JP2012241291A - Modifier for additive type elastic fiber, method for producing elastic fiber, and elastic fiber - Google Patents

Abstract

[PROBLEMS] To achieve excellent unwinding properties and scouring properties without causing solid fine particles such as higher fatty acid metal salts to separate or settle in the spinning solution, and to prevent clogging of the nozzle holes and yarn breakage during spinning. An additive-type elastic fiber modifier capable of producing high-quality elastic fibers having adhesion to a hot melt adhesive, etc., an elastic fiber production method using such a modifier, and an elastic fiber obtained by such production method provide.
As an additive type elastic fiber modifier, specific solid fine particles are dispersed in a predetermined proportion in a specific dispersion medium containing a specific smoothing agent component and a specific nitrogen-containing compound in a predetermined proportion. A thing was used.
[Selection figure] None

Description

  The present invention relates to an additive-type elastic fiber modifier, an elastic fiber manufacturing method, and an elastic fiber. When spinning elastic fibers such as polyurethane, a modifier is added to the spinning dope. The present invention relates to an improvement of such an additive-type elastic fiber modifier, and also relates to an elastic fiber manufacturing method using the improved additive-type elastic fiber modifier and an elastic fiber obtained by this manufacturing method.

  Conventionally, those containing higher fatty acid metal salts such as magnesium stearate are known as additive type elastic fiber modifiers as described above (see, for example, Patent Documents 1 to 3). However, when a higher fatty acid metal salt such as magnesium stearate is included in the elastic fiber, the unraveling property and runnability from the package of the elastic fiber and the sticking of the yarns are improved. Higher fatty acid metal salts are prone to separation and sedimentation, and as a result, it is difficult to produce elastic fibers having uniform characteristics, and the higher fatty acid metal salts tend to clog the die holes during spinning, There is a problem that cutting is likely to occur, and further, when processing is performed using a hot melt adhesive, there is a problem that poor adhesion between the elastic fiber and the hot melt adhesive is likely to occur.

Japanese Patent Laid-Open No. 9-217227 JP 2001-214332 A JP 2003-129376 A

  The problem to be solved by the present invention is that the fine fine particles such as higher fatty acid metal salts are separated or settled in the spinning solution while having good unwinding from the package and preventing sticking between yarns. In addition, it is possible to produce a high-quality elastic fiber having excellent scouring properties, adhesiveness to a hot melt adhesive, etc. without causing clogging of the die hole or yarn breakage during spinning. An object of the present invention is to provide a quality material, a method for producing an elastic fiber using the modifier, and an elastic fiber obtained by the production method.

  As a result of researches to solve the above problems, the present inventors have dispersed specific solid fine particles at a predetermined ratio in a specific dispersion medium containing a specific smoothing agent component and a specific nitrogen-containing compound at a predetermined ratio. It was found that the use of the additive-type elastic fiber modifier was correct and suitable.

  That is, the present invention is an additive-type elastic fiber modifier used by adding to a spinning dope for producing elastic fibers, comprising the following A component, B component and C component, and the A component / B component = 100 / 0.01 to 100/30 (mass ratio), and the total of the A component and B component / the C component = 100 / 0.01 to 100/100 (mass ratio) The additive component is characterized in that the component C is colloidally dispersed and the average particle size measured by the following average particle size measurement method is 0.01 to 100 μm. It relates to a modifier for elastic fibers. The present invention also relates to a method for producing an elastic fiber for spinning a spinning dope added with such an additive elastic fiber modifier, and an elastic fiber obtained by such a production method.

Component A: containing 50 to 100% by mass of mineral oil and 0 to 50% by mass (total 100% by mass) of silicone oil and / or ester oil, and a viscosity at 25 ° C. of 2 × 10 ⁻⁶ to 1000 × 10 ⁻⁶ m ² / s liquid.

  Component B: One or two or more selected from a nitrogen-containing compound represented by the following chemical formula 1, a nitrogen-containing compound represented by the chemical formula 2, a nitrogen-containing compound represented by the chemical formula 3 and a nitrogen-containing compound represented by the chemical formula 4.

In Chemical Formulas 1 to 4,
R ^{1 to} R ⁶ : a residue obtained by removing one terminal hydrogen atom from a polyolefin having a number average molecular weight of 200 to 8000 X ^{1 to} X ⁴ : an alkylene group having 2 to 6 carbon atoms Y ¹ , Y ² : carbon number 1 -20 alkyl group, alkenyl group having 1-20 carbon atoms, hydroxyalkyl group having 1-20 carbon atoms, or hydrogen atom (however, when p = 0 or r = 0, the hydrogen atom is excluded)
p to s: integer of 0 to 10

Component C: One or two or more solid fine particles selected from silicon oxide, the following metal atom oxide, the following metal atom carbonate and the following metal atom salt of a fatty acid having 12 to 22 carbon atoms Element: sodium, magnesium, calcium, barium, zinc, titanium, aluminum

Measuring method of average particle diameter: The modifier for additive type elastic fiber is 1/1 (mass ratio) of polydimethylsiloxane and mineral oil whose viscosities at 25 ° C. are both 10 × 10 ⁻⁶ m ² / s. Using the mixed solution, dilute so that the concentration of component C in the additive-type elastic fiber modifier is 1000 mg / L, and use the diluted solution at a liquid temperature of 25 ° C. for a laser diffraction particle size distribution analyzer. The method of measuring the volume-based average particle diameter.

  First, the additive elastic fiber modifier according to the present invention (hereinafter referred to as the modifier of the present invention) will be described. The modifier of the present invention comprises a specific A component, a specific B component, and a specific C component as described above. The A component and the B component are not only used as a mere dispersion medium for the C component, but are essential components for preventing clogging of the mouthpiece hole due to the C component when the elastic fiber is spun and manufactured.

The mineral oil of component A includes a general petroleum fraction composed of a paraffin component, a naphthene component, an aroma component, etc., and the viscosity at 25 ° C. is 2 × 10 ^{−6 to} 100 × 10 ⁻⁶ m ^2. / S is preferred.

  Examples of the component A silicone oil include 1) polydimethylsiloxanes having repeating units composed of dimethylsiloxane units, and 2) polydialkyls having repeating units composed of dimethylsiloxane units and dialkylsiloxane units having 2 to 4 carbon atoms. Siloxanes, and 3) polysiloxanes in which the repeating units are composed of dimethylsiloxane units and methylphenylsiloxane units are exemplified, among which polydimethylsiloxanes are preferable.

  As the A component ester oil, 1) aliphatic monohydric alcohols and aliphatics such as butyl stearate, octyl stearate, oleyl laurate, oleyl oleate, isotridecyl stearate, isopentacosanyl isostearate Esters with monocarboxylic acids, 2) 1,6-hexanediol didecanoate, trimethylolpropane monooleate monolaurate, trimethylolpropane trilaurate, castor oil, aliphatic polyhydric alcohols and aliphatic monocarboxylic acids 3) Esters of aliphatic monohydric alcohols and aliphatic polyhydric carboxylic acids such as dilauryl adipate and dioleyl azelate, among others, octyl stearate and isotridecyl stearate Aliphatic monohydric alcohol and aliphatic monocarboxylic Esters of 15 to 40 carbon atoms, esters of aliphatic polyhydric alcohols such as trimethylolpropane trilaurate and castor oil, and aliphatic monocarboxylic acids, and esters having 15 to 40 carbon atoms in total Is preferred.

  The component A contains 50 to 100% by mass of mineral oil and 0 to 50% by mass (total of 100% by mass) of silicone oil and / or ester oil. 100% by mass, preferably containing silicone oil and / or ester oil in a proportion of 0 to 30% by mass (total 100% by mass), 70 to 90% by mass of mineral oil, and silicone oil and / or ester oil Is more preferable in a ratio of 10 to 30% by mass (total 100% by mass). When the total ratio of the silicone oil and the ester exceeds 50% by mass in the component A, the adhesiveness and scouring property with the hot melt adhesive are significantly reduced.

The component A has a viscosity at 25 ° C. of 2 × 10 ^{−6 to} 1000 × 10 ⁻⁶ m ² / s, but preferably has a viscosity of 2 × 10 ^{−6 to} 100 × 10 ⁻⁶ m ² / s. . When the viscosity is less than 2 × 10 ⁻⁶ m ² / s, the solid fine particles in the modifier are liable to settle and secondary agglomeration, and clogging of the die holes is likely to occur when spinning elastic fibers. . On the contrary, if the viscosity exceeds 1000 × 10 ⁻⁶ m ² / s, it becomes difficult to make the particle size of the solid fine particles in the modifier uniform and small during the production of the modifier, Due to the exothermic heat, the modifier itself is easily altered. In the present invention, the viscosity is a value measured by a method using a Canon Fenceke viscometer described in JIS-K2283 (Petroleum product kinematic viscosity test method).

  The B component used for the modifier of the present invention is any of the nitrogen-containing compound represented by the chemical formula 1, the nitrogen-containing compound represented by the chemical formula 2, the nitrogen-containing compound represented by the chemical formula 3 and the nitrogen-containing compound represented by the chemical formula 4 One or two or more selected from compounds. These nitrogen-containing compounds are essential components for improving the scourability and the adhesiveness with the hot melt adhesive. The above-mentioned A component can be used for dilution of B component.

X ^{1 to} X 4 in Chemical Formulas ^{1 to 4} are alkylene groups having 2 to 6 carbon atoms. Examples of the alkylene group include an ethylene group, a propylene group, a methylethylene group, a tetramethylene group, a 2-methylpropylene group, a pentamethylene group, a 2-methyltetramethylene group, a hexamethylene group, and a 2-methylpentamethylene group. Among them, an alkylene group having 2 to 4 carbon atoms such as an ethylene group, a propylene group, a methylethylene group, a tetramethylene group, and a 2-methylpropylene group is preferable.

Y ¹ and Y ^{2 in} Chemical Formula 1 and Chemical Formula 3 are an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a hydrogen atom, for example, a methyl group , Ethyl group, ethenyl group, propyl group, propenyl group, isopropyl group, isopropenyl group, butyl group, butenyl group, isobutyl group, isobutenyl group, pentyl group, pentenyl group, isopentyl group, isopentenyl group, hexyl group, octyl group 2-methylheptyl group, nonyl group, decyl group, 2-methylheptyl group, dodecyl group, 2-methylundecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, icosyl group, hydroxymethyl group, hydroxyethyl group , Hydroxypropyl group, hydroxyisopropyl group, hydroxybutyl group, Examples include droxyisobutyl group, hydroxypentyl group, hydroxyhexyl group, hydroxyoctyl group, hydroxydecyl group, hydroxydodecyl group, hydroxytetradecyl group, hydroxyhexadecyl group, hydroxyoctadecyl group, hydroxyicosyl group, hydrogen atom, etc. However, among these, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, a hydroxyalkyl group having 1 to 12 carbon atoms, or a hydrogen atom is preferable. However, when p = 0 in Chemical Formula 1 or r = 0 in Chemical Formula 3, a hydrogen atom is excluded.

  P to s in Chemical Formulas 1 to 4 are integers of 0 to 10, and an integer of 1 to 6 is particularly preferable.

R ^{1 to} R ⁶ in Chemical Formulas 1 to 4 are polyolefins made of a polymer such as propene, butene, pentene, hexene, octene, and the like, and one terminal hydrogen atom from a polyolefin having a number average molecular weight of 200 to 8000 Of these residues, a residue obtained by removing one terminal hydrogen atom from a polyolefin having a number average molecular weight of 500 to 5,000 is preferable.

  The component B is one or more selected from the nitrogen-containing compound represented by the chemical formula 1, the nitrogen-containing compound represented by the chemical formula 2, the nitrogen-containing compound represented by the chemical formula 3 and the nitrogen-containing compound represented by the chemical formula 4 Of these, the nitrogen-containing compounds represented by Chemical Formula 1 and / or the nitrogen-containing compounds represented by Chemical Formula 2 are preferred.

As described above, the C component to be provided to the modifier of the present invention includes silicon oxide, the following metal atom oxide, the following metal atom carbonate, and the following metal atom of a C12-22 fatty acid. One or two or more solid fine particles selected from a salt are preferable, and among them, solid fine particles that are a magnesium salt of a fatty acid having 12 to 22 carbon atoms and / or a calcium salt of a fatty acid having 12 to 22 carbon atoms are preferable.
Metal elements: sodium, magnesium, calcium, barium, zinc, titanium, aluminum

  Examples of the silicon oxide of the C component include silicon oxide, and examples of the metal atom oxide include sodium oxide, magnesium oxide, calcium oxide, barium oxide, zinc oxide, titanium oxide, and aluminum oxide.

  Furthermore, examples of the carbon oxide of the C metal atom include sodium carbonate, magnesium carbonate, calcium carbonate, barium carbonate, and zinc carbonate.

  Furthermore, the salt of the metal atom of the fatty acid of component C includes sodium laurate, sodium myristic acid, sodium palmitate, sodium stearate, sodium arachilate, sodium behenate, magnesium dilaurate, di- Lauric acid calcium salt, dilauric acid zinc salt, dilauric acid barium salt, dimyristic acid magnesium salt, dimyristic acid calcium salt, dimyristic acid zinc salt, dimyristic acid barium salt, dipalmitic acid magnesium salt, dipalmitic acid calcium salt, Zinc dipalmitate, barium dipalmitate, magnesium distearate, calcium distearate, zinc distearate, barium distearate, magnesium diarachiate, calcium diarachiate, di Lacic acid zinc salt, diarachic acid barium salt, dibehenic acid magnesium salt, dibehenic acid calcium salt, dibehenic acid zinc salt, dibehenic acid barium salt, myristic acid palmitate magnesium salt, myristic acid palmitic acid calcium salt, myristic acid palmitic acid zinc salt , Myristic acid palmitic acid barium salt, myristic acid magnesium stearate, myristic acid calcium stearate, myristic acid zinc stearate, myristic acid barium stearate, palmitic acid magnesium stearate, palmitic acid stearate, palmitic acid Examples include zinc stearate, barium palmitate, and aluminum tristearate. Among them, dimyristic acid magnesium salt, dimyristic acid calcium salt, dipalmitic acid magnesium salt, dipalmitic acid calcium salt, distearic acid magnesium salt, myristic acid palmitic acid magnesium salt, myristic acid palmitic acid calcium salt, Magnesium and calcium salts of fatty acids having 14 to 18 carbon atoms, such as magnesium palmitate stearate, calcium palmitate stearate, magnesium palmitate stearate, calcium palmitate stearate and mixtures thereof, are preferred.

  The A component, the B component, and the C component used for the modifier of the present invention described above can be easily prepared by a known method.

  The modifier of the present invention is composed of the A component, the B component and the C component described above, but is contained at a ratio of A component / B component = 100 / 0.01 to 100/30 (mass ratio). Preferably, it is contained at a ratio of A component / B component = 100 / 0.1 to 100/20 (mass ratio). By setting the content ratio of the B component to the A component in this way, the thixotropy of the modifier of the present invention can be moderately suppressed, and the kneading property with the spinning dope can be kept good.

  Moreover, the modifier of this invention is contained in the ratio of the sum total of A component and B component / C component = 100 / 0.01-100 / 100 (mass ratio), Preferably, it is a component of A component and B component. The total / C component = 100 / 0.01 to 100/50 (mass ratio). By making the content ratio of the C component to the total of the A component and the B component in this way, the solid fine particles of the C component are prevented from separating or settling in the modifier of the present invention, and the stability is improved. As a result, it is possible to prevent clogging of the die hole due to the C component during spinning.

  Furthermore, as described above, the modifier of the present invention is a liquid in which solid fine particles of component C are colloidally dispersed. The modifier of the present invention is a dispersion in which a mixture of component A and component B is used as a dispersion medium and solid fine particles of component C are dispersed in a colloidal form at the above-described mass ratio.

  Furthermore, as described above, the modifier of the present invention has an average particle size of 0.01 to 100 μm as measured by the following average particle size measurement method. The thing of ~ 30 micrometers is preferable.

Measuring method of average particle size: 1/1 (mass ratio) mixed liquid of polydimethylsiloxane and mineral oil having both viscosities at 25 ° C. of 10 × 10 ⁻⁶ m ² / s. Is diluted so that the concentration of the C component in the modifier becomes 1000 mg / L, and the diluted solution is supplied to a laser diffraction particle size distribution analyzer at a liquid temperature of 25 ° C. How to measure. As a laser diffraction particle size distribution measuring apparatus at this time, LA-920 manufactured by Horiba, Ltd. or the like can be used.

  In using the modifier of the present invention, other components can be used in combination as necessary. Examples of such other components include 1) modified silicone oils such as amino-modified polydimethylsiloxane, polyether-modified polydimethylsiloxane, carboxy-modified polydimethylsiloxane, epoxy-modified polydimethylsiloxane, mercapto-modified polydimethylsiloxane, and alkyl-modified polydimethylsiloxane. And silicone resins, 2) binders such as nonionic surfactants and higher alcohols, 3) antistatic agents such as ionic surfactants, 4) other wettability improvers, UV absorbers, antioxidants, Examples of the synthetic fiber treating agent such as a smoothing agent, an antistatic agent, and an antiseptic are known.

  The method for preparing the modifier of the present invention is not particularly limited, and a known method can be applied. For example, after the A component, the B component, and the C component are mixed at a predetermined ratio to obtain a mixture, the mixture is subjected to wet pulverization to prepare the modifier of the present invention as a dispersion.

  Examples of the pulverizer used for the wet pulverization include known wet pulverizers such as a vertical bead mill, a horizontal bead mill, a sand grinder, and a colloid mill. Moreover, although it does not restrict | limit especially as temperature in the case of mixing each component and the temperature in the case of wet grinding, 20-35 degreeC is preferable. The viscosity of the modifier of the present invention thus prepared is within a range of 50 to 30000 mPa · s when measured using an E-type viscometer at a temperature of 30 ° C. under the conditions of rotor E and 20 rpm. Preferably.

  The modifier of the present invention is used by adding to a spinning dope for producing elastic fibers. Examples of the elastic fiber include polyester-based elastic fiber, polyamide-based elastic fiber, polyolefin-based elastic fiber, polyurethane-based elastic fiber, and the like, and the effect is particularly high when added to the spinning solution of polyurethane-based elastic fiber. The form of the elastic fiber is not particularly limited, and can be used for either a filament-based elastic fiber or a span-based elastic fiber.

  The amount of the modifier of the present invention added to the spinning dope is not particularly limited. However, when the elastic fiber is a polyurethane-based elastic fiber, it is usually 0.1 to 100 parts by mass of the polyurethane solid content in the spinning dope. It adds so that it may become a ratio of 20 mass parts.

  Further, the modifier of the present invention may be added to the spinning dope during any step of producing the spinning dope. The modifier of the present invention needs to be added to the spinning dope between the polymerization step and the spinning step, and it is particularly preferred to add it immediately before the spinning step.

  Next, a method for producing an elastic fiber according to the present invention (hereinafter referred to as a production method of the present invention) will be described. The production method of the present invention is a method of spinning a spinning solution obtained by adding the modifier of the present invention to a spinning solution of elastic fibers. Examples of the spinning method include a dry spinning method, a melt spinning method, a wet spinning method, and the like, and the effect is particularly high when spinning by the dry spinning method.

  Finally, the elastic fiber according to the present invention (hereinafter referred to as the elastic fiber of the present invention) will be described. The elastic fiber of the present invention is an elastic fiber obtained by the production method of the present invention. There are no limitations on the type of elastic fiber, and any of polyester-based elastic fiber, polyamide-based elastic fiber, polyolefin-based elastic fiber, polyurethane-based elastic fiber, and the like may be used. In particular, the effect of polyurethane-based elastic fiber is high.

  According to the present invention described above, high-quality elasticity having excellent twisting shape, unwinding property, scouring property, and adhesiveