KR20130042463A - Agent for treating polyurethane elastic fiber, and polyurethane elastic fiber - Google Patents

Abstract

SUMMARY OF THE INVENTION An object of the present invention is to solve the problems of the prior art, and to provide stable and excellent anti-sticking property, uniform dissolvability, antistatic property, smoothness and productivity. It is providing the processing agent for polyurethane elastic fibers, and the polyurethane elastic fiber to which the said processing agent was provided.
The present invention contains at least one base component (A) selected from silicone oil, mineral oil and ester oil, and an acidic phosphate ester salt (B) of a divalent cation of a Group 2 element metal. The acidic phosphate ester salt (B) has an acidic hydroxyl group, and the molar ratio of the divalent cation of the acidic hydroxyl group and the group 2 element metal is 95/5 to 5/95, and the acidic phosphate ester salt (B) occupies the entire treatment agent. It is a processing agent for polyurethane elastic fibers whose weight ratio is 0.001-60 weight%.

Description

AGENT FOR TREATING POLYURETHANE ELASTIC FIBER, AND POLYURETHANE ELASTIC FIBER}

The present invention relates to a treatment agent for polyurethane elastic fibers and polyurethane elastic fibers.

In the spinning step, the elastic fiber is wound into a cheese shape after the treatment agent is applied to form a wound body. Since elastic fibers have viscoelastic properties, they are fibers that are easily interlocked. In particular, in the inner layer part of the winding body, deadlock progresses with time by the pressure applied at the time of winding. Therefore, when using an elastic fiber winding body, it will become bad and a thread will be broken.

When the yarn is wound from the winding body and processed into a beam or a letter, as described above, when the degree of deadlock is significantly different in the inner and outer layers of the winding body, that is, the uniformity is poor. If it falls, the difference between the tension of the inner layer and the tension of the outer layer becomes large. As a result, beam shape defects and letter deterioration are caused.

The processing agent for elastic fibers uses hydrophobic base components, such as a silicone oil, mineral oil, and ester oil. Therefore, the antistatic property was insufficient. If the antistatic property is insufficient, when the elastic fiber and the cotton yarn are interlaced, the wind surface is adsorbed to the elastic fiber by static electricity, and the suction port is blocked, and the thread breaks at the suction hole. Lose. As a result, there is a problem that you must clean occasionally.

In the beam forming step, the threads are close to each other by static electricity, causing breakage of the yarn and poor beam shape. Smoothness is required for stabilization of operability in the processing step.

Patent Document 1 proposes a method of using a treatment agent in which a higher fatty acid metal soap is dispersed in polydimethylsiloxane or mineral oil as a method of preventing the deadlock. However, as this treatment agent, higher fatty acid metal soap aggregates over time, segregates, and becomes nonuniform. When the non-uniform treatment agent is applied to the elastic yarn, the higher fatty acid metal soap is unevenly attached onto the elastic yarn, so that uniform smoothness and anti-deadlock cannot be obtained. In addition, since the degree of deadlock in the inner layer portion and outer layer portion of the winding body is also greatly different, there may be a breakage of the thread or deterioration in the quality of the letter in post-processing. In addition, agglomerates of higher fatty acid metal soaps became scum in the process, requiring periodic cleaning. Moreover, since this processing agent has a low friction between a fiber and a fiber, it may cause the shape defect of a winding body, may be insufficient in antistatic property, and wind surface adsorption may generate | occur | produce in post-processing.

As an antistatic agent, the method of using the alkali metal salt of an alkyl phosphate as a processing agent (patent document 2), the method of using the alkali metal salt and alkyl phosphate amine salt of an alkyl phosphate as a processing agent (refer patent document 3), an organic sulfonic acid compound or organic sulfuric acid The method of using a compound as a processing agent (refer patent document 4), the method of using a sulfosuccinic acid salt as a processing agent (refer patent document 5), etc. are proposed. However, since these antistatic agents are strong in polarity, the solubility with respect to the base component of the processing agent which consists of a hydrophobic component is not good, and it adheres unevenly on an elastic yarn. Therefore, uniform antistatic property may not be obtained, and it may fall out from an elastic yarn in post-processing, and may become scum. Moreover, it may adversely affect smoothness and anti-adhesion, and may cause a break | break of a thread when post-processing an elastic yarn. In addition, since organic sulfonic acid and organic sulfuric acid are strong acids, and alkali metal is a strong base, these strong acids and strong bases are liberated when wet winding a winding body, and the strength of a thread may fall.

Japanese Patent Application Publication No. 37-4586 Japanese Patent Application Publication No. Hei 4-146276 Japanese Patent Application Publication No. Hei 9-49167 Japanese Patent Application Publication No. Hei 11-61651 Japanese Patent Application Publication No. 10-298864

SUMMARY OF THE INVENTION An object of the present invention is to solve the problems of the prior art, and to provide a polyurethane elastic fiber treating agent and the treating agent which are capable of providing stable and excellent anti-adhesion resistance, uniform stability, antistatic property, smoothness, and productivity. It is to provide a polyurethane elastic fiber.

MEANS TO SOLVE THE PROBLEM The present inventors, in order to solve the said subject, as a result of repeated examination, this subject is solved by the processing agent for polyurethane elastic fibers containing a base component (A), and also containing a specific acidic phosphate ester salt (B). I found something that could be solved. That is, this invention contains the acidic phosphoric acid ester salt (B) of at least 1 sort (s) of base component (A) chosen from silicone oil, mineral oil, and ester oil, and the divalent cation of a group 2 element metal. The ester salt (B) has an acidic hydroxyl group, and the molar ratio of the divalent cation of the acidic hydroxyl group and the Group 2 element metal is 95/5 to 5/95, and the weight of the acidic phosphoric acid ester salt (B) in the whole treatment agent. It is a processing agent for polyurethane elastic fibers whose ratio is 0.001-60 weight%.

The Group 2 element 2 of the metal cations, Be ^{+ 2,} Mg ^{+ 2,} Ca ^{+ 2,} Sr ^{+ 2,} and preferably at least one species selected from Ba ^{+ 2.}

The acidic phosphoric acid ester salt is at least one component selected from an acidic phosphoric acid ester (C), a hydroxide of a Group 2 element metal, a Group 2 element metal, an oxide of a Group 2 element metal, and a carbonate of a Group 2 element metal (D ), And the molar ratio of the acidic hydroxyl group of the acidic phosphate ester (C) to the component (D) is preferably 100/5 to 100/95.

It is preferable that the said acidic phosphoric acid ester (C) is a compound represented by following General formula (1).

[Formula 1]

(R <^1> in Formula (1) represents a C1-C30 hydrocarbon group. X represents a C2-C4 alkylene group, XO represents an oxyalkylene group. A represents the added mole number of an oxyalkylene group. , 0 or an integer of 1 to 15. b and c are 1 or 2, respectively, and are integers satisfying b + c = 3.)

Moreover, the present inventors discovered that this subject can be solved also in the processing agent for polyurethane elastic fibers which mix | blends an acidic phosphate ester (C) and a component (D) with a base component (A) in a specific ratio. That is, the present invention provides at least one base component (A) selected from silicone oil, mineral oil and ester oil, acidic phosphate ester (C), a Group 2 element metal, a hydroxide of a Group 2 element metal, and a Group 2 element. At least one component (D) selected from oxides of metals and carbonates of group 2 element metals is blended, and the molar ratio of the acidic hydroxyl group of the acidic phosphate ester (C) to the component (D) is from 100/5 to It is 100/95 and is a processing agent for polyurethane elastic fibers whose weight ratio of the sum total of the said acidic phosphate ester (C) and the said component (D) which occupies for the whole processing agent is 0.001-60 weight%.

