WO1999064663A1

WO1999064663A1 - Fiber treating agent and fiber treated with the same

Info

Publication number: WO1999064663A1
Application number: PCT/JP1999/003110
Authority: WO
Inventors: Nanae Hizumi; Yasuyuki Nomura; Tetsuo Doi
Original assignee: Matsumoto Yushi-Seiyaku Co., Ltd.
Priority date: 1998-06-12
Filing date: 1999-06-10
Publication date: 1999-12-16
Also published as: KR20010042583A; JP4090693B2; EP1160371A1; EP1160371A4

Abstract

A fiber treating agent which not only prevents polyamide fibers and the like from suffering scum deposition on the fiber surface during long-term storage to thereby prevent the fibers from fluffing or breaking during post-processing and from giving a knit of reduced quality, but imparts high collectability to synthetic fiber filaments. The treating agent contains either (a) a urethane compound obtained from a C12+ polyhydric alcohol and an organic diisocyanate or (b) an amide compound obtained from a C12+ polycarboxylic acid and an organic diisocyanate. Especially preferably, the urethane compound is one obtained from a dimer alcohol having a molecular weight of 300 to 1,000 and an organic diisocyanate, while the amide compound is one obtained from a dimer acid having a molecular weight of 300 to 1,000 and an organic diisocyanate.

Description

Description Fiber treatment agent and fiber treated with it Technical field

The present invention relates to a treatment agent and fibers treated therewith. More specifically, it imparts high convergence to synthetic fiber filaments and prevents the deposition of oligomers and internal additives during long-term storage of polyamide fibers or polyamide fibers or force-balancing yarns covered with polyamide fibers. And fiber treated with the same.

Background art

In the manufacturing process of synthetic fibers represented by nylon 6, nylon 66, polyester, etc., especially filaments, streamlining by streamlining the process and improving the productivity are aimed at by omitting the process. Polyamide fibers such as Nylon 6 and Nylon 66 produced by the P OY (Pre Oriented Yarn) method of about 0,000 m / min or the high-speed spinning method of more than 5,00 Om / min. During storage, the oligomers inside the fiber precipitate on the fiber surface, so they accumulate and accumulate (called scum) on various contacts (for example, guides, mouth rollers, heaters, etc.) in the post-processing step. For this reason, there is a problem that friction increases, and the generation of fluff and breakage due to fiber damage increases.

In the sock production process called support pantyhose, which has been increasing in demand in recent years, yarn in which polyurethane fibers are covered with polyamide fibers is used for knitting. Yarns in which polyurethane fibers are covered with polyamide fibers (hereinafter referred to as covering yarns) are manufactured because not only polyamide oligomers but also internal additives and urethane oligomers in polyurethane fibers precipitate on the surface of the power-balancing yarns during storage. In the knitting process, scum adheres and accumulates on guides, knitting nails, and the like, and there is a problem in that the occurrence of thread breakage due to an increase in friction increases and the quality of the knitted articles decreases. These problems are remarkably observed in polyamide fibers produced by the OY method or the high-speed spinning method, particularly in multifilament yarns having a large surface area. Therefore, in order to improve the operability of the post-processing step and the quality of the knitted article, there has been a strong demand for a treating agent that prevents scum generated during long-term storage of polyamide fiber and polyamido polyurethane polyurethane balling yarn.

A 30% water-based emulsion is applied to the fiber in the spinning process. Once the yarn has been drawn, it can be drawn further. The draw-twisting method (UDY-DT method), POY-DT method, POY-DT method, P〇Y method — Synthetic fibers are produced by a two-stage method such as the DTY method, a spin-draw method in which spinning and stretching are performed continuously and winding, or a one-step method in which a high-speed spinning method is used in which winding is performed without stretching. Is the current situation.

