WO2016017336A1 - Elastic fiber treatment agent, and elastic fibers - Google Patents

Abstract

The problem to be solved by the present invention is to provide: an elastic fiber treatment agent which generates little scum following high temperature storage and which exhibits good anti-static properties and unraveling properties; and elastic fibers which generate little scum following high temperature storage and which exhibit good anti-static properties and unraveling properties. This problem can be solved by an elastic fiber treatment agent which contains, as essential components, (A) at least one type of base component selected from among mineral oils, silicone oils and ester oils, (B) a fatty acid metal salt, and (C) an organic phosphoric acid ester, and in which the average molecular weight of the fatty acid that constitutes the fatty acid metal salt (B) is 150-256.

Description

Elastic fiber treatment agent and elastic fiber

The present invention relates to an elastic fiber treatment agent and an elastic fiber to which the treatment agent is applied.

Since elastic fibers have a property that is rich in stretchability, fiber / metal friction that occurs when contacting with a friction body such as a guide is large in the yarn making process and the post-processing process, and thread breakage occurs. There is a case.
Therefore, the elastic fiber uses a treatment agent for elastic fiber that uses a smoothing agent such as silicone oil, mineral oil, and ester oil as a base component.
Since the smoothing agent has poor antistatic properties, an antistatic agent is usually used in combination, and a method of adding an alkyl phosphate metal salt as the antistatic agent has been proposed (Patent Document 1).
In addition, the elastic fiber is a fiber that easily sticks because it has viscoelasticity. In particular, in the inner layer portion of the silk thread body (hereinafter sometimes referred to as cheese), the sticking progresses with time due to the pressure applied during winding. Therefore, when using an elastic fiber thread body, unwinding is poor and thread breakage is caused. In order to improve this unwinding failure, various treatment agents for elastic fibers have been developed.
For example, Patent Document 2 describes an elastic fiber treatment agent containing a silicone resin (MQ resin).
However, with conventional antistatic agents and unwinding improvers, there are no problems with scum, static electricity, or unwinding properties when using a yarn body immediately after spinning elastic fibers. When the yarn body is used after it has been stored, there are cases where scum is generated, static electricity is increased, and the unraveling property is insufficient due to the progress of sticking.

Japanese Patent Publication No. 41-21956 Japanese Laid-Open Patent Publication No. 09-078460

An object of the present invention is to provide an elastic fiber treatment agent that has low scum generation even after high temperature storage and has good antistatic and unwinding properties, and low antistatic and scum generation even after high temperature storage. It is to provide an elastic fiber having unwinding property.

As a result of intensive studies, the inventors of the present invention can solve the above problems as long as the treatment agent is an elastic fiber containing a base component (A), a specific fatty acid metal salt (B), and an organic phosphate (C). The present invention has been found.
That is, at least one base component (A) selected from mineral oil, silicone oil, and ester oil, a fatty acid metal salt (B), and an organic phosphate ester (C) are essentially contained, and the fatty acid metal salt A processing agent for elastic fibers, wherein the fatty acid constituting (B) has an average molecular weight of 150 to 256.

The content of the organic phosphate ester (C) is preferably 5 to 2000 parts by weight with respect to 100 parts by weight of the fatty acid metal salt (B).
The fatty acid metal salt (B) is preferably at least one selected from sodium salt, potassium salt, magnesium salt, calcium salt, zinc salt and aluminum salt.
The molar ratio of the fatty acid having 10 to 14 carbon atoms in the fatty acid constituting the fatty acid metal salt (B) is preferably 50 mol% or more.
The organic phosphate ester (C) is preferably represented by the following general formula (1) and / or the following general formula (2).

(In the general formula (1), R ¹ is a hydrocarbon group having 6 to 24 carbon atoms, A ¹ O is an oxyalkylene group having 2 to 4 carbon atoms, and a is a number from 0 to 30. m Is a number from 1 to 2. When there are two R ¹ and (A ¹ O) _{a in the} molecule, they may be the same or different from each other.

(In the general formula (2), R ² is a hydrocarbon group having 6 to 24 carbon atoms, A ² O is an oxyalkylene group having 2 to 4 carbon atoms, and b is a number from 0 to 30. Q ¹ is a hydroxyl group or R ² O (A ² O) _b n is 1 or 2. When there are two R ² and (A ² O) _{b in the} molecule, they are identical to each other. It may or may not be.)
The weight ratio of the base component (A) to the treating agent is preferably 50 to 99.99% by weight.
The weight ratio of the fatty acid metal salt (B) to the treating agent is preferably 0.01 to 30% by weight.
The weight ratio of the organophosphate (C) to the treating agent is preferably 0.01 to 30% by weight.
The elastic fiber of the present invention is obtained by applying the elastic fiber treatment agent to the elastic fiber main body.

The treatment agent for elastic fibers of the present invention generates little scum even after high temperature storage and can impart good antistatic and unwinding properties to the elastic fiber. The elastic fiber of the present invention can be used even after high temperature storage. Low scum generation and good antistatic and unwinding properties.

The schematic diagram explaining a scum evaluation method. The schematic diagram explaining the evaluation method of unwinding speed ratio. The schematic diagram explaining the measuring method of knitting tension | tensile_strength. The schematic diagram explaining the measuring method of the friction between fibers. The schematic diagram explaining the measuring method of fluff adsorption.

The treatment agent for elastic fibers of the present invention is used when producing elastic fibers, and contains a base component (A), a specific fatty acid metal salt (B) and an organic phosphate ester (C). This will be described in detail below.

(Base component (A))
The base component (A) is at least one selected from silicone oil, mineral oil, and ester oil. The base component (A) is an essential component for the elastic fiber treatment agent, and is an agent that reduces the friction between fibers and metals.