It is preferable that the said group 2 element metal is at least 1 sort (s) chosen from Be, Mg, Ca, Sr, and Ba. It is preferable that the said acidic phosphoric acid ester (C) is a compound represented by the said General formula (1).

The treatment agent of the present invention is at least one selected from alkyl modified silicones, ester modified silicones, polyether modified silicones, carbinol modified silicones, carboxy modified silicones, amino modified silicones, organic phosphate ester neutralizers of amino modified silicones and silicone resins. It is preferable that the component of further contains and the weight ratio of the said component to the whole processing agent is 0.01 to 10 weight%.

As for the polyurethane elastic fiber of this invention, 0.1-15 weight% of said processing agents are provided to the polyurethane elastic fiber main body.

The processing agent for polyurethane elastic fibers of this invention can provide a polyurethane elastic fiber which is stable and excellent anti-adhesion property, uniform scalability, antistatic property, smoothness, and productivity. Since the processing agent of this invention is provided with the polyurethane elastic fiber of this invention, it is stable, and has the outstanding anti-adhesion property, uniform tack property, antistatic property, smoothness, and productivity.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram explaining the measuring method of roller static electricity generation amount.
It is a schematic diagram explaining the measuring method of knitting tension, and the measuring method of static electricity generation amount.
It is a schematic diagram explaining the measuring method of the interfiber friction coefficient.
It is a schematic diagram explaining the measuring method of a speed ratio and scum.
It is a schematic diagram explaining the measuring method of real strength.

The processing agent for polyurethane elastic fibers (henceforth "the processing agent") of this invention contains a base component (A), and also contains the specific acidic phosphate ester salt (B). Moreover, the processing agent of this invention is also the processing agent which mix | blends a base component (A), an acidic phosphate ester (C), and a component (D). Hereinafter, it demonstrates in detail.

Base component (A)

The base component (A) of this invention is at least 1 sort (s) chosen from silicone oil, mineral oil, and ester oil. Therefore, you may use 1 type or use 2 or more types together as a base component.

Although it does not specifically limit as silicone oil, For example, polydimethylsiloxane, polyalkylsiloxane, polyalkylphenylsiloxane, etc. are mentioned. 1 type may be used or 2 or more types may be used together. 700 or more are preferable, as for the number average molecular weight of silicone oil, 800-4000 are more preferable, and 1000-3000 are further more preferable. 5-50 mm <^2> / s is preferable, as for the viscosity (25 degreeC) of silicone oil, 6-40 mm <^2> / s is more preferable, and 9-30 mm <^2> / s is more preferable.

Siloxane bonds of the silicone oil: combined amount of ^{(SiOR 2 R 3 R 2,} R 3 each independently represents an organic group) is 10 to 55 are preferred, and, and 12-45 more preferably 14-40 more preferably Do. The organic group of R <^2> , R <^3> is a C1-C24 hydrocarbon group, A methyl group, an ethyl group, a propyl group, isopropyl group, a butyl group, an isobutyl group, a pentyl group, an isopentyl group, a hexyl group, and a cyclopropyl group , A cyclohexyl group, a phenyl group, a benzyl group, etc. are mentioned, Especially a methyl group and a phenyl group are preferable. 40 weight% or more is preferable, as for the ratio of the silicone oil to the whole base component, 50 weight% or more is more preferable, and 60 weight% or more is more preferable. When it is less than 40 weight%, the smoothness of a thread may be insufficient.

Although it does not specifically limit as mineral oil, A mechanical oil, a spindle oil, a liquid paraffin, etc. are mentioned as an example. Among these, liquid paraffin is preferable as the mineral oil because of the low occurrence of odors. Mineral oil may use 1 type or may use 2 or more types together.

5 mm <^2> / s or more is preferable, as for the viscosity (25 degreeC) of mineral oil, 5-50 mm <^2> / s is more preferable, and 5-30 mm <^2> / s is still more preferable. If the viscosity (25 ° C) is less than 5 mm ² / s, the yarn may be swollen, which is not preferable.

Although the ratio of the mineral oil which occupies for the whole base component is not specifically limited, 40 weight% or more is preferable, 50 weight% or more is more preferable, 60 weight% or more is more preferable. When mineral oil is less than 40 weight%, compatibility with acidic phosphate ester salt (B) may deteriorate.

Although it does not specifically limit as ester oil, The ester manufactured from fatty acid and alcohol is mentioned. As ester oil, although the ester manufactured from the fatty acid and alcohol chosen from what is described below can be illustrated, for example, ester which does not use the following fatty acid or alcohol as a raw material may be sufficient. Ester oil may use 1 type or may use 2 or more types together.

The fatty acid is not particularly limited with respect to the carbon number, the presence or absence of a branch, a valence, and the like, and may be a higher fatty acid, a cyclic fatty acid, or a fatty acid containing an aromatic ring. Examples of the fatty acid include caprylic acid, 2-ethylhexyl acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, arachnic acid, and behenic acid. , Lignoserine acid, adipic acid, sebacic acid, benzoic acid and the like. The alcohol is not particularly limited with respect to the carbon number, the presence or absence of a branch, a valence, or the like, and may be a higher alcohol, a cyclic alcohol, or an alcohol containing an aromatic ring. Examples of the alcohol include octyl alcohol, 2-ethylhexyl alcohol, decyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, ethylene glycol, hexanediol, Glycerin, trimethylolpropane, pentaerythritol, sorbitol, sorbitan and the like.

5 mm <^2> / s or more is preferable, as for the viscosity (25 degreeC) of ester oil, 5-50 mm <^2> / s is more preferable, and 5-30 mm <^2> / s is still more preferable. If the viscosity (25 ° C) is less than 5 mm ² / s, the yarn may be swollen, which is not preferable.

Although the ratio of the ester oil to the whole base component is not specifically limited, 50 weight% or less is preferable, 40 weight% or less is more preferable, 30 weight% or less is further more preferable. If the ester oil exceeds 50% by weight, the smoothness of the yarn may be insufficient.

Acidic Phosphate Ester Salts (B)

The processing agent for polyurethane elastic fibers of this invention contains the acidic phosphoric acid ester salt (B) of the divalent cation of a group 2 element metal essentially. The acidic phosphoric acid ester salt (B) may be one kind or a mixture of two or more kinds.

The acidic phosphoric acid ester salt (B) of this invention has an acidic hydroxyl group. That is, the acidic phosphoric acid ester salt (B) has a group in which the hydrogen atom of the acidic hydroxyl group is substituted with a divalent cation of a group 2 element metal, and has an acidic hydroxyl group which is not substituted with a divalent cation of a group 2 element metal. By having the group which substituted the hydrogen atom of the acidic hydroxyl group by the divalent cation, the outstanding decomposability and antistatic property are exhibited. At the same time, it is believed that by having a non-substituted acidic hydroxyl group at a predetermined ratio, the solubility in the base component is excellent, the decomposability and the antistatic property are stable and uniform, and the scum falling off in post processing is also reduced. .