For the purpose of preventing the rolled-up yarn from wrapping, looping, etc., and smoothly passing through the post-processing step, the yarn is usually entangled with an inter-laser before winding to impart a bunching property to the yarn. As the yarn-making speed increases, it becomes difficult to impart sufficient entanglement to the yarn using an interleaver, and there is a problem that fluffing and yarn breakage occur when attempting to forcibly entangle the yarn by increasing the air pressure. .

In order to solve this problem, there has been a strong demand for a treating agent having excellent convergence. Disclosure of the invention

An object of the present invention is to provide a fiber treatment agent.

It is another object of the present invention to provide a fiber treating agent capable of effectively preventing synthetic fibers such as polyamide fibers from generating oligomers and internal additives during long-term storage.

Still another object of the present invention is to provide a fiber treating agent capable of preventing generation of scum due to oligomers and internal additives, and preventing fluff, yarn breakage or quality deterioration of a knitted fabric in a post-processing step. It is in.

Still another object of the present invention is to provide a fiber treating agent capable of giving synthetic fibers high bunching properties. Still another object of the present invention is to provide a synthetic fiber which has been treated with the fiber treating agent of the present invention, has high convergence, and suppresses generation of scum to prevent fluff, yarn breakage or quality deterioration of a knitted fabric. It is in.

Still other objects and advantages of the present invention will become apparent from the following description.

According to the present invention, the above objects and advantages of the present invention are, firstly, obtained from a urethane compound obtained from an alcohol having 12 or more carbon atoms and an organic diisocyanate and a carboxylic acid having 12 or more carbon atoms and an organic diisocyanate. The mi-treating agent is characterized by containing at least one compound selected from the group consisting of amide compounds.

According to the present invention, the above objects and advantages of the present invention are secondly achieved by a synthetic fiber treated with the fiber treating agent of the present invention.

Furthermore, according to the present invention, the above objects and advantages of the present invention are, thirdly, a urethane compound obtained from a ^ ffi alcohol having 12 or more carbon atoms and an organic diisocyanate, and a carboxylic acid having 12 or more carbon atoms and an organic compound. This is achieved by using at least one compound selected from the group consisting of amide compounds obtained from diisocyanate as a fiber treatment agent.

Detailed description of the invention

The perylene compound used in the present invention can be obtained as a reaction product of a polyhydric alcohol and an organic disocyanate.

As the alcohol, a ^ fffi alcohol having 12 or more carbon atoms, preferably a polyhydric alcohol having 12 to 60 carbon atoms, particularly preferably a polyhydric alcohol having 20 to 40 carbon atoms, for example, a diol is used.

Examples of the polyalcohol include alkylene diols such as dodecamethylene diol and octane decamethylene diol, dimer monoalcohol obtained by reducing and converting dimer monoacid obtained by dimerizing unsaturated fatty acid, and poly (ethylene oxide) or propylene oxide added thereto. Oxyalkylene polyhydric alcohol and the like. These are used alone or in combination of two or more.

The organic diisocyanate used in the present invention includes, for example, tolylene diisocyanate. Examples include isocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, and hexylmethane-1,4,4-diisocyanate. These are used alone or in combination of two or more.

The amide compound used in the present invention is obtained as a reaction product involving decarboxylation between a polycarboxylic acid and an organic diisocyanate.

As the planar carboxylic acid, a polycarboxylic acid having 12 or more carbon atoms, preferably a polycarboxylic acid having 12 to 60 carbon atoms, particularly preferably a molecular weight such as dimeric acid obtained by dimerizing unsaturated fatty acid A dicarboxylic acid of 300 to 10,000 is preferred.

As the carboxylic acid, for example, a dimer obtained by dimerizing an unsaturated fatty acid such as an alkylenedicarboxylic acid such as dodecamethylene dicarboxylic acid or octadecylenedicarboxylic acid, an alkenyl succinic acid such as dodecenylsuccinic acid or octadecenyl succinic acid, or linoleic acid. Monoacid and the like. These are used alone or in combination of two or more. An aromatic carboxylic acid having less than 12 carbon atoms, such as phthalic acid, isophthalic acid, and terephthalic acid, can be used together with a polyvalent carboxylic acid having 12 or more carbon atoms.