Although it does not specifically limit as silicone oil, Polydimethylsiloxane, polymethylphenylsiloxane, polymethylalkylsiloxane etc. can be mentioned, You may use 1 type (s) or 2 or more types. Viscosity at 25 ° C. of the silicone oil is preferably ² ~ 100mm 2 / s, more preferably 5 ~ 70mm ² / s, more preferably 5 ~ 50mm ² / s. When the viscosity is less than 2 mm ² / s, the silicone oil may volatilize, and when it exceeds 100 mm ² / s, the solubility of other components blended in the treatment agent may deteriorate.
The average amount of siloxane bonds (SiOR ³ R ⁴ : R ³ and R ⁴ each independently represents an organic group) in the silicone oil is preferably 3 to 100, more preferably 5 to 60, and 7 to 50 Is more preferable. The organic groups of R ³ and R ⁴ are hydrocarbon groups having 1 to 24 carbon atoms, and are methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, isopentyl group, hexyl group, cyclohexane A propyl group, a cyclohexyl group, a phenyl group, a benzyl group and the like can be mentioned, and a methyl group and a phenyl group are particularly preferable.

The mineral oil is not particularly limited, and examples thereof include machine oil, spindle oil, liquid paraffin, and the like, and one or more kinds may be used. The viscosity of the mineral oil at 30 ° C. with a Redwood viscometer is preferably 30 seconds to 350 seconds, more preferably 35 seconds to 200 seconds, and even more preferably 40 seconds to 150 seconds. As the mineral oil, liquid paraffin is preferable because of low odor generation. When the viscosity of the mineral oil is less than 30 seconds, the quality of the obtained elastic fiber may be deteriorated. On the other hand, when the viscosity of the mineral oil exceeds 350 seconds, the solubility of other components blended in the treatment agent may deteriorate.

The ester oil is not particularly limited as long as it is an ester of a monohydric alcohol and a monovalent carboxylic acid, an ester of a monohydric alcohol and a polyvalent carboxylic acid, or an ester of a polyhydric alcohol and a monovalent carboxylic acid. You may use a seed | species or 2 or more types. As monohydric alcohols, monohydric aliphatic alcohols, aromatic alcohols, alicyclic alcohols, phenols and the like described later can be used. Among these, monovalent aliphatic alcohols and aromatic alcohols are preferable.

The monovalent aliphatic alcohol is not particularly limited. For example, octanol, 2-ethylhexanol, 1-nonanol, 1-decanol, undecyl alcohol, lauryl alcohol, tridecyl alcohol, isotridecyl alcohol, myristyl alcohol , Pentadecyl alcohol, 1-hexadecanol, palmitoleyl alcohol, 1-heptadecanol, stearyl alcohol, oleyl alcohol, isostearyl alcohol, nonadecyl alcohol, 1-eicosanol, behenyl alcohol, 1-tetracosanol, erucyl alcohol And lignoceryl alcohol.
Examples of the aromatic alcohol include phenol and benzyl alcohol.
Examples of the alicyclic alcohol include cyclooctanol, cyclododecanol, cyclohexanol, cycloheptanol, cyclopentanol, and menthol.

As the monovalent carboxylic acid, the following monovalent aliphatic carboxylic acid, aromatic carboxylic acid, hydroxycarboxylic acid, and the like can be used. Among these, monovalent aliphatic carboxylic acids and aromatic carboxylic acids are preferable.

The monovalent carboxylic acid is not particularly limited. For example, valeric acid, caproic acid, enanthic acid, caprylic acid, 2-ethylhexylic acid, capric acid, lauric acid, myristic acid, pentadecylic acid, palmitic acid, palmitic acid , Margaric acid, stearic acid, oleic acid, isostearic acid, vaccenic acid, linoleic acid, linolenic acid, arachidic acid, behenic acid, lignoceric acid, cetylonic acid, benzoic acid and the like.

The polyvalent carboxylic acid is not particularly limited. For example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, phthalic acid, trimellitic acid, pyromellitic acid, citric acid, isocitric acid, etc. Is mentioned.

The polyhydric alcohol is not particularly limited. For example, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, cyclohexanediol, glycerin, diglycerin , Triglycerin, tetraglycerin, sorbitol, trimethylolpropane, pentaerythritol and the like.

Specific examples of the ester oil include, but are not limited to, for example, heptyl valerate, heptyl caproate, octyl caproate, cetyl caprylate, isooctyl laurate, isopropyl myristate, isopropyl palmitate, isostearyl palmitate, stearin Butylate, octyl stearate, oleyl laurate, isotridecyl stearate, octyl stearate, isooctyl stearate, tridecyl stearate, isobutyl stearate, methyl oleate, isobutyl oleate, heptyl oleate, oleyl oleate, polyethylene dilaurate Glycol, polyethylene glycol dimyristate, polyethylene glycol dioleate, polyethylene glycol distearate, polylaurate Pyrene glycol, polypropylene glycol dimyristate, polypropylene glycol dioleate, polypropylene glycol distearate, dicetyl oxalate, diisooctyl malonate, dilauryl succinate, diisodecyl adipate, isononyl adipate, dioctyl adipate, diisooctyl fumarate, diisooctyl phthalate Dioctyl phthalate, dinonyl phthalate, diisodecyl phthalate, diundecyl phthalate, triisooctyl trimellitic acid, triisobutyl trimellitic acid, triisodecyl trimellitic acid, triisostearyl trimellitic acid, glycerin triisooctyl, glycerin trilauryl , Glycerin trimyristyl, glycerin trioleyl, glycerin tristearyl, sorbitan mono Ureto, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate, sorbitan sesquioleate, sorbitan trilaurate, sorbitan tristearate, include sorbitan tanto tripalmitate like.

(Fatty acid metal salt (B))
The fatty acid metal salt (B) is an essential component of the present invention, and is used in combination with the organic phosphate ester (C) described later, so that it has good scum suppression, antistatic properties and unraveling even after high-temperature storage. It is a component which shows the property and smoothness does not fall.
The effect of the present application is exhibited by the interaction between the salt portion of the fatty acid metal salt and the phosphate ester.
When the fatty acid metal salt (B) is contained at a specific ratio together with the organic phosphate ester (C) described later, the effect of the present application is further exhibited, which is preferable.
Although the factors that show good antistatic and unwinding properties after storage at a higher temperature than when each component alone is not clear, the effect improves at a specific ratio, so the fatty acid metal salt (B) and the organic phosphoric acid It is presumed that this may be due to interaction with the ester (C) through salt exchange or the like. The fatty acid metal salt (B) may be a mixture, or may be used alone or in combination of two or more.