The molar ratio of the divalent cation of the acidic hydroxyl group and the Group 2 element metal contained in the acidic phosphoric acid ester salt (B) (mole number (I) of the number of moles of acidic hydroxyl group (H) / 2 of the divalent cation of the group element metal) is 95 / 5-5 / 95 are preferable, 90 / 10-30 / 70 are more preferable, 85 / 15-40 / 60 are more preferable, 80 / 20-50 / 50 are especially preferable. When the molar ratio (H) / (I) is greater than 95/5, the effects of anti-adhesion, uniformity, and antistatic properties may be insufficient, and the strength of the yarn may deteriorate. If the molar ratio (H) / (I) is less than 5/95, compatibility with the base component may be insufficient, scum may occur in post-processing, uniform deterioration may not be obtained, or smoothness may be insufficient. .

And in the case of unneutralization (H / I is 100/0), ie, when the acidic phosphate ester which does not constitute a salt is used, the strength of the yarn tends to be further deteriorated. In addition, swelling of the yarn may occur, causing the yarn to break during post-processing, or lack of smoothness. In addition, the effects of anti-deadlock, antistatic properties, and smoothness may be insufficient. On the other hand, in the case of complete neutralization (H / I is 0/100), that is, when a phosphate ester salt having no acidic hydroxyl group is used, compatibility with the base component is insufficient, so scum is likely to occur during post-processing. This becomes nonuniform. In addition, the effects of anti-adhesion and antistatic properties may not be sufficiently exhibited. Moreover, the friction with respect to a metal is high, and smoothness may be inadequate.

As a group 2 of a divalent cation of the elemental metal which is contained in the acidic phosphate salt (B) of the present invention, it is preferable Be ^2+, Mg ^2+, Ca ^2+, Sr ²⁺ and Ba, at least one member selected from a ^{2 +} . In view of safety for the human ^{body, Mg 2 +, Ca 2 +} , Sr 2 + is more preferred.

Then, the acidic phosphate salt, Na ^+, K ^+, NH ₄ ^+, if the salt 1 is composed of a cation, such as, compared with the acidic phosphate salt (B) of the present invention, a low compatibility with the base element, and Since it is insufficient, scum is apt to occur in post-processing. Moreover, these salts are inferior to the acidic phosphate ester salt (B) of this invention in the effects of sea-resistance, smoothness, and antistatic property.

The acidic phosphate ester salt (B) of the present invention is at least one selected from an acidic phosphate ester (C), a Group 2 element metal, a hydroxide of a Group 2 element metal, an oxide of a Group 2 element metal, and a carbonate of a Group 2 element metal. It is the product which made the component (D) of a species react. At this time, the molar ratio of the acidic hydroxyl group of the acidic phosphate ester (C) and the component (D) (the number of moles of the acidic hydroxyl group of the acidic phosphate ester (C) / the number of components (D)) is 100/5 to 100/95 It is preferable, 100/10-100/70 are more preferable, 100/15-100/60 are still more preferable, 100/20-100/50 are especially preferable. When the molar ratio exceeds 100/5, the effects of anti-adherence, uniformity, and antistatic properties are insufficient, and the strength of the yarn may deteriorate. When the molar ratio is less than 100/95, compatibility with the base component may be insufficient, scum may occur in post-processing, uniformity may not be obtained, or the smoothness may be insufficient.

As acidic phosphoric acid ester (C), the compound represented by the said General formula (1) is preferable.

In General formula (1), R <^1> is a hydrocarbon group in the range of C1-C30. When the carbon number of R ¹ exceeds 30, the solubility in the base component of the acidic phosphate ester salt (B) prepared using the acidic phosphate ester (C) is insufficient. 4-22 are preferable, as for carbon number of R <^1> , 6-20 are more preferable, and 8-18 are especially preferable. As a hydrocarbon group, the saturated or unsaturated aliphatic hydrocarbon group which may have a branch, the aromatic hydrocarbon group which may have a substituent, or the cyclic aliphatic hydrocarbon group can be mentioned. From the solubility viewpoint with respect to the base component of the acidic phosphoric acid ester salt (B) manufactured using an acidic phosphoric acid ester (C), it is preferable that R <^1> is a hydrocarbon group which has a branch rather than a linear hydrocarbon group. More preferably, it is a C4-C22 hydrocarbon group which has a branch.

As oxyalkylene group XO, Preferably, they are oxyethylene, oxypropylene, and oxybutylene, It is preferable to have these in a molecule | numerator 1-15. When the number of oxyalkylene groups XO in the molecule exceeds 15, the solubility in the base component of the acidic phosphate ester salt (B) produced using the acidic phosphate ester (C) is insufficient. More preferable number of oxyalkylene groups is 1-5.

Acidic phosphate ester (C) represented by the said General formula (1) is acidic phosphate monoester (C-1) represented by following General formula (2) by the combination of b and c in a formula, and the following general formula ( It can be distinguished by acidic phosphoric acid diester (C-2) represented by 3).

[Formula 2]

(R ¹ , X, XO, a in Formula (2) are the same as in the case of Formula (1).)

(3)

(R ¹ , X, XO, and a in Formula (3) are the same as in the case of Formula (1).)

Specific examples of the acidic phosphate ester (C) include monomethyl phosphate ester, dimethyl phosphate ester, trimethyl phosphate ester, butyl phosphate ester, hexyl phosphate ester, octyl phosphate ester, decyl phosphate ester, lauryl phosphate ester, myristyl phosphate ester, cetyl Phosphoric acid ester, stearyl phosphate ester, behenyl phosphate ester, trioctacosanyl phosphate ester, oleyl phosphate ester, 2-ethylhexyl phosphate ester, isoheptyl phosphate ester, isooctyl phosphate ester, isononyl phosphate ester, isodecyl phosphate Ester, Isodecyl Phosphate Ester, Isolauryl Phosphate Ester, Isotridecyl Phosphate Ester, Isomyristyl Phosphate Ester, Isocetyl Phosphate Ester, Isostearyl Phosphate Ester, Tert-Butyl Phosphate Ester, Benzyl Phosphate Ester, Octylphenyl Phosphate Ester , Cyclo Hexyl Phosphate Ester, Polyoxyethylene 5 Mole Addition Cetyl Ether Phosphate Ester, Polyoxyethylene 15 Mole Addition Cetyl Ether Phosphate Ester, Polyoxyethylene 7 Mole Addition Polyoxypropylene 3.5 Mole Addition sec-alkylether Phosphate Ester, Polyoxyethylene 2 Mole 5 mole addition polyoxypropylene addition, polyoxyethylene 3 mole addition sec-alkylether phosphate ester, polyoxyethylene 2 mole addition lauryl ether phosphate ester, polyoxy ethylene 4 mole addition phenol phosphate ester, and the like.

Acidic phosphoric acid ester (C) can be synthesize | combined by a well-known method. For example, P ₂ O _5, etc. are of the inorganic phosphoric acid obtained by, reacting an alcoholic hydroxyl group, such as alcohol or a polyoxyalkylene alkylene alkyl ether is added to the compound and having, any molar ratio of the molecule.