Such an aromatic dicarboxylic acid is used in an amount of 1 mol or less, more preferably 0.5 mol or less, per 1 mol of the polycarboxylic acid.

As the organic disocyanate, the same compounds as those described above can be used.

In the above-mentioned reaction for producing a urethane compound and an amide compound, the polyhydric alcohol or polycarboxylic acid is in a stoichiometric excess with respect to the organic diisocyanate compound, that is, the molecular weight of the urethane compound or amide compound to be produced is 8 It is preferable to use them in such a ratio that the ratio becomes from 0.000 to 30,000, more preferably from 1,000 to 100,000.

If the molecular weight of the urethane compound or amide compound exceeds 30,000, the compatibility with other components in the fiber treatment agent becomes poor. On the other hand, if the molecular weight of the urethane compound or amide compound is less than 800, for example, polyamide fiber The effect of preventing precipitation of the polyamide oligomer during storage is small, and the effect of imparting convergence to the synthetic fiber filament is not sufficient.

Further, when the polyhydric alcohol or polycarboxylic acid used has less than 12 carbon atoms, the compatibility of the resulting perylene compound with other components in the fiber treatment agent is reduced, and For example, the effect of preventing precipitation of amide oligomers during storage of polyamide fibers or polyurethane oligomers during storage of polyurethane fibers is reduced. From the viewpoints of compatibility with other components in the fiber treatment agent, an effect of preventing amide oligomer precipitation, an effect of preventing precipitation of urea oligosaccharide, and a property of converging, preferably, the carboxylic acid is used in a liver volume of 300 to 1,000. The dimer monoacid is 0, and the alcohol is dimer mono alcohol obtained by reducing and converting these dimer monoacids.

The stoichiometric ratio of the polyhydric alcohol or polycarboxylic acid and the organic diisocyanate in the reaction is preferably 2 to 10 equivalents of the alcohol or polycarboxylic acid per 1 equivalent of the organic diisocyanate. .

When the amount is less than 2 equivalents, a high molecular weight urethane compound or amide compound is formed, and the compatibility with other components in the difficult-to-treat agent is deteriorated. On the other hand, when the amount exceeds 10 equivalents, for example, an amide oligomer of polyamide fiber This is not preferred because the effect of preventing precipitation is reduced.

When the terminal of the amide compound of the present invention is a hydroxyl group, it may be partially or entirely neutralized with an alkali such as an alkali metal, ammonia, amine, or alkanolamine.

The urethane compound in the present invention also includes a urethane compound having an amide structure, which is produced by substituting less than 50 mol% of a polyhydric alcohol with a carboxylic acid.

Further, the amidohi compound in the present invention also includes an amide compound having a urethane structure produced by substituting less than 50 mol% of a polycarboxylic acid with a polyhydric alcohol.

As described above, the urethane compound having an amide structure and the amide compound having a urethane structure are also considered to be applicable with the necessary replacement. Should be understood.

The urethane compound and the amide compound in the present invention are obtained, for example, by reacting a polyhydric alcohol, a polyhydric carboxylic acid or a mixture of a polyhydric alcohol and a polyhydric carboxylic acid with an organic diisocyanate at, for example, 50 to 180. It can be manufactured by

The fiber treatment agent of the present invention may use the above-mentioned perylene compound or amide compound or a composite compound thereof alone, but if necessary, other known components generally compounded in the fiber treatment agent, For example, lubricants such as fatty acid esters, mineral oil, PO / E0 polyether, polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, PEG fatty acid ester, polyhydric alcohol ester, polyoxyethylene polyhydric alcohol Nonionic emulsifier components such as esters, alkali metal salts such as alkanesulfonates and alkyl phosphates, amine salts, antistatic agents such as alkylimidazoline-based activators and betaine-based activators may be blended. Commonly used ingredients include aliphatic esters such as dodecyl stearate, isooctyl palmitate and isopropyl palmitate, and polyoxyethylene alkyl ethers.

