adhere to each other, resulting in insufficient prevention of sticking.

The viscosity of the oil agent containing the amino-modified polyorganosiloxane resin of the present invention is 100 c at 30 ° C.
It is preferable to adjust the viscosity of the base oil and the content of the amino-modified polyorganosiloxane resin so that the viscosity is not more than St.

The method of applying (also referred to as adhering) the oil agent of the present invention to the elastic fiber includes a method of contacting with an oiling roller until the filament yarn discharged from the spinneret is wound up, or a lubrication with a metering and discharging nozzle. The method can be performed by using an oil supply device.

The oil agent of the present invention is usually used in an amount of 2 times for elastic fiber.
It is recommended to add 10 to 10% by mass, preferably 3 to 6% by mass.

Examples of elastic fibers in which the oil agent of the present invention can be used include polyurethane, and composite elastic yarn in which thermoplastic resin other than polyurethane is uniformly kneaded at the same time using polyurethane as a base material. However, in terms of elastic recovery,
Elastic fibers of polyurethane alone can be preferably used.

As the thermoplastic resin other than polyurethane, addition-polymerization type polyethylene, polypropylene,
Examples thereof include polystyrene, polymethylmethacrylate polycondensation type polyamide, polyester, polycarbonate, polyphenylene oxide ring-opening polymerization type polyacetal and the like.

Further, the oil agent of the present invention can be applied to any method such as a melt spinning method, a dry spinning method and a wet spinning method which have been conventionally used as a method for producing an elastic fiber, but particularly melt It can be suitably applied to a spinning method.

In particular, when the polyurethane elastic fiber is manufactured by the melt spinning method, the following specific manufacturing methods can be mentioned.

After synthesizing a prepolymer having NCO groups at both terminals obtained from a polymer diol and a diisocyanate,
A method in which a low molecular weight diol is added and continuously extruded and cut to obtain pellets, which are melt-extruded in an extruder and spun, or the melted pellets are further terminated with NCO obtained from a polyol and a diisocyanate. Of adding a prepolymer having a base group and discharging from a nozzle and spinning, and a prepolymer having NCO groups at both ends obtained from a polyol and a diisocyanate, and a hydroxyl group at both ends obtained from a polyol, a diisocyanate and a low molecular weight diol The method obtained by a melt spinning method in which the prepolymer of (1) is supplied to a reactor and the polymer is continuously extruded from the nozzle without solidifying after the reaction is completed.

In the present invention, in the melt spinning step as described above, the oil agent of the present invention is applied to the filament by the oil supply device before the filament is wound on the roller.

Among the above-mentioned melt spinning methods, particularly in the latter two spinning methods, it is preferable to leave the NCO group in the obtained yarn. This is because after the NCO group in the yarn is wound up, further chain extension or crosslinking reaction proceeds, and a polyurethane having improved heat resistance can be obtained. Therefore, in the melt-spinning method of the polyurethane elastic fiber, it is more effective to apply the oil agent of the present invention to the filament discharged with the isocyanate remaining in the yarn in an amount of 0.3% by mass or more and 2.0% by mass or less.

[0033]

EXAMPLES The present invention will be described more specifically by way of examples. As a method for evaluating the effects of the present invention, unwinding tension, running friction against metal, thread-yarn friction, presence / absence of spinning scum, winding shape, strength retention after dipping in oil, and presence / absence of shape collapse by unwinding test went. Each measuring method is as follows. Unwinding tension As shown in Fig. 1, the yarn is sent from the cheese at the over end, and after passing through the guide, the change in tension when winding at a winding speed of 200 m / min is measured for 10 minutes, and the average value of tension is calculated. It was the unwinding tension. Metal running friction (F / M friction) As shown in Fig. 2, the winding speed of the yarn delivered by the delivery roller at 100 m / min was adjusted so that the initial tension (T2) was 3.0 g. The tension (T1) was measured and the coefficient of friction was calculated. The following formula was used for the friction coefficient.