The molar ratio of P ₂ O ₅ for one mole of the compound such as alcohol is of 0.4 ~ 0.15 is preferred. 0.335-0.2 are more preferable, and 0.3-0.25 are especially preferable. When it exceeds 0.4, the solubility in the base component of the acidic phosphate ester salt (B) produced using the acidic phosphate ester (C) may be insufficient or the smoothness may be lowered. If it is less than 0.15, the performance of decomposability and antistatic property may fall.

Reacted with an inorganic acid and an alcohol, such as P ₂ O _5, it is possible to obtain a mixture of acid phosphate mono-ester (C-1) and acid phosphoric acid diester (C-2). At this time, by adjusting the molar ratio of P ₂ O ₅ for one mole of alcohol, it is possible to adjust the ratio of the phosphoric acid monoester (C-1) and acid phosphoric acid diester (C-2) is obtained. As an acidic phosphate ester (C) used for manufacture of the acidic phosphate ester salt (B) of this invention, an acidic phosphate monoester (C-1) and an acidic phosphate diester (C-2) may respectively be individual, or may be a mixture. , Mixtures are preferred. As for molar ratio (C-1) / (C-2) of an acidic phosphoric acid monoester (C-1) and an acidic phosphoric acid diester (C-2), 5 / 95-80 / 20 is preferable and 10 / 90-70 / 30 is more preferable, and it is further more preferable that it is 15 / 85-50 / 50 from a viewpoint of the antistatic property, the acid resistance, and the solubility with respect to a base component of the acidic phosphoric acid ester salt (B) obtained by reaction.

The molar ratio of (C-1) and (C-2) in the mixture of the acidic phosphoric acid monoester (C-1) and the acidic phosphoric acid diester (C-2) is determined by a known potentiometric titration. You can check with

As a component (D), the following are mentioned. As the hydroxide of the Group 2 element metal, Be (OH) ₂ , Mg (OH) ₂ , Ca (OH) ₂ , Sr (OH) ₂ , Ba (OH) ₂ are preferable, and Mg (OH) ₂ and Ca (OH) ) ₂ and Sr (OH) ₂ are more preferred. As an oxide of a group 2 element metal, BeO, MgO, CaO, SrO, BaO is preferable, and MgO, CaO, SrO is more preferable. Group 2 as the elemental metal _{carbonate, BeCO 3, MgCO 3, CaCO} 3, SrCO 3, BaCO 3 are preferred, MgCO _3, and more preferably CaCO _3, SrCO ₃ (a) As group 2 element metal, Be, Mg, Ca, Sr, Ba is preferable, and Mg, Ca, Sr is more preferable.

The method for producing the acidic phosphoric acid ester salt (B) is not particularly limited, but the acidic hydroxyl group of the acidic phosphoric acid ester (C) may be a hydroxide of a group 2 element metal, an oxide of a group 2 element metal, a carbonate of a group 2 element metal, or the like. The method of preparing by neutralizing using and the method of preparing by directly reacting an acidic phosphate ester (C) and a group 2 element metal are preferable. Moreover, as mentioned later about a processing agent, a base component (A), an acidic phosphate ester (C), and a component (D) are mix | blended directly at the above-mentioned ratio, and it mixes and stirs, makes it react in a processing agent, and makes it acidic phosphate ester salt (B ) May be contained.

When the acidic hydroxyl group of the acidic phosphate ester (C) is neutralized using a hydroxide of a group 2 element metal, an oxide of a group 2 element metal, a carbonate of a group 2 element metal, or the like, an acidic phosphate ester (C) and a group 2 element metal; In order to react directly, it is preferable to carry out by diluting these substrates with a solvent as needed. As a solvent, a thing with favorable compatibility with a base component is preferable, and mineral oil, alcohol, a nonionic activator, ester oil, etc. are mentioned as an example. As mineral oil, liquid paraffin is preferable. As alcohol, octyl alcohol, 2-ethylhexyl alcohol, decyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, ethylene glycol, hexanediol, glycerin, trimethylol propane And pentaerythritol, sorbitol, sorbitan and the like. Although it does not specifically limit as a nonionic activator, The sec-alkyl ether to which polyoxyalkylene was added, the alkyl ether to which polyoxyalkylene was added, the sorbitan ester to which polyoxyalkylene was added, etc. are mentioned, for example. . Although it does not specifically limit as ester oil, The ester manufactured from fatty acid and alcohol is mentioned.

In the reaction mentioned above, in order to promote reaction, it is preferable to mix water. Although it does not specifically limit about the quantity of the water mixed at the time of reaction, When water remains in a reaction material, compatibility with the base component of a processing agent may deteriorate. Therefore, as little as 0.1-5% with respect to the substrate total amount is preferable. After the reaction, it is more preferable to remove the water remaining in the reactant by treatment such as heating. From the same point of view, the water generated when the acidic hydroxyl group of the acidic phosphate ester (C) is neutralized by using a hydroxide of a Group 2 element metal, an oxide of a Group 2 element metal, a carbonate of a Group 2 element metal, or the like is heated by heating or the like. , Dehydration treatment is preferred. And although the amount of moisture in a processing agent is smaller, it is preferable, 5% or less is preferable, 1% or less is more preferable, 0.1% or less is still more preferable.

The molar ratio (H) / (I) of the acidic hydroxyl group contained in the acidic phosphate ester salt (B) of the present invention and the divalent cation of the Group 2 element metal is equal to the acid value (F) of the acidic phosphate ester (C) before the reaction. From the acid value (G) of the acidic phosphoric acid ester salt (B) obtained by reaction, it can calculate by following formula (1).

(H) / (I) = (G) / [(F)-(G)]... Formula (1)

[Reactor of component (D)]

The reactor value (L) of at least one component (D) selected from Group 2 element metals, hydroxides of Group 2 element metals, oxides of Group 2 element metals and carbonates of Group 2 element metals is the food content of component (D). It can calculate by following formula (2) using (K).

(L) = [56100 / (K)] x 2. Equation (2)

[Calculation of Molar Ratio of Acidic Hydroxyl Group of Acidic Phosphate Ester (C) and Component (D)

When the molar ratio of the acidic hydroxyl group of the acidic phosphoric acid ester (C) and the component (D) is 100 / (P), (P) is the reactor (L) of the component (D) and the weight% of the component (D) ( It can calculate by following formula (3) using N), acid value (F) of acidic phosphate ester (C), and weight% (O) of acidic phosphate ester (C).

(P) = [(L) × (N)] ÷ [(F) × (O)] × 100. Formula (3)

[Other components]

The treatment agent of the present invention may further contain modified silicone in order to improve antistatic properties and degradability. The modified silicone is generally at least one of both terminal, one terminal, side chain and side chain terminal of polysiloxane, such as dimethyl silicone (polydimethylsiloxane), wherein the reactive (functional) group or the non-reactive (functional) group is at least It is said to have one bonded structure.

As modified silicone, For example, Alkyl modified silicones, such as modified silicone which has a long-chain alkyl group (C6 or more alkyl group, 2-phenylpropyl group, etc.); Ester modified silicone which is a modified silicone which has an ester bond; Polyether modified silicones such as modified silicone having a polyoxyalkylene group (eg, polyoxyethylene group, polyoxypropylene group, polyoxyethyleneoxypropylene group, etc.); Carbinol-modified silicone which is a modified silicone having an alcoholic hydroxyl group; Carboxy modified silicone which is modified silicone which has an acid anhydride group or a carboxyl group; Amino modified silicone which is modified silicone which has an amino group; And organic phosphate ester neutralizers of amino modified silicone in which the amino group of the amino modified silicone is neutralized with organic phosphate ester.

In addition, the treatment agent of the present invention may further contain silicone resin in order to improve the antistatic properties and the degradability. Silicone resin means the silicone which has a three-dimensional crosslinked structure, and may contain other modified silicone etc. further. Silicone resin is generally at least 1 type of structural unit selected from the monofunctional structural unit (M), the bifunctional structural unit (D), the trifunctional structural unit (T), and the tetrafunctional structural unit (Q). It is.

Examples of the silicone resin include silicone resins such as MQ silicone resin, MQT silicone resin, T silicone resin, DT silicone resin and the like.

Examples of MQ silicone resin, for example, a R ^a R ^b R ^c SiO _1/2 a (where, R ^a, R ^b and R ^c are all hydrocarbon group) and a 4-functional constitutional unit monofunctional structural unit a silicon resin, etc. containing SiO _4/2.

As MQT silicone resins, for example, a R ^a R ^b R ^c SiO _1/2 a (where, R ^a, R ^b and R ^c are all hydrocarbon group) and a 4-functional constitutional unit monofunctional structural unit SiO _4/2 and trifunctional structural units of RSiO _3/2, such as a silicon resin containing a (where, R is a hydrocarbon group).

As the T silicon resin, for example, trifunctional structural units of RSiO _3/2 search silicone resin (the terminal which may consist of a group other than groups hydrocarbons, silanol groups or alkoxy, including (where, R is a hydrocarbon group) ).

As the DT silicone resin, for example, bifunctional structural units of R ^a R ^b SiO _2/2 and (where, R ^a, and R ^b are both hydrocarbon groups), 3-functional constitutional unit RSiO _3/2 (Wherein R is a hydrocarbon group).

As the hydrocarbon groups R, R ^a, R ^b and R ^c, it is a hydrocarbon group having a carbon number of 1-24, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, an isopentyl group , A hexyl group, a cyclopropyl group, a cyclohexyl group, a phenyl group, a benzyl group, etc. are mentioned, Especially a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a phenyl group are preferable.

These modified silicones and silicone resins can be suitably used because they do not impair the compatibility of the acidic phosphate ester with the base component.

The treating agent of the present invention may further contain a component usually used as a treating agent for elastic fibers, such as a linking agent, an antistatic agent, an antioxidant, and an ultraviolet absorber. As the coupling agent, for example, nonylphenol, oxyethylene adduct of nonylphenol, oxypropylene adduct of nonylphenol, dioctyl phthalate, isostearyl alcohol, oxyethylene adduct of isostearyl alcohol, isostearyl alcohol Oxypropylene adducts, isostearic acid, oleic acid, palmitic acid, stearic acid and the like. Examples of the antistatic agent include alkanesulfonic acid salts, dodecylbenzenesulfonic acid salts, amine salts of alkyl phosphate esters, and monovalent metal salts of alkyl phosphate esters.

[Processing Agent for Polyurethane Elastic Fiber]

As for the weight ratio of the base component (A) which occupies for the whole processing agent of this invention, 40-99.999 weight% is preferable, 50-99.99 weight% is more preferable, 70-99.9 weight% is still more preferable, 90-99 weight % Is particularly preferred. When it is less than 40% by weight, the solubility of the acidic phosphate ester salt (B) in the base component (A) is lowered and does not adhere uniformly to the elastic yarn, but falls off in post-processing, whereby scum or smoothness is reduced. There is.

The weight ratio of the acidic phosphoric acid ester salt (B) in the whole processing agent of this invention is 0.001-60 weight%, 0.01-50 weight% is preferable, 0.1-30 weight% is more preferable, 1-10 weight% More preferred. When it exceeds 60 weight%, the solubility to a base component falls, it does not adhere uniformly to an elastic yarn, falls off in post processing, a scum may arise, or smoothness may fall.

When the treatment agent of the present invention contains modified silicone, the polymerization ratio of the modified silicone occupied in the entire treatment agent is not particularly limited, but is preferably 0.01 to 10% by weight, more preferably 0.05 to 7% by weight, and 0.1 to 5% by weight is particularly preferred. When the weight ratio of modified silicone is less than 0.01 weight%, since it is too small, the effect by addition may not be seen. On the other hand, when it exceeds 10 weight%, the performance of a processing agent may not be sufficient.

When the treatment agent of the present invention contains silicone resin, the weight ratio of the silicone resin to the whole treatment agent is not particularly limited, but is preferably 0.01 to 10% by weight, more preferably 0.05 to 7% by weight, and 0.1 to 5% by weight is particularly preferred. When the weight ratio of silicone resin is less than 0.01 weight%, the effect by addition may not be seen. On the other hand, when it exceeds 10 weight%, the appropriate balance of processing agent performance may not be maintained.

Although it does not specifically limit about the manufacturing method of a processing agent, A base component (A) and an acidic phosphate ester salt (B) can be mix | blended in a predetermined ratio, it can mix and stir, and it can prepare.

In addition, as mentioned above, the base component (A), the phosphate ester (C) and the component (D) which become raw materials of an acidic phosphate ester salt (B) are mix | blended in a predetermined ratio, and it mixes and stirs, and acidic phosphate ester You may prepare the processing agent containing a salt (B). In this case, this invention can be expressed by the processing agent which mix | blended the above-mentioned base component (A), acidic phosphate ester (C), and a component (D). That is, this invention consists of mix | blending a base component (A), an acidic phosphate ester (C), and a component (D), and the molar ratio of the acidic hydroxyl group of the acidic phosphate ester (C) and the said component (D) is 100 It is / 5-100/95 and can express with the processing agent for polyurethane elastic fibers whose weight ratio of the sum total of the said acidic phosphate ester (C) and the said component (D) which occupies for the whole processing agent is 0.001-60 weight%.

The molar ratio of the acidic hydroxyl group of the acidic phosphoric acid ester (C) and the component (D) is as described in connection with the acidic phosphoric acid ester salt (B).

The weight ratio of the sum total of the acidic phosphate ester (C) and the component (D) which occupies for the whole processing agent is 0.001-60 weight%, 0.01-50 weight% is preferable, 0.1-30 weight% is more preferable, 1- 10% by weight is more preferred. When it exceeds 60 weight%, the solubility to a base component falls, it does not adhere to an elastic yarn, falls off in post processing, a scum may arise, or smoothness may fall.

Moreover, this invention includes the process of mix | blending and mixing and mixing a base component (A), an acidic phosphate ester (C), and a component (D), The acidic hydroxyl group of the said acidic phosphate ester (C), and the said component For polyurethane elastic fibers, the molar ratio of (D) is 100/5 to 100/95, and the weight ratio of the sum total of the acidic phosphate ester (C) and the component (D) in the whole treatment agent is 0.001 to 60% by weight. It can also be expressed by the manufacturing method of a processing agent.

As for the viscosity (25 degreeC) of the processing agent of this invention, 3-3,000 mm <^2> / s is preferable, 5-1,500 mm <^2> / s is more preferable, 8-500 mm <^2> / s is especially preferable. If it is less than 3 mm ² / s, volatilization of the treatment agent may be a problem, and if it exceeds 3,000 mm ² / s, the polyurethane elastic fibers may be swept away by the rollers and the thread may break.