The fiber treating agent of the present invention preferably contains the urethane compound and the Z or amide compound in an amount of 0.5 to 80% by weight, more preferably 2 to 30% by weight. When applying the fiber treating agent to the fiber, the urethane compound and the amide compound or the amide compound are dissolved in crude oil (neat oil), an organic solvent or a low-viscosity mineral oil, and diluted. It is applied in a spinning, drawing, false twisting, rewinding or warping process by a known lubrication system such as a metering pump system, a spraying system, and an immersion method. The applied amount is preferably from 0.01 to 3.0% by weight, particularly preferably from 0.02 to 1.0% by weight, as the urethane compound or the amide compound, based on the weight of the fiber. In many cases, the smoothing agent component is blended at 15 to 90% by weight based on the fiber treating agent, and the nonionic emulsifier component is blended at 5 to 50% by weight based on the fiber treating agent.

According to the present invention, therefore, synthetic fibers, such as poly, treated with the fiber treatment agent of the present invention. A covering yarn is provided in which a polyamide fiber is used to cover a polyamide fiber, a polyurethane fiber and a polyurethane fiber.

In addition, conventionally, it has not been known to use the urethane compound or the amide compound used in the present invention for a fiber treatment agent, and the present invention also provides such use. Power for describing the present invention in detail by giving examples below The present invention is not limited to these.

Example 1

A predetermined amount of the compound shown in Table 1 below was blended with the reference treatment agent A shown in Table 2 below, and the treatment agents 1 to 8 and comparative treatment agents 9 to 11 of the present invention shown in Table 3 were used as aqueous emulsions. Prepared as These treatment agents are attached to a nylon 6, 6, filament 50 d / 13 f defatted yarn so that the solid content of the treatment agent is 1% based on the fiber weight. The prevention was evaluated. Table 3 shows the evaluation results.

table 1

In Table 1, P〇 indicates propylene oxide, and EO indicates ethylene oxide.

Table 2 (Standard treatment agent A)

POE in reference treatment agent A indicates polyoxyethylene. Table 3

The evaluation test was performed by the following method.

(1) Focusability

Fix the upper end of a 30 cm long sample thread, cut a 15 cm section from above with sharp scissors while applying a load of 30 g to the lower end. ) Was measured. The length (fluff) of the disturbed part is expressed in mm, and the smaller the value, the better the convergence.

(2) Prevention of oligomer precipitation

The sample wound on a paper tube is stored in an environmental tester at 50 and 90% RH at 50 for 1 week, and is allowed to run on a black velvet at a yarn speed of 20 OmZ for 5 minutes, and then accumulated on the black velvet. The amount of white scum (polyamide oligomer) was visually determined.

瞧 Standard

◎: No scum at all 〇: Scum is slightly present △: Scum is quite present

X: High scum XX: Extremely high scum

Example 2

Compounds A, B and D shown in Table 1 were blended with reference treating agent B shown in Table 4 below to prepare treating agents 12 to 16 of the present invention and comparative treating agents 17 and 18 shown in Table 5. did. These treatment agents nylon 66 filament 10 dZ7 f, polyurethane yarn 20ά / 2ά, and covering yarn made using these yarns, as it is crude oil, 2% by weight of treatment agent solids based on fiber weight The evaluation was carried out by attaching them so that Simultaneous evaluation was also performed on the unoiled after oil yarn to which the above-mentioned treating agent was not attached. Table 5 shows the evaluation results. Table 4 (Standard treatment agent Β) Isooctyl palmitate 45

Isopropyl palmitate 45

ΡΟΕAlkyl ether 10 Table 5 Test No. Treatment agent of the present invention Comparative treatment agent

1 2 1 3 1 4 1 5 1 6 1 7 1 8 1 9 Reference agent B 1 0 0 1 0 0 1 0 0 1 0 0 1 0 0 1 0 0