The average molecular weight of the fatty acid constituting the fatty acid metal salt (B) is 150 to 256. From the viewpoint of exerting the effect of the present application, the lower limit of the average molecular weight of the fatty acid constituting the fatty acid metal salt (B) is preferably 155, more preferably 160, further preferably 165, particularly preferably 170, and most preferably 180. . From the viewpoint of exerting the effect of the present application, the upper limit of the average molecular weight of the fatty acid constituting the fatty acid metal salt (B) is preferably 250, more preferably 245, further preferably 240, particularly preferably 235, and most preferably 230. . In addition, the fatty acid which comprises the said fatty-acid metal salt (B) here means what is shown by RCOOH.
Moreover, the average molecular weight of the fatty acid in this application means the number average molecular weight calculated from the molecular weight of each fatty acid and its molar ratio.
Although the factor that the effect of the present application depends on the average molecular weight of the fatty acid constituting the fatty acid metal salt (B) is not certain, the fatty acid metal salt exhibits a great effect when used in combination with the organic phosphate ester (C). It is presumed that the average molecular weight of the fatty acid constituting (B) is within a specific range, so that salt exchange with the organic phosphate ester (C) is likely to occur.

The fatty acid constituting the fatty acid metal salt (B) has 6 to 24 carbon atoms.
Specific examples of fatty acids constituting the fatty acid metal salt (B) include caproic acid, enanthic acid, caprylic acid, 2-ethylhexylic acid, capric acid, lauric acid, myristic acid, pentadecylic acid, myristoleic acid, palmitic acid, Palmitoleic acid, margaric acid, isocetyl acid, stearic acid, isostearic acid, behenic acid, oleic acid, elaidic acid, linoleic acid, linolenic acid, arachidic acid, eicosenoic acid, isodocosanoic acid, erucic acid, lignoceric acid, isotetradocosanoic acid Etc.

The fatty acid constituting the fatty acid metal salt (B) preferably contains a fatty acid having 10 to 14 carbon atoms as essential from the viewpoint of exerting a great effect when used in combination with the organic phosphate ester (C).
The molar ratio of the fatty acid having 10 to 14 carbon atoms in the fatty acid constituting the fatty acid metal salt (B) is 50 mol% from the viewpoint of reducing the amount of adsorbed fluff when used in combination with the organic phosphate ester (C). The above is preferable, 60 mol% or more is more preferable, 70 mol% or more is further preferable, and 80 mol% or more is particularly preferable. A preferable upper limit of the molar ratio of the fatty acid having 10 to 14 carbon atoms in the fatty acid constituting the fatty acid metal salt (B) is 100 mol%.

As metal salt (BM) which comprises the said fatty-acid metal salt (B), when it is at least 1 sort (s) chosen from sodium salt, potassium salt, magnesium salt, calcium salt, zinc salt, aluminum salt, organophosphate ester ( It is preferable from the viewpoint that salt exchange with C) easily occurs and the effect of the present application is easily obtained. Among these, magnesium salts, calcium salts, zinc salts, and aluminum salts are more preferable.

When the fatty acid metal salt (B) has no distribution, the fatty acid metal salt (B) includes calcium caprate, calcium laurate, calcium myristate, magnesium caprate, magnesium myristate, magnesium laurate, and laurin. Zinc acid, zinc caprate and zinc myristate are preferred.
Conventionally, when the main component is magnesium stearate, which is applied to almost all elastic fiber treatment agents, the effect of the present application cannot be exhibited.

A known method can be adopted as a method for producing the fatty acid metal salt in the present invention. Examples thereof include a metathesis method in which a fatty acid and sodium hydroxide are subjected to a saponification reaction and metathesis with an aqueous metal salt solution, and a direct method in which a fatty acid is reacted with a metal oxide or hydroxide. The fatty acid used may be an animal-derived fatty acid or a plant-derived fatty acid.

(Organic phosphate ester (C))
The organic phosphate ester (C) is a component comprising an organic phosphate ester having a hydrocarbon group having 6 to 24 carbon atoms and / or a polyoxyalkylene group-containing organic phosphate ester having a hydrocarbon group having 6 to 24 carbon atoms. It is. From the viewpoint of easily obtaining good antistatic properties after high-temperature storage by the combined use with the fatty acid metal salt (B), selected from the compound represented by the general formula (1) and the compound represented by the general formula (2) It is preferable that the compound includes at least one compound represented by the general formula (1) and the compound represented by the general formula (2).

In the general formulas (1) and (2), R ¹ and R ² are hydrocarbon groups having 6 to 24 carbon atoms. A ¹ O and A ² O are oxyalkylene groups having 2 to 4 carbon atoms. a and b are numbers from 0 to 30. m is a number from 1 to 2. When there are two R ¹ , (A ¹ O) _a, R ² , and (A ² O) _{b in the} molecule, they may be the same or different from each other. Q ¹ is a hydroxyl group or R ² O (A ² O) _b . n is 1 or 2.

The organic phosphate ester (C) is a phosphoric acid monoester compound represented by m = 1 in the general formula (1) (sometimes simply referred to as monoester (C1)), and represented by m = 2 in the general formula (1). Phosphoric acid diester compounds (sometimes simply referred to as diesters (C2)), pyrophosphoric acid ester compounds represented by n = 1 in the general formula (2), triphosphoric acid ester compounds represented by n = 2 in the general formula (2) It is preferable that it is a mixture. The pyrophosphate ester compound and the triphosphate ester compound may be simply referred to as polyphosphate ester (C3).

In the general formula (1), when m is 1 <m <2, it means that the organic phosphate ester (C) is a mixture of a monoester and a diester. For example, when m is 1.3, the ratio of the number of moles of monoester to the number of moles of diester is 7: 3.
The weight ratio of the monoester (C1) in the organic phosphate ester (C) is preferably 20 to 80% by weight, more preferably 23 to 60% by weight, and further preferably 25 to 50% by weight. When the weight ratio is less than 20% by weight, the antistatic performance may be deteriorated because the hydrophilicity of the treatment agent is low. When the weight ratio is more than 80% by weight, the hydrophilicity of the treatment agent becomes too high, so that the moisture content in the treatment agent becomes high when the treatment agent is used, and the stability of the treatment agent may be deteriorated. .