[impurities]

500 ppm or less is preferable, as for trace metals, such as Fe, Al, and Si contained in the processing agent of this invention, 200 ppm or less is more preferable, 100 ppm or less is especially preferable. These trace metals are mixed from the hydroxide of the Group 2 element metal, the oxide of the Group 2 element metal, the carbonate of the Group 2 element metal, and the Group 2 element metal used for the reaction of the base component or the acidic hydroxyl group of the acidic phosphate ester (C). It is considered to be. When these impurities exceed 500 ppm, scum may generate | occur | produce in post-processing.

[Polyurethane Elastic Fiber]

The polyurethane elastic fiber of this invention is a polyurethane elastic fiber in which 0.1 to 15 weight%, Preferably 1 to 10 weight% of the processing agent of this invention is provided to the polyurethane elastic fiber main body. Less than 0.1% by weight is insufficient for the effect of the present invention, and more than 15% by weight is not economical. As a provision method, a well-known method can be employ | adopted.

The polyurethane elastic fiber (elastic fiber main body) of this invention is a fiber which has elasticity using polyether polyurethane or polyester polyurethane.

Polyurethane elastic fiber of this invention prepares polytetramethylene glycol (PTMG) and diphenylmethane diisocyanate (MDI) of the molecular weight 1000-3000, and it is dimethyl by PTMG / MDI = 1 / 2-1 / 1.5 (molar ratio). Dry spinning a solution of 20 to 40% of a polyurethaneurea polymer obtained by reacting in a solvent such as acetamide or dimethylformamide and reacting with 80 to 100% of excess isocyanate with diamine such as ethylenediamine or propanediamine. The polyurethaneurea elastic fiber which can be manufactured by spinning at 400-1000 m / min of spinning speed is preferable.

It is preferable to use the processing agent of this invention for the fiber whose fineness of a polyurethane elastic fiber is 5-40 dtex. As a use of the polyurethane elastic fiber of this invention, it can be used as cloth surface by processing yarns, such as cover yarns, such as CSY, a single cover, a PLY, an air cover, circular knitting, a tricot, etc. . These processed yarns and fabrics are also used for the purpose of imparting elasticity for comfort to products requiring elasticity such as stockings, socks, underwear, swimwear, and outerwear such as jeans and clothes. In recent years, it has also been applied to paper diapers.

Example

The present invention will be described in detail with reference to the following Examples, but the present invention is not limited to the Examples described herein. In addition, unless otherwise indicated, the percentage (%) and a part shown to a following example show "weight%" and a "weight part." Evaluation of each characteristic in the Example was performed according to the following method.

[Evaluation Method of Processing Agent]

(Viscosity)

Using a Cannon-Fenske viscometer, the kinematic viscosity of the sample liquid at a constant temperature (25 ° C.) was measured.

(Acid value)

Automatic potentiometric titration device (COM-900, manufactured by Hiranuma Co., Ltd.) with a 0.1 N potassium hydroxide ethylene glycol isopropyl alcohol solution dissolved in a solvent in which isopropyl alcohol and xylene / isopropyl alcohol (1/1) were mixed. ), The potential difference was titrated, and the titration amount (ml) of the neutralization endpoint was measured, and the acid value was calculated from the following equation (4). The acid value is represented by the number of mg of KOH required to neutralize 1 g of the sample.

Acid value (KOHmg / g) = (A × F × 5.61) / W. Formula (4)

(In Formula (4), A = titration amount (ml), F = titer of 0.1 N potassium hydroxide, W = sample weight (g))

(Roller static electricity)

In FIG. 1, the cheese 1 of the polyurethane elastic fiber which provided the processing agent to the seam side of the speed ratio measuring instrument is set, it rotates at the circumferential speed of 50 m / min, and becomes 2 cm on cheese. At this point, the casing potentiometer 2 was used to measure the static electricity generated 1 hour after the start of rotation.

(Organization tension)

In FIG. 2, the polyurethane elastic yarn 4 pulled out longitudinally from the cheese 3 is passed through a compensator 5, through a roller 6, a knitting needle 7, and a U gauge 8 Is connected to the speedometer 10 and the winding roller 11 via the roller 9 attached to the. The rotational speed of the winding roller is adjusted so that the traveling speed in the speedometer 10 becomes a constant speed (for example, 10 m / min, 100 m / min), the coil is wound around the winding roller, and the knitting tension at that time is U gauge It measures with (8) and measures the friction g between a fiber / knitting needle. The generated static electricity was measured by the casing potentiometer 12 at the place becoming 1 cm from a traveling thread.

(Coefficient between fibers (F / FμS))

In FIG. 3, the monofilament of the polyurethane elastic fiber to which the processing agent was provided is taken about 50-60 cm, the load T1 (13) is suspended on one end, and the other to the U gauge 15 through the roller 14 The end is tensioned at constant speed (for example, 3 cm / min), the secondary tension T2 at that time is measured by the U gauge 15, and the interfiber friction is obtained by the following formula (5). Coefficients were obtained.

Friction coefficient (F / FμS) = 1 /? Ln (T2 / T1). Equation (5)

(Equation (5), θ = 2π, ln = natural logarithm, T1 is 1g per 22dtex)

(Speed ratio)

In FIG. 4, the cheese 16 of the polyurethane elastic fiber which provided the processing agent to the underside of the speed ratio measuring instrument is set, and the paper tube 17 is set to the winding side. After setting the winding speed to a constant speed, the rollers 18 and 19 are simultaneously operated. In this state, since the tension is hardly applied to the thread 20, the thread is stuck on the cheese and is not spaced apart, so the sea point 21 is in the state shown in FIG. By changing the speed, the breaking point 21 of the yarn 20 from the cheese is changed. Therefore, the speed is set so that this point coincides with the contact point 22 of the cheese and the roller. Therefore, the speed ratio is obtained by the following formula (6). The smaller this value, the better the resolving ability.

Speed ratio (%) = (winding speed-speed) ÷ speed x 100. Equation (6)

The speed ratio measured in the layer which entered 1 cm inside from the cheese surface layer was made into the speed ratio of the outer layer part, and was measured in the layer of 1 cm distance from the paper tube of cheese, and the speed ratio was made into the speed ratio of the innermost part. The smaller the difference between the solution speed ratios of the outer layer and the innermost layer is, the better the uniformity is.

(Scum)

In FIG. 4, the winding body 16 of the polyurethane elastic fiber which provided the processing agent to the delivery side is set, and the paper tube 17 is set to the winding side. After setting the speed of the delivery roller 18 to 100 m / min and the speed of the winding roller 19 to 200 m / min, the delivery roller 18 and the winding roller 19 are simultaneously operated. After traveling for 1 hour, the presence or absence of scum accumulation on the delivery roller 18 is determined by visual observation according to the following criteria.

○: No scum, △: Small amount of scum is recognized, ×: Scum is recognized

(Thread strength)

In Fig. 5, one polyurethane elastic fiber is taken from the cheese and 20 cm, hooked on the U gauge 8, and pulled at a constant speed of 20 cm / min until broken, thereby breaking the point load (thread strength). Measured.

(Water content, inorganic salt content)

The water content of the acidic phosphoric acid ester salt (B), the treatment agent of the example, and the treatment agent of the comparative example and the content of the inorganic salt were measured by Karl-Fischer method and ion chromatography, respectively.