Friction coefficient = 6 / (5π) × 1n (T2 / T1) Thread-thread friction (F / F friction) As shown in FIG. 3, the yarn path from the load part to the tensiometer via the free roller is free. Twist the yarn twice at the roller, and apply a tension of 2 g when wound at a speed of 0.2 m / min.
The value divided by was calculated as the thread-yarn friction. Occurrence of spinning scum Immediately after spinning for 2 hours, the surface of the winding roller was scraped off with a metal spatula to visually confirm the presence or absence of solid matter. The uniformity of the rolled cheese side surface was visually inspected, and it was confirmed whether it was twill-fall or step-wound. Strength retention after immersion in oil solution Immediately after spinning, a thread was cut out from cheese, immersed in a predetermined oil solution whose humidity was adjusted to 40 ° C, and shaken for 4 hours. After removing the excess oil agent, the strength of the yarn after 3 days was measured, and the strength of the cheese yarn was also measured and calculated by the following formula.

Strength retention rate (%) = (strength of each sample / strength of yarn) × 100 Deformation by unwinding test Existence of 5 m / meter using a device excluding the tensiometer and the friction body shown in FIG. Min., The winding speed was set to 15 m / min, and rewinding was performed for 24 hours to confirm the presence or absence of yarn breakage or twill drop.

(Spinning Example 1) As polymer diol, 575 parts by weight of poly-3-methyl-pentamethylene adipate having a molecular weight of 2,000 (hereinafter, also referred to as "PMPA") and 4,4'-diphenylmethane diisocyanate as diisocyanate (hereinafter 218 parts by weight of "MDI") was reacted at a reaction temperature of 80 ° C. and a reaction time of 60 minutes to obtain an NCO-terminated prepolymer.

As a polymer diol, polytetramethylene ether glycol having hydroxyl groups at both ends (hereinafter,
Also referred to as "PTMG"; molecular weight 1,000) at 97 parts by weight and MDI as diisocyanate at 47 parts by weight at a reaction temperature of 80 ° C. for a reaction time of 60 minutes to obtain a precursor, which is then obtained. 1,4-butanediol as a low molecular weight diol (hereinafter referred to as “BD
(Also referred to as "O") at a reaction temperature of 115 parts by weight of 115 parts by weight.
The reaction was carried out at a temperature of 60 ° C. for 60 minutes to obtain a hydroxyl group-terminated prepolymer.

A ratio of 803 parts by weight of NCO-terminated prepolymer to 197 parts by weight of hydroxyl-terminated prepolymer was continuously fed to a twin-screw extruder, and mixed and stirred under the conditions of a reaction temperature of 220 ° C. and a reaction time of 15 minutes. did. The obtained viscous material was directly sent to a spinning pump, discharged from a nozzle at 189 ° C., and wound on a paper tube at a spinning speed of 700 m / min to obtain a filament of 22 dtex.

(Spinning Example 2) 671 parts by weight of PMPA having a molecular weight of 2,000 as a polymer diol and 269 parts by weight of MDI as a diisocyanate were used at a reaction temperature of 80.
The reaction was carried out under conditions of a temperature of 60 ° C. and a reaction time of 60 minutes to obtain an NCO-terminated prepolymer. Then B as a low molecular weight diol
60 parts by weight of DO was continuously supplied to the biaxial reactor, and mixed and stirred under the conditions of a reaction temperature of 220 ° C. and a reaction time of 15 minutes. A filament was obtained from the obtained viscous material in the same manner as in Spinning Example 1.

(Spinning Example 3) PT as polymer diol
366 parts of MG (molecular weight 1965) and 84 parts of MDI as a diisocyanate were reacted by stirring in a synthesis tank at 60 ° C. for 90 minutes to obtain a prepolymer having NCO groups at both ends, and 175 parts of dimethylacetamide (hereinafter, "DMA
c)).

9 parts of ethylenediamine, 1 part of dibutylamine
A solution of 22 parts of DMAc was added dropwise onto the prepolymer solution to stir to complete the reaction.
Is added to obtain a spinning dope having a polymer concentration of 25%.

This stock solution was spun (600 m / min) by an ordinary dry spinning method to prepare a polyurethane elastic yarn of 22 dtex (two constituent filaments).

[0043]

Examples 1 to 6 Experiments were conducted using the filaments obtained by the method of Spinning Example 1 above.

Before the filament was wound up, each oil agent shown below was applied to the filament by 4.5% by mass by contacting it with an oiling roller.

In the structure represented by the general formula (1),
The molar ratio of a, b and c is a / b / c = 112/160 / 1.1 and d is 1
And R ₁ , R ₂ , R ₃ and R ₄ are CH ₃ , R ₅ is C ₃ H ₆ and R ₆ is C ₂ H ₄ , the amino equivalent is 9,000 and the molecular weight is 18,000.
An oil agent prepared by mixing 3% by mass of dimethylsiloxane with the amino-modified polyorganosiloxane resin is used. The viscosity of the oil solution was 7.3 cps. A similar experiment was conducted by changing each oil agent adjusted to a predetermined amino equivalent and amino-modified polyorganosiloxane resin concentration by appropriately changing the range of molar ratio and the molecular weight. Table 1 shows each oil agent used and the spinning results corresponding to the oil agent.
Shown in. In Table 1, the amino-modified polyorganosiloxane resin of the present invention is referred to as AR.

[0046]

[Table 1]

[0047]

Example 7 An experiment was conducted using the filaments obtained by the method of spinning example 2 described above.

The oil agent similar to that used in Example 1 was applied to the filament by 4.5% by mass by bringing the filament into contact with an oiling roller before winding.

The spinning results are shown in Table 1.

[0050]

Example 8 An experiment was conducted using the filament obtained by the method of spinning example 3 described above.

Before the filament was wound up, it was brought into contact with an oiling roller to apply the same oil agent as in Example 1 to the filament in an amount of 4.5% by mass.

The spinning results are shown in Table 1.

[0053]

[Comparative Examples 1 to 7] Using the filaments obtained by the method of Spinning Example 1, the oil agent containing the amino-modified polyorganosiloxane resin of the present invention was prepared, and the polyorganosiloxane resin (denoted as SR) shown in Table 1 was used. The same experiment as in Example 1 was conducted by replacing each oil solution containing The results are shown in Table 1.

In Comparative Examples 2 to 7, either an amino-modified polyorganosiloxane (denoted as AS) or an ether-modified polyorganosiloxane (denoted as ES) having a bifunctional repeating structure was used as an additive. Was included (see Table 1).

As is clear from the above experimental results, when the oil agent for elastic fibers contains the amino-modified polyorganosiloxane resin of the present invention, the anti-sticking effect is increased.

This is because the residual NCO group in the polymer reacts with the amino group in the amino-modified polyorganosiloxane resin, whereby the amino-modified polyorganosiloxane resin can be chemically bonded to the polyurethane elastic fiber. , N on the surface of polyurethane fiber
It seems that the CO group could be surely deactivated and the effect of preventing sticking could be improved. Further, the chemical bond between the amino-modified polyorganosiloxane resin and the polyurethane elastic fiber did not cause the deposit to fall off, and the release effect of the amino-modified polyorganosiloxane resin was effective in preventing sticking.

In Comparative Example 1, the F / M friction was high and thread breakage occurred. In Comparative Example 2 and later, although the F / M friction could be reduced by using AS and ES together, the F / F friction was decreased. However, in this example, the friction against metal running (F / M friction) was low and the friction between threads (F / F friction) was low.
Was maintained, the cheese did not collapse, and good results were shown on both sides.

By the way, the amino-modified polyorganosiloxane resin of the present invention is a resin having a three-dimensional structure which does not have fluidity at room temperature and has monofunctional and tetrafunctional structures as structural units. For example, as compared with the amino-modified silicone described in Japanese Patent No. 2788097 described in the section of the prior art (which is a linear structure that is fluid at ordinary temperature by repeating only a bifunctional structure), the amino-modified silicone of the present invention The polyorganosiloxane resin has a large molecular size per amino group and takes advantage of the fact that it has a resin structure, and shows better results.