The weight ratio of the diester (C2) in the organic phosphate ester (C) is preferably 10 to 60% by weight, more preferably 20 to 55% by weight, and further preferably 30 to 50% by weight. When the weight ratio is less than 10% by weight, the stability of the treatment agent may deteriorate.

The weight proportion of the polyphosphate ester (C3) in the organic phosphate ester (C) is preferably 0 to 45 wt%, more preferably 0.1 to 40 wt%, still more preferably 0.5 to 35 wt%, Most preferred is 1 to 30% by weight. When the weight ratio exceeds 45% by weight, the hydrophilicity of the treatment agent becomes too high, so that the moisture content in the treatment agent becomes high when the treatment agent is used, and the stability of the treatment agent may be deteriorated.

Organic phosphoric acid ester (C) contains heavy metal compounds such as arsenic as impurities derived from anhydrous phosphoric acid and inorganic phosphorus. The processing agent for elastic fibers of the present invention may contain a heavy metal compound such as arsenic. The weight ratio of the heavy metal compound in the nonvolatile content of the treatment agent for elastic fibers is preferably 0.01% by weight or less, more preferably 0.005% by weight or less, from the viewpoint of influence on the human body and environmental safety. More preferably 0.001% by weight or less.

When producing the organic phosphate ester (C), inorganic phosphoric acid and / or a salt thereof (hereinafter referred to as component (X)) is produced as a by-product. The processing agent for elastic fibers of the present invention may contain component (X). The weight ratio of the component (X) in the nonvolatile content of the treatment agent for elastic fibers is preferably 5% by weight or less, more preferably 4% by weight or less, and still more preferably 3% by weight or less from the viewpoint of further exerting the effect of the present application. .

The weight proportion of the phosphoric acid monoester (C1), phosphoric acid diester (C2) and polyphosphoric acid ester (C3) in the organic phosphoric acid ester (C) and the weight proportion of the component (X) are the phosphorus atom in ³¹ P-NMR. It can be calculated from the integration ratio of the peak derived from.

R ¹ and R ² are alkyl groups or alkenyl groups having 6 to 24 carbon atoms. R ¹ and R ² preferably have 8 to 22 carbon atoms, more preferably 10 to 20 carbon atoms, and still more preferably 10 to 18 carbon atoms. If R ¹ and R ² have less than 6 carbon atoms or more than 24 carbon atoms, the antistatic property may be insufficient. R ¹ and R ² may be linear or branched, and may be saturated or unsaturated. R ¹ and R ² are preferably branched and / or unsaturated alkyl groups because of excellent stability in the treating agent.

A ¹ O and A ² O represent an oxyalkylene group having 2 to 4 carbon atoms. a represents the average number of moles of A ¹ O added. b represents the average number of moles of A ² O added. a and b are each a number of 0 to 30, preferably 0 to 20, and more preferably 0 to 10 from the viewpoint of smoothness. When a and b are 0, the stability in the treating agent is particularly excellent. When a or b exceeds 30, the stability in the treatment agent may be insufficient.

In the present invention, the weight ratio of the organophosphate (C) to 100 parts by weight of the fatty acid metal salt (B) is preferably 2 to 5000 parts by weight, more preferably 5 to 2000 parts by weight. More preferred is 1500 parts by weight, even more preferred is 25 to 1000 parts by weight, and particularly preferred is 30 to 400 parts by weight. When the amount is 30 to 400 parts by weight, the effect that the unraveling property after high-temperature storage is hardly lowered can be obtained. The reason for this is that when the component (B) and the component (C) are used in an appropriate ratio, they are sufficiently effective to prevent penetration into the fiber by salt exchange or the like even after high-temperature storage. ing. On the other hand, when the above components are used alone, or when either one of them is excessively used, these components penetrate into the fiber by being exposed to a high temperature, so that a sufficient effect is obtained. Estimated to disappear.

The organic phosphate ester (C) is not particularly limited, but from the viewpoint of easily obtaining good antistatic properties after high-temperature storage in combination with the fatty acid metal salt (B), hexyl phosphate ester and octyl phosphate Ester, decyl phosphate ester, dodecyl phosphate ester, tetradecyl phosphate ester, hexadecyl phosphate ester, octadecyl phosphate ester, behenyl phosphate ester, trioctacosanyl phosphate ester, octadecenyl phosphate ester, 2-ethylhexyl phosphorus Acid ester, isoheptyl phosphate ester, isooctyl phosphate ester, isononyl phosphate ester, isodecyl phosphate ester, isoundecyl phosphate ester, isododecyl phosphate ester, isotridecyl phosphate ester, isotetradecyl phosphate ester , Isohexadecyl phosphate, isooctadecyl phosphate, t-butyl phosphate, benzyl phosphate, octylphenyl phosphate, cyclohexyl phosphate, polyoxyethylene 5-mol addition hexadecyl ether phosphate, poly Oxyethylene 15 mol addition hexadecyl ether phosphate ester, polyoxyethylene 7 mol addition polyoxypropylene 3.5 mol addition secondary alkyl ether phosphate ester, polyoxyethylene 2 mol addition polyoxypropylene 5 mol addition dodecyl phosphate ester, poly Oxyethylene 3 mol addition secondary alkyl ether phosphate ester, polyoxyethylene 2 mol addition dodecyl ether phosphate ester, polyoxyethylene 4 mol addition phenol And phosphoric acid esters.