(Production of Acidic Phosphate Ester Salts)

As a manufacturing method of an acidic phosphoric acid ester salt, a specific example is shown with respect to the acidic phosphoric acid ester salt A-1 of Table 1. Of isooctyl alcohol and phosphoric anhydride P ₂ O ₅ molar ratio of 1: to 4 hours at 80 ~ 110 ℃ to 0.35, to obtain a phosphoric acid isooctyl ester (A-1P in Table 2). The acid value of the obtained isooctyl phosphate ester was 324 (KOHmg / g), and the molar ratio of the phosphate monoester and the phosphate diester was 40/60.

Mg (OH) ₂ which is a hydroxide of the Group 2 element metal Mg was added to the obtained isooctyl phosphate ester, followed by neutralization reaction, and then dehydrated to obtain an acidic phosphate ester salt A-1 shown in Table 1. The molar ratio (I) of the resulting acidic phosphate salt A-1 molar ratio of the acid (H) a group 2 a divalent cation of a metal element of the hydroxyl group is Mg ^{2 +} (H) / (I) = a 80/20.

As a raw material, by the same production method except that the acidic phosphate ester of Table 2 and the hydroxide of the Group 2 element metal of Table 1 were neutralized and reacted so that it might become the molar ratio of the acidic hydroxyl group and divalent cation of Table 1, The acidic phosphoric acid ester salts A-2 to A-6 used in the examples of Table 1 and B-1 to B-2 used in the comparative examples were obtained.

A specific example is shown about acidic phosphoric acid ester salt A-7. Polyoxyethylene 15 mol added iso cetyl etereugwa anhydrous phosphoric acid P ₂ O ₅ molar ratio of 1 to 3 hours at 80 ~ 110 ℃ to 0.25, polyoxyethylene 15 mol added to obtain iso cetyl ether phosphoric acid ester. The acid value of the obtained polyoxyethylene 15 mol addition isocetyl ether phosphate ester was 51 (KOHmg / g), and the molar ratio of the phosphate monoester and phosphate diester was 25/75.

CaCO ₃ which is a carbonate of a group 2 element metal was added to the obtained polyoxyethylene 15-mole addition isocetyl ether phosphate ester, it decarboxylate- neutralized at 80-115 degreeC, and the acidic phosphate ester salt A-7 was obtained. The molar ratio of the obtained acidic phosphate salt A-7 hydroxyl group molar ratio of acid (H) a group 2 element divalent cation of a metal of Ca ^{2 + (I)} is (H) / (I) was 35 = / 65. As a raw material, by the same production method, except that the acidic phosphate ester of Table 2 and the carbonate of the Group 2 element metal of Table 1 were used for neutralization reaction so that it might become the molar ratio of the acidic hydroxyl group and divalent cation of Table 1, The acidic phosphoric acid ester salt A-8 used in the examples described in Table 1 was obtained.

[Table 1]

[Table 2]

"Division" of Table 2 corresponds to "Division" of Table 1, respectively. In other words, "Division" A-1P in Table 2 represents the acidic phosphoric ester used as a raw material of "Division" A-1 in Table 1.

[Examples 1-5 and Comparative Examples 1-3]

(Adjustment of spinning stock)

Polytetramethylene ether glycol having a number average molecular weight of 2000 and 4,4'-diphenylmethane diisocyanate were reacted at a molar ratio of 1: 2. Subsequently, chain extension was carried out using a dimethylformamide solution of 1,2-diaminopropane to obtain a dimethylformamide solution having a polymer concentration of 27%. The concentration at 30 ° C. was 1500 mPaS.

A polyurethane spinning solution was dry spinning by discharging the N ₂ gas flow of 190 ℃. During spinning, 6% by weight of the treating agent shown in Table 3 was applied to the running yarn with respect to the fiber by an oil ring roller. Then, it wound up in the bobbin at the speed | rate of 500 m per minute, and obtained 77 dtex of monofilament cheese (winding amount 400g). The obtained cheese was left to stand in 35 degreeC and 50% RH atmosphere for 48 hours, and it evaluated. Table 3 shows the evaluation results of the treatment agent performance. In addition, the processing agent mix | blends and mixes each component of Table 3 (the compounding quantity of a table | surface shows a weight part), and is mixed and prepared. Acidic phosphoric acid ester salts of Tables 3 to 5 are as described in Table 1. H / I of Tables 3-5 shows the molar ratio (H) / (I) of the acidic hydroxyl group in the acidic phosphoric acid ester salt, and the divalent cation of a group 2 element metal.

[Table 3]

[Examples 6-10 and Comparative Examples 4-5]

In the same manner as in Examples 1 to 5, the polyurethane spinning stock solution was discharged into a 190 ° C N ₂ air stream and dry-spun. During spinning, the treating agent of Table 4 was given to the traveling yarn with respect to the fiber by the oiling roller 6 weight%. Then, it wound up in the bobbin at the speed | rate of 500 m per minute, and obtained 44 dtex of monofilament cheese (winding amount 400g). The obtained cheese was left to stand in 35 degreeC and 50% RH atmosphere for 48 hours, and it evaluated. These results are shown in Table 4. And the processing agent mix | blends each component of Table 4 (the compounding quantity shown in a table is a weight part), and it mixes and stirs, and is prepared.

[Table 4]

[Examples 11-15 and Comparative Examples 6-8]

(Adjustment of spinning stock)

100 parts by weight of polytetramethylene glycol having a number average molecular weight of 2000 and 25 parts by weight of 4,4'-diphenylmethane diisocyanate are reacted at 70 ° C, and 250 parts by weight of N, N'-dimethylacetamide is added to the reaction mixture for cooling. Was dissolved. The thing which melt | dissolved 5 weight part of 1, 2- diamino propane in 184 weight part of N, N'- dimethylacetamide was added, and 0.2 weight% of dimethyl silicone 10000 mm <^2> / s was added.

The polyurethane spinning stock solution was discharged in a N ₂ air stream at 180 ° C. from the spinning mouthpiece having four pores, and dry spinning. During spinning, 6% by weight of the treating agent shown in Table 5 was given to the traveling yarn with respect to the fiber by an oiling roller. Then, it wound up in the bobbin at the speed | rate of 500 m per minute, and obtained 22 dtex multifilament cheese (winding amount 400g). The obtained cheese was left to stand in 35 degreeC and 50% RH atmosphere for 48 hours, and it evaluated. These results are shown in Table 5. And the processing agent mix | blends each component of Table 5 (the compounding quantity shown in a table is a weight part), and it mixes and stirs and prepares.

[Table 5]

[Examples 16-20 and Comparative Examples 9-10]

In the same manner as in Examples 6 to 10, the polyurethane spinning stock solution was discharged into a N ₂ air stream at 190 ° C. to dry spinning. During spinning, 6% by weight of the treating agent shown in Table 7 was given to the traveling yarn with respect to the fiber by an oiling roller. Then, it wound up in the bobbin at the speed | rate of 500 m per minute, and obtained 44 dtex of monofilament cheese (winding amount 400g). The obtained cheese was left to stand in 35 degreeC and 50% RH atmosphere for 48 hours, and it evaluated. These results are shown in Table 7. And the processing agent mix | blends each component of Table 7 (the compounding quantity shown in a table is a weight part), and it mixes and stirs and prepares. The acidic phosphoric acid ester (C) of Table 7 and Table 8 is as having described in Table 2. The foodstuffs and reactor number of component (D) of Table 7 and Table 8 are as having shown in Table 6. Tables 7 and 8 show (P) in the molar ratio 100 / (P) of the acidic hydroxyl group of the acidic phosphoric acid ester (C) and the component (D).