That is, it is considered that the resin structure of the amino-modified polyorganosiloxane resin enhances the anti-sticking effect even by physical adsorption with the polyurethane elastic fiber.

Further, due to the resin structure of the amino-modified polyorganosiloxane resin, the NCO group existing on the yarn surface can be chemically bonded to the urethane elastic fiber by reacting with the amino group in the amino resin. NCO groups other than the bonding points are coated with resin,
It does not react with the active hydrogen on the surface of another yarn and does not contribute to adhesion. Therefore, finally, it was possible to obtain a urethane elastic fiber that reacted (crosslinked) with active hydrogen in the polymer and maintained heat resistance.

Further, due to the resin structure of the amino-modified polyorganosiloxane resin, the amino group does not penetrate into the inside of the polymer (thread) and reacts only with the NCO group on the surface. On the other hand, the linear structure amino-modified polyorganosiloxane may enter the inside of the polymer, and the chain extension or crosslinking reaction after spinning does not proceed, and the strength may be insufficient. In that respect, the amino-modified polyorganosiloxane resin of the present invention does not hinder the progress of further chain extension or crosslinking reaction in the yarn,
As shown in the examples, the strength retention of the polymer after immersion in the oil solution showed good results.

Further, when the amino-modified polyorganosiloxane of the present invention is used, the effect of suppressing the charging property can be recognized. When the cheese (thread wound on the paper tube) rolls on the roller and the thread is wound up, static electricity is usually generated due to continuous friction between the metal and the organic substance. However, 5% of the amino-modified polyorganosiloxane of the present invention is used. It was confirmed that the amount of charge was reduced when spinning was performed using the oil agent contained at the above concentration.

[0063]

As described above, the elastic fiber oil agent containing the amino-modified polyorganosiloxane resin of the present invention is used in the spinning step in the production of elastic fibers to prevent the fibers from sticking to each other on the spun bobbin. In the subsequent processing step, the unwinding balance between the inner and outer layers of cheese is made good, the slippage of the yarn is kept moderate and the spinning bobbin, etc. is prevented from falling and collapsing, and falls off to the guide etc. while the yarn is running. It was possible to suppress the generation of deposits (scum), to make the metal friction with the knitting needles used in the product processing process appropriate, and to prevent the yarn breakage. That is, it was possible to provide an elastic fiber oil agent effective for stably performing the operations in the spinning step and the subsequent processing steps.

[Brief description of drawings]

FIG. 1 is a diagram for explaining an unwinding tension measurement method, which is one of the evaluation methods used in the examples.

FIG. 2 is a diagram for explaining a method of measuring running friction with respect to metal, which is one of the evaluation methods used in the examples.

FIG. 3 is a diagram for explaining a method of measuring the thread-thread friction with respect to the thread-thread friction, which is one of the evaluation methods used in the examples.

Claims (5)

[Claims] 1. An oil agent for elastic fibers comprising an amino-modified polyorganosiloxane resin represented by the general formula (1). [Chemical 1] (Here, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , and R ₆ are each independently an alkyl group having 1 to 5 carbon atoms, and the molar ratio of a, b, and c is a / b / c. = 80 to 127/160 / 1.0 to 2.4, and d is 0.
Or 1, and the amino modified polyorganosiloxane resin has an amino equivalent of 3,400 to 42,000 and a number average molecular weight of 6,800 to 42,000. ) 2. The oil agent for elastic fibers according to claim 1, wherein the content of the amino-modified polyorganosiloxane resin is 0.1 to 20 mass% with respect to the total oil agent. 3. The oil agent for elastic fiber according to claim 1, wherein the elastic fiber is polyurethane. 4. A process for producing an elastic fiber, which comprises applying the oil agent for elastic fiber according to claim 1 to the yarn before winding up the yarn after spinning in the step of spinning the elastic fiber. . 5. The method for producing an elastic fiber according to claim 4, wherein the elastic fiber is polyurethane.