There is no limitation in particular as a manufacturing method of organic phosphate ester (C), A well-known method is employable. For example, the method for producing the organic phosphate ester (C) includes the step (I) of obtaining a reaction product by reacting an organic hydroxyl compound represented by R ¹ O (A ¹ O) aH with phosphoric anhydride P ₂ O _5. Is included. The molar ratio of inorganic phosphoric acid P ₂ O ₅ to 1 mol of the organic hydroxyl compound is preferably 0.15 to 0.4. 0.2 to 0.335 is more preferable, and 0.25 to 0.3 is particularly preferable. When it exceeds 0.4, smoothness may be lowered when used in combination with the fatty acid metal salt (B). If it is less than 0.15, the antistatic performance after high-temperature storage may be reduced when used in combination with the fatty acid metal salt (B).
In step (I), the reaction may be carried out by adding inorganic phosphoric acid or water. The method for producing the organic phosphate ester (C) may include, after the step (I), a step (II) in which water is added to the reaction product for hydrolysis. By including process (II), the ratio of the polyphosphate ester contained in the component which is an organic phosphoric acid compound can be adjusted. The amount of water added to the reaction product is preferably 0.01 to 1 mol, more preferably 0.03 to 0.8 mol, and even more preferably 0.05 to 0.5 mol with respect to the organic hydroxyl compound. The amount is preferably 0.07 to 0.3 mol. When the amount of water added is less than 0.01 mol and more than 1 mol, it may be difficult to adjust the amount of polyphosphate ester.

(Other ingredients)
In addition to the components described above, the treatment agent for elastic fibers of the present invention has an alkyl-modified silicone, an ester-modified silicone, a polyether-modified silicone, an amino-modified silicone, a carbite in addition to the components described above. It may further contain at least one other component selected from a diol-modified silicone, an epoxy-modified silicone, a carboxy-modified silicone, a mercapto-modified silicone, an organopolysiloxane resin, a nonionic surfactant, a cationic surfactant and an anionic surfactant. . One or more other components may be used.

The modified silicone is generally a reactive (functional) group or a non-reactive group at least at one of both ends, one end, side chain, and both side chains of polysiloxane such as dimethyl silicone (polydimethylsiloxane) ( It has a structure in which at least one functional group is bonded.

More specifically, the modified silicone is an alkyl-modified silicone such as a modified silicone having a long-chain alkyl group (such as an alkyl group having 6 or more carbon atoms or a 2-phenylpropyl group); an ester that is a modified silicone having an ester bond. Modified silicones; polyether-modified silicones that are modified silicones having polyoxyalkylene groups (for example, polyoxyethylene groups, polyoxypropylene groups, polyoxyethyleneoxypropylene groups, etc.); aminopropyl groups and N- (2-amino) Ethyl) modified silicone having aminopropyl group, etc., amino modified silicone; modified carbinol modified silicone having alcoholic hydroxyl group; modified silicone having epoxy group such as glycidyl group or alicyclic epoxy group Epoxy-modified silicone: can be mentioned a mercapto-modified silicone is a modified silicone having a mercapto group; a carboxyl group carboxyl-modified silicone is a modified silicone having a.

The above-mentioned organopolysiloxane resin (hereinafter simply referred to as silicone resin) means silicone having a three-dimensional cross-linked structure. The silicone resin is generally at least one component selected from a monofunctional constituent unit (M), a bifunctional constituent unit (D), a trifunctional constituent unit (T), and a tetrafunctional constituent unit (Q). It consists of units.

The silicone resin is not particularly limited, and examples thereof include silicone resins such as MQ silicone resin, MQT silicone resin, T silicone resin, and DT silicone resin.

Examples of the MQ silicone resin include R ^a R ^b R ^c SiO _1/2 that is ^a monofunctional structural unit (provided that R ^a, R ^b, and R ^c are all hydrocarbon groups) and 4 Examples thereof include a silicone resin containing SiO _4/2 which is a functional constituent unit.

Examples of the MQT silicone resin include R ^a R ^b R ^c SiO _1/2 that is ^a monofunctional structural unit (provided that R ^a , R ^b, and R ^c are all hydrocarbon groups), and 4 Examples thereof include a silicone resin containing SiO _{4/2 which} is a functional structural unit and RSiO _3/2 which is a trifunctional structural unit (where R is a hydrocarbon group).

Examples of the T-silicone resin include a silicone resin containing RSiO _3/2 (where R is a hydrocarbon group) which is a trifunctional structural unit (the end of which is a hydrocarbon group, silanol group or alkoxy group). And may be a base).

Examples of the DT silicone resin include R ^a R ^b SiO _2/2 which is ^a bifunctional structural unit (wherein R ^a and R ^b are both hydrocarbon groups) and a trifunctional structural unit. RSiO _3/2 (wherein R is a hydrocarbon group).

The hydrocarbon group for R, R ^a , R ^b and R ^{c is} a hydrocarbon group having 1 to 24 carbon atoms, such as 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 and the like can be mentioned, and a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a phenyl group are particularly preferable.

The nonionic surfactant is not particularly limited, and examples thereof include polyoxyethylene alkyl ether having 1 to 20 carbon atoms (EO1 to 20 mol) and polyoxypropylene having 8 to 22 carbon atoms. Alkyl ether (PO1-20 mol), sorbitan fatty acid ester, EO adduct of sorbitan fatty acid ester (EO1-20 mol), PO adduct of sorbitan fatty acid ester (PO1-20 mol), alkyl group having 6-22 carbon atoms EO adducts of alkylphenols having alkyl groups having 6 to 22 carbon atoms (EO 1 to 20 mol), fatty acid polyoxyethylene glycol esters (EO 1 to 20 mol), fatty acid polyoxypropylene glycol esters (PO 1 to 20 mol) Etc. .

The cationic surfactant is not particularly limited, and examples thereof include alkylamines such as primary amines, secondary amines and tertiary amines or salts thereof, and quaternary ammonium salts. Specifically, laurylamine, myristylamine, cetylamine, stearylamine, oleylamine, diethylamine, dioctylamine, distearylamine, methylstearylamine, polyoxypropylene-added laurylamine, polyoxyethylene-added laurylamine, polyoxyethylene-added stearyl Amine, polyoxyethylene-added oleylamine, monoethanolamine, diethylethanolamine, dibutylethanolamine, triethanolamine, laurylethanolamine, oleylpropylenediamine, trioctylamine, dimethyllaurylamine, dimethylmyristylamine, dimethylstearylamine, didecyl Dimethylammonium salt, decyltrimethylammonium salt, dioctyldimethylammonium Salt, octyl trimethyl ammonium salts and the like.