Compound A 2 5 1 0 Commercial mineral oil-based oil Yuichi Oil Compound B 5 Koichi ^ ^ Qualile Unlubricated Compound D 5

Nylon oligomer

〇〇〇 X X X X X Precipitation prevention ◎ 〇

Polyurethane yarn oligomer

〇〇〇 Δ X X X Precipitation prevention ◎

Internal additives

Δ 〇 X X Precipitation prevention ◎ 〇 Δ X

Covering yarn oligomer

Δ 〇 X X Precipitation prevention ◎ △ Δ X X X X

Internal additives

Δ 〇

Precipitation prevention ◎ 〇 Δ XXX

(3) Evaluation test of internal additive precipitation prevention

After storing the polyurethane yarn and the covering yarn sample in an o: freezer for one month, the state of generation of scum (an internal additive of the urethane yarn) on the fiber surface was determined by taking an electron micrograph.

Criterion

◎: No scum at all 〇: Scum is slightly present △: Scum is quite present

X: Scum is much X X: Scum is remarkably many

By applying the treating agent of the present invention to the polyamide fiber, the amide oligomer can be prevented from depositing on the fiber surface during long-term storage, so that scum is less generated in the post-processing step, and fluff and yarn breakage are reduced. it can.

By applying the treating agent of the present invention to the polyamide / polyurethane covering yarn, not only the amide oligomer but also the urethane oligomer and the internal additive in the urethane can be prevented from being precipitated on the surface of the material. Scum generation during knitting is suppressed and scum is reduced, so that knitting efficiency and knitting quality can be improved.

The use of the treating agent of the present invention significantly improves the bunching properties of the yarns in the spinning step and the post-processing step, reduces fluff and yarn breakage, improves quality, and enables streamlining of the process. In other words, sufficient bunching properties can be obtained only by lubricating the treating agent of the present invention to the synthetic fiber filament yarn, so that it is possible to reduce or omit the entanglement treatment (interlace) of the yarn in the yarn making process.

Claims

The scope of the claims

1. At least one compound selected from the group consisting of urethane compounds obtained from ^ ffi alcohols having 12 or more carbon atoms and organic diisocyanates and amide compounds obtained from polyvalent carboxylic acids having 12 or more carbon atoms and organic diisocyanates A fiber treating agent comprising:

2. The fiber treating agent according to claim 1, further comprising an aliphatic ester and a polyoxyethylene alkyl ether.

3. The fiber treating agent according to claim 1, wherein the polyhydric alcohol having 12 or more carbon atoms is a dimer-based alcohol having a molecular weight of 300 to 1,000.

4. The fiber treating agent according to claim 1, wherein the polyvalent carboxylic acid having 12 or more carbon atoms is a dimeric acid having a molecular weight of 300 to L, 000.

5. The urethane compound according to claim 1, wherein the urethane compound is a urethane compound obtained by reacting a polyhydric alcohol having 12 or more carbon atoms with an organic diisocyanate at an equivalent ratio of the former to the latter of 2 to 10. Fiber treatment agent.

6. The amide compound according to claim 1, wherein the amide compound is an amide compound obtained by reacting a polyvalent carboxylic acid having 12 or more carbon atoms with an organic diisocyanate at an equivalent ratio of the former to the latter of 2 to 10. Fiber treatment agent.

7. Synthetic fibers treated with the fiber treating agent of claim 1.

8. Synthetic fiber is made of polyamide fiber, polyurethane fiber or polyurethane fiber. 8. The synthetic fiber according to claim 7, wherein the synthetic fiber is a power-balancing yarn covered with a amide fiber.

9. At least one selected from the group consisting of urethane compounds obtained from ^ ffi alcohols having 12 or more carbon atoms and organic diisocyanates and amide compounds obtained from polyvalent carboxylic acids having 12 or more carbon atoms and organic diisocyanates. Use of certain compounds as fiber treatment agents.