TABLE 6

[Table 7]

[Examples 21-22 and Comparative Examples 11-14]

In the same manner as in Examples 11 to 15, the polyurethane spinning undiluted solution was discharged in a 180 ° C N ₂ stream to dry spinning. During spinning, the treatment agent shown in Table 8 was given 6% by weight with respect to the fibers by an oiling roller. Then, it wound up in the bobbin at a speed | rate of 500 m per minute, and obtained 22 dtex of monofilament cheese (winding amount 400g). The obtained cheese was left to stand in 35 degreeC and 50% RH atmosphere for 48 hours, and it evaluated. These results are shown in Table 8. And the processing agent mix | blends each component of Table 8 (the compounding quantity shown in a table is a weight part), and it mixes and stirs and prepares.

[Table 8]

The various physical properties of the component of Tables 3-8 are shown below. And the viscosity was measured at 25 degreeC.

1) Base Component (A)

Dimethyl silicone (viscosity 5 mm ² / s): Average molecular weight 700

Dimethyl silicone (viscosity 15 mm ² / s): Average molecular weight 2000

Dimethyl silicone (viscosity 10 mm ² / s): Average molecular weight 1000

Liquid paraffin 40 seconds: Mineral oil, viscosity 6.4mm ² / s

Floating paraffin 60 seconds: Mineral oil, viscosity 15.7mm ² / s

Floating paraffin 80 seconds: Mineral oil, viscosity 21.8mm ² / s

Isooctylaurate: ester oil, viscosity 7.3mm ² / s

Isooctyl stearate: Ester oil, viscosity 15.2mm ² / s

Isooctyl palmitate: ester oil, viscosity 13.1mm ² / s

2) Other ingredients

 Stearyl Phosphate Potassium Phosphate: Complete Neutralization, Acid Value 0 KOHmg / g

 Magnesium distearate: 99%, 200 mesh passables

 Dioctylsulfosuccinic acid Na: Completely neutralized, acid value 0 KOHmg / g

 Isodecyl phosphate ester: Acid value 300 KOHmg / g

Amino modified silicone KF-880: Viscosity 650 mm ² / s, amino equivalent 1800 g / mol, amine value 30 KOHmg / g, Shin-Etsu Chemical Co., Ltd. make

Polyether modified silicone KF-351: Viscosity 100mm ² / s, Shin-Etsu Chemical Co., Ltd. product

MQ silicone resin TSF4600: Viscosity 700mm ² / s, moment performance material Japan joint venture manufacturing

 Isotridecyl Phosphate Ester Potassium: 40% neutralization of Isotridecyl Phosphate Ester (A-5P)

[Industrial applicability]

The treating agent of the present invention is preferably used when producing a polyurethane elastic fiber. The polyurethane elastic fiber of this invention is stable, and has the outstanding anti-adhesion property, uniform tack property, antistatic property, smoothness, and productivity.

1: Cheese of polyurethane elastic fiber 2: Casing potentiometer
3: cheese of polyurethane elastic fiber 4: polyurethane elastic yarn
5: Compassator 6: Roller
7: knitting needle 8: U gauge
9: roller 10: speedometer
11: winding roller 12: casing potentiometer
13: load 14: roller
15: U gauge 16: cheese
17: winding paper tube 18: roller
19: roller 20: driving
21: seam point 22: contact point of cheese and roller

Claims (9)

At least one base component (A) selected from silicone oil, mineral oil and ester oil, and an acidic phosphate ester salt of a divalent cation of a Group 2 element metal (B),
The acidic phosphoric acid ester salt (B) has an acidic hydroxyl group, the molar ratio of the divalent cation of the acidic hydroxyl group and the Group 2 element metal is 95/5 to 5/95, and the acidic phosphoric acid ester salt (B) occupies the entire treatment agent. The processing agent for polyurethane elastic fibers whose weight ratio of) is 0.001-60 weight%. The method of claim 1,
The group 2 is a divalent cation of a metal element, Be ^{+ 2,} Mg ^{+ 2,} Ca ^{+ 2,} Sr ^{+ 2} and Ba ^{+ 2,} at least one member, the polyurethane elastic fiber treatment agent selected from a. The method according to claim 1 or 2,
The acidic phosphoric acid ester salt is at least one component selected from an acidic phosphoric acid ester (C), a hydroxide of a Group 2 element metal, a Group 2 element metal, an oxide of a Group 2 element metal, and a carbonate of a Group 2 element metal (D ) Is a product reacted,
The processing agent for polyurethane elastic fibers whose molar ratio of the acidic hydroxyl group of the said acidic phosphoric acid ester (C) and the said component (D) is 100/5-100/95. The method of claim 3,
The processing agent for polyurethane elastic fibers whose said acid phosphate ester (C) is a compound represented by following General formula (1):
[Formula 1]

(R <^1> in Formula (1) represents a C1-C30 hydrocarbon group, X represents a C2-C4 alkylene group, XO represents an oxyalkylene group, a shows the added mole number of an oxyalkylene group, 0 or an integer of 1 to 15, b and c are 1 or 2, respectively, and are integers satisfying b + c = 3. At least one base component (A) selected from silicone oil, mineral oil and ester oil, acidic phosphate ester (C), Group 2 element metal, hydroxide of Group 2 element metal, oxide of Group 2 element metal, and It is made by mix | blending at least 1 sort (s) of component (D) chosen from the carbonate of the said group 2 element metal,
The molar ratio of the acidic hydroxyl group of the said acidic phosphoric acid ester (C) and the said component (D) is 100/5-100/95,
The processing agent for polyurethane elastic fibers whose weight ratio of the sum total of the said acidic phosphate ester (C) and the said component (D) occupies for the whole processing agent is 0.001-60 weight%. The method of claim 5,
The processing agent for polyurethane elastic fibers whose said Group 2 element metal is at least 1 sort (s) chosen from Be, Mg, Ca, Sr, and Ba. The method according to claim 5 or 6,
The processing agent for polyurethane elastic fibers whose said acid phosphate ester (C) is a compound represented by following General formula (1):
(2)

(R <^1> in Formula (1) represents a C1-C30 hydrocarbon group, X represents a C2-C4 alkylene group, XO represents an oxyalkylene group, a shows the added mole number of an oxyalkylene group. , 0 or an integer of 1 to 15, b and c are integers of 1 or 2, respectively, and satisfy b + c = 3. 8. The method according to any one of claims 1 to 7,
It further contains at least one component selected from alkyl modified silicones, ester modified silicones, polyether modified silicones, carbinol modified silicones, carboxy modified silicones, amino modified silicones, organic phosphate ester neutralizations of amino modified silicones and silicone resins. The processing agent for polyurethane elastic fibers whose weight ratio of the said additional component to the whole said processing agent is 0.01 to 10 weight%. The polyurethane elastic fiber which is provided 0.1 to 15 weight% of the processing agent in any one of Claims 1-8 to the polyurethane elastic fiber main body.

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