The anionic surfactant is not particularly limited, and examples thereof include alkane sulfonic acid, dialkyl sulfosuccinic acid, alkyl benzene sulfonic acid, alkyl naphthalene sulfonic acid, alkyl sulfuric acid, polyoxyethylene alkyl ether sulfuric acid, and salts of these components. . Specifically, an alkanesulfonic acid having an alkyl group having 6 to 22 carbon atoms and / or an alkali metal salt thereof, a dialkylsulfosuccinic acid having an alkyl group having 6 to 22 carbon atoms and / or an alkali metal salt thereof, Alkylbenzenesulfonic acid having an alkyl group of ˜22 and / or alkali metal salt thereof, alkylsulfuric acid having an alkyl group of 1 to 20 carbon atoms and / or salt thereof, polyoxyethylene alkyl having an alkyl group of 6 to 22 carbon atoms Examples include ether sulfuric acid and / or a salt thereof.

[Treatment agent for elastic fibers]
The viscosity of the elastic fiber treating agent of the present invention at 30 ° C. is preferably 5 to 50 mm ² / s, more preferably 5 to 40 mm ² / s, and still more preferably 6 to 20 mm ² / s. If the viscosity is too low, when the elastic fiber is run in the spinning and post-processing steps, the treatment agent may scatter in the form of a mist, and the surroundings may be soiled or the operator may inhale. On the other hand, if the viscosity is too high, when the elastic fiber is run in the spinning and post-processing steps, the running roller may wind the yarn around the running roller due to adhesiveness, which may cause yarn breakage.

The method for producing the treatment agent for elastic fiber of the present invention is not particularly limited, and a known method can be adopted. For example, a method in which some components are blended in advance and mixed with other components may be used, or a method in which all components are mixed at once.

The processing agent for elastic fibers containing a fatty acid metal salt may be produced by mixing an already pulverized fatty acid metal salt with the base component, or mixing the fatty acid metal salt with the base component to obtain a vertical bead mill or a horizontal bead mill. Alternatively, a known wet pulverizer such as a colloid mill or a sand grinder may be used for pulverization to obtain a predetermined average particle size. When the fatty acid metal salt is pulverized, dispersion aids described in JP-A-10-259577, JP-A-2000-328459 and the like may be used.

The weight ratio of the base component (A) in the elastic fiber treatment agent is preferably 50 to 99.99% by weight, more preferably 55 to 99.9% by weight, still more preferably 60 to 98% by weight, and 65 to 95% by weight. % Is particularly preferred. If the proportion of the base component (A) is too small, the smoothness is lowered and the quality of the fabric product may be lowered.

The weight ratio of the fatty acid metal salt (B) in the entire elastic fiber treatment agent is preferably 0.01 to 30% by weight, more preferably 0.05 to 20% by weight, and further preferably 0.1 to 10% by weight. preferable. If the proportion of the fatty acid metal salt (B) is less than 0.01% by weight, the intended effect may be insufficient, and if it exceeds 30% by weight, the effect depending on the amount added may not be obtained. May be disadvantageous.

The weight ratio of the organic phosphate ester (C) to the entire elastic fiber treatment agent is preferably 0.01 to 30% by weight, more preferably 0.05 to 20% by weight, and 0.1 to 10% by weight. Further preferred. If the ratio of the organic phosphate ester (C) is less than 0.01% by weight, the intended effect may be insufficient, and if it exceeds 30% by weight, the effect depending on the amount added may not be obtained. May be disadvantageous.

When the elastic fiber treatment agent contains other components, the weight ratio of the other components to the entire elastic fiber treatment agent is preferably 0.01 to from the viewpoint of maintaining fluidity when using the treatment agent. It is preferably 15% by weight, more preferably 0.1 to 13% by weight, still more preferably 0.5 to 10% by weight.

[Elastic fiber]
The elastic fiber of the present invention is obtained by applying the elastic fiber treatment agent of the present invention to an elastic fiber main body. The adhesion ratio of the elastic fiber treatment agent to the entire elastic fiber is not particularly limited, but is preferably 0.1 to 15% by weight, and more preferably 0.5 to 10% by weight. The method for applying the elastic fiber treatment agent of the present invention to the elastic fiber body is not particularly limited, and a known method can be employed.

The elastic fiber (elastic fiber body) of the present invention is a fiber having elasticity using polyether polyurethane, polyester polyurethane, polyether ester elastomer, polyester elastomer, polyethylene elastomer, polyamide elastomer, etc., and its elongation is usually 300% or more.

The elastic fiber of the present invention is made of polyurethane or polyurethane urea obtained by reacting PTMG or polyester diol with an organic diisocyanate and then extending the chain with 1,4 butanediol, ethylenediamine, propylenediamine, pentanediamine or the like. Can be mentioned. For example, polyurethane urea elastic fiber is prepared with polytetramethylene glycol (PTMG) having a molecular weight of 1000 to 3000 and diphenylmethane diisocyanate (MDI), and dimethyl at PTMG / MDI = 1/2 to 1 / 1.5 (molar ratio). A 20 to 40% solution of a polyurethane urea polymer obtained by reacting in a solvent such as acetamide or dimethylformamide and chain-extending with a diamine such as ethylenediamine or propanediamine is spin-spun at a spinning speed of 400 to 1200 m / min. Can be manufactured. The adaptive fineness of the elastic fiber body is not particularly limited.

The elastic fiber body of the present invention may contain inorganic substances such as titanium oxide, magnesium oxide, hydrotalcite, zinc oxide, and divalent metal soap. Divalent metal soaps include calcium 2-ethylhexylate, calcium stearate, calcium palmitate, magnesium stearate, magnesium palmitate, magnesium laurate, barium stearate, zinc caprate, zinc behenate, zinc stearate, etc. Can be mentioned. 1 type (s) or 2 or more types may be used for an inorganic substance.

When the elastic fiber body contains an inorganic substance, the uniform unwinding property may be poor, but the uniform unwinding property can be improved by applying the treatment agent of the present invention to the elastic fiber body. Therefore, the processing agent for elastic fibers of the present invention can be suitably used when the elastic fiber main body contains an inorganic substance. The content of the inorganic substance in the elastic fiber body is not particularly limited, but is preferably 0.01 to 5% by weight, more preferably 0.1 to 3% by weight.

As an application of the elastic fiber of the present invention, it can be used as a cloth by processing yarn such as covering yarn such as CSY, single covering, PLY, air covering, circular knitting, tricot and the like. In addition, using these processed yarns and fabrics, products that require elasticity such as stockings, socks, underwear and swimwear, and outerwear such as jeans and suits are given elasticity for comfort. Also used for purposes. More recently, it has been applied to disposable diapers.

Hereinafter, the present invention will be specifically described by way of examples and comparative examples, but the present invention is not limited to the examples described herein. Note that “percent (%)” and “parts” shown in the following examples indicate “% by weight” and “parts by weight” unless otherwise specified. In Examples and Comparative Examples, evaluation of each characteristic of the elastic fiber treatment agent was performed according to the following method.

[Scum evaluation method]
In FIG. 1, the elastic fiber cheese (1) which provided the processing agent on the delivery side is set, and the paper tube (2) is set on the winding side. After setting the speed of the delivery roller (3) to 200 m / min and the speed of the take-up roller (4) to 400 m / min, the delivery roller (3) and the take-up roller (4) are started simultaneously. After running for 1 hour, the presence or absence of scum accumulation on the delivery roller (3) is visually determined according to the following criteria.
In the following evaluation criteria, ○ or more was considered acceptable.
◎: Almost no scum ○: Small amount of scum adhering, but no problem in workability ×: Adhering scum is observed, reducing workability

[Static generation evaluation method]
In FIG. 1, the Kasuga-type static electricity measuring device is set at the position (5), and the elastic fiber cheese (1) to which the treatment agent is applied is set on the unwinding side of the scum evaluation measuring device. 2) is set. After setting the unwinding speed ratio to a constant speed of unwinding speed / winding speed = 1/2, the rollers (3) and (4) are started simultaneously. The amount of static electricity generated at 1 cm on the yarn (6) unwound from cheese under the conditions of 20 ° C. and 60% RH is measured.
In the following evaluation criteria, ○ or more was considered acceptable.
A: Static electricity generation before and after high-temperature storage is less than 0.3 kV (very good)
○: Static electricity generation before and after high-temperature storage is less than 1 kV (good)
×: Other than above (defect)

[Evaluation method of unraveling speed ratio]
In FIG. 2, the fiber cheese (7) to which the treatment agent is applied is set on the unwinding side of the unwinding speed ratio measuring machine, and the paper tube (8) is set on the winding side. After setting the winding speed to a constant speed, the rollers (9) and (10) are started simultaneously. In this state, since the tension is hardly applied to the yarn (11), the yarn is stuck on the cheese and does not leave, so that the unwinding point (12) is in the state shown in FIG. By changing the unwinding speed, the unwinding point (12) of the yarn (11) from the cheese changes, so the unwinding speed is set so that this point coincides with the contact point (13) between the cheese and the roller. The unraveling speed ratio is obtained by (Equation 1). The smaller this value is, the better the unpacking property is.
Moreover, the above evaluation criteria set ○ or more as acceptable.
A: The difference between the unwinding speed ratio before high-temperature storage and the unwinding speed ratio after high-temperature storage is less than 10 (very good)
○: The difference between the unwinding speed ratio before high-temperature storage and the unwinding speed ratio after high-temperature storage is 10 or more and less than 30 (good)
Δ: The difference between the unwinding speed ratio before high-temperature storage and the unwinding speed ratio after high-temperature storage is 30 to less than 50 (somewhat poor)
×: The difference between the unwinding speed ratio before high-temperature storage and the unwinding speed ratio after high-temperature storage is 50 or more (defect)

Unwinding speed ratio (%) = (Winding speed−Unwinding speed) ÷ Unwinding speed × 100 (Formula 1)

[Knitting tension measurement method]
The knitting tension measuring method is a method for measuring the friction between the fiber and the metal. In FIG. 3, the elastic yarn (15) vertically taken from the cheese (14) is passed through the compensator (16), the roller (17), the knitting needle (18), and the roller (20 ) Was wound around a speedometer (21) and a winding roller (22), the knitting tension at that time was measured with a U gauge (19), and the friction (g) between the fibers / knitting needles was measured. The measurement was performed at two levels of winding speed of 10 m / min and 100 m / min.

[Friction coefficient between fibers]
In FIG. 4, the elastic yarn to which the treatment agent is applied is taken about 50 to 60 cm, the load (23) is suspended at one end, and the other end is attached to the U gauge (25) via the roller (24). The secondary tension at that time is measured with a U gauge (25), and the friction coefficient between fibers is obtained by (Equation 2).
Friction coefficient between fibers = 1 / θ · In (U gauge measured value / load) (Formula 2)
(In Equation 2, θ = 2π, In = natural logarithm, load is 1 g per 22 dtex)

[Cheese shape evaluation method]
It was visually confirmed whether or not the cocoon shape of the cheese (rolling amount 450 g) provided with the treatment agent used for the evaluation had cracks such as bulges and ayado.

[Fablow adsorption test method]
In FIG. 5, the elastic yarn is taken out from the cheese (26) at a speed of 30 m / min. Wind up in minutes. The cotton yarn (31) is wound from the guide (32) through the roller (33) and the knitting needle (34) by the winding roller (35) at a speed of 100 m / min. Cotton is generated by twisting the cotton yarn once between the roller (33) and the knitting needle (34). The weight of the fluff accumulated at the yarn suction port when the elastic fiber is run for 60 minutes is measured. Elastic fibers and cotton yarns were conditioned for 3 days in an atmosphere of 20 ° C. and 45% RH. The measurement atmosphere was 20 ° C. and 45% RH. The yarn suction port has a diameter of 0.2 mm, a length of 10 mm, and the material thereof is alumina.
The smaller the fluff adsorption amount, the lower the yarn breakage occurrence frequency and the cleaning work frequency in the processing step where the fluff is generated, such as during the production of covering yarn, and the better.

[Skin disorder test]
2% by weight of each treatment agent is dissolved in acetone and dipped in Japanese pharmacopoeia gauze. The gauze is left to dry for 30 minutes, then cut into 1.5 cm sides and affixed to the back of the upper arm and kept for 48 hours. It peeled 48 hours afterward, and determined based on Table 1 at intervals for 30 minutes. The determination was scored as shown in the table, and the average reaction intensity of each treatment agent was calculated by multiplying these numerical values by the number of subjects who showed it and dividing by the total number of subjects.
Moreover, the above evaluation criteria set ○ or more as acceptable.
○: 0 to less than 1 (good)
Δ: 1 point or more and less than 2 points (slightly poor)
×: 2 points or more (defect)

[Fiber tensile strength retention]
Measurement was performed according to JIS1013.

(Examples 1 to 29, Comparative Examples 1 to 20)
A polytetramethylene ether glycol having an average molecular weight of 1600 is reacted with 4,4-diphenylmethane diisocyanate at a molar ratio of 1: 2, then chain-extended using a dimethylacetamide solution of 1,2-diaminopropane, and a polymer concentration as a spinning dope A 33% dimethylacetamide solution was obtained. The concentration of the spinning dope was 1900 mPaS (measurement temperature: 30 ° C.).

The obtained spinning dope was discharged from a spinneret having four pores into a N ₂ gas stream at 195 ° C. for dry spinning. 6% by weight of the elastic fiber treating agent was applied to each running yarn (elastic fiber main body) being spun by an oiling roller. Therefore, 5.66% by weight of the elastic fiber treatment agent was applied to the entire elastic fiber. Then, the elastic fiber processed with the processing agent for elastic fibers was wound around a bobbin at a speed of 500 m / min, respectively, to obtain 77 dtex multifilament cheese (wound amount 450 g). It evaluated by the said evaluation method using the obtained cheese, respectively.
Tables 2 to 9 and 11 show the compositions applied to the elastic fiber treatment agent. The evaluation results are shown in Table 10 and Table 12.

Moreover, what evaluates after a high temperature storage process evaluated the obtained cheese after leaving it to stand in the atmosphere of 50 degreeC and 80% RH for 15 days, and then leaving it in the atmosphere of 20 degreeC and 45% RH for 48 hours. It was used for.

As can be seen from Table 10, in Examples 1 to 29, at least one base component (A) selected from mineral oil, silicone oil and ester oil, fatty acid metal salt (B), and organic phosphate ester (C ) And the treatment agent for elastic fibers in which the average molecular weight of the fatty acid constituting the fatty acid metal salt (B) is 150 to 256 is used. Has antistatic and unwinding properties.
On the other hand, when it does not contain the organic phosphate ester (C) (Comparative Examples 1 to 4), when it does not contain the fatty acid metal salt (B) (Comparative Examples 5 to 8), it contains the fatty acid metal salt but the fatty acid metal salt ( When the average molecular weight of the fatty acid constituting B) is not in the range of 150 to 256 (Comparative Examples 9 to 20), any of the problems of the present application cannot be solved.

The treatment agent for elastic fibers of the present invention is suitably applied to the production process of elastic fibers because it generates little scum even after high temperature storage and has good antistatic and unwinding properties.

DESCRIPTION OF SYMBOLS 1 Thread body 2 Winding side paper tube 3 Roller 4 Roller 5 Set position of Kasuga-type electrostatic measuring device 6 Yarn released from cheese 7 Cheese 8 Winding side paper tube 9 Roller 10 Roller 11 Yarn unwound from cheese 12 Unwinding point 13 Contact with roller 14 Cheese 15 Elastic thread 16 Compensator 17 Roller 18 Knitting needle 19 U gauge 20 Roller 21 Speedometer 22 Winding roller 23 Load 24 Roller 25 U gauge 26 Cheese 27 Compensator 28 Roller 29 Suction port 30 Winding roller 31 Cotton thread 32 Guide 33 Roller 34 Knitting needle 35 Winding roller

Claims (9)

1. Containing at least one base component (A) selected from mineral oil, silicone oil and ester oil, a fatty acid metal salt (B), and an organic phosphate ester (C),
   The average molecular weight of the fatty acid constituting the fatty acid metal salt (B) is 150 to 256.
   Treatment agent for elastic fibers.
2. The treatment agent for elastic fibers according to claim 1, wherein the content of the organic phosphate (C) is 5 to 2000 parts by weight with respect to 100 parts by weight of the fatty acid metal salt (B).
3. The elastic fiber treatment agent according to claim 1 or 2, wherein the fatty acid metal salt (B) is at least one selected from a sodium salt, a potassium salt, a magnesium salt, a calcium salt, a zinc salt, and an aluminum salt.
4. The treatment agent for elastic fibers according to any one of claims 1 to 3, wherein a molar ratio of the fatty acid having 10 to 14 carbon atoms to the fatty acid constituting the fatty acid metal salt (B) is 50 mol% or more.
5. The treatment agent for elastic fibers according to any one of claims 1 to 4, wherein the organic phosphate ester (C) is represented by the following general formula (1) and / or the following general formula (2).
   

   

   (In the general formula (1), R ¹ is a hydrocarbon group having 6 to 24 carbon atoms, A ¹ O is an oxyalkylene group having 2 to 4 carbon atoms, and a is a number from 0 to 30. m Is a number from 1 to 2. When there are two R ¹ and (A ¹ O) _{a in the} molecule, they may be the same or different from each other.
   

   

   (In the general formula (2), R ² is a hydrocarbon group having 6 to 24 carbon atoms, A ² O is an oxyalkylene group having 2 to 4 carbon atoms, and b is a number from 0 to 30. Q ¹ is a hydroxyl group or R ² O (A ² O) _b n is 1 or 2. When there are two R ² and (A ² O) _{b in the} molecule, they are identical to each other. It may or may not be.)
6. The elastic fiber treatment agent according to any one of claims 1 to 5, wherein a weight ratio of the base component (A) to the treatment agent is 50 to 99.99% by weight.
7. The elastic fiber treatment agent according to any one of claims 1 to 6, wherein a weight ratio of the fatty acid metal salt (B) to the treatment agent is 0.01 to 30% by weight.
8. The elastic fiber treatment agent according to any one of claims 1 to 7, wherein a weight ratio of the organophosphate (C) to the treatment agent is 0.01 to 30% by weight.
9. An elastic fiber obtained by applying the treatment agent according to any one of claims 1 to 8 to an elastic fiber main body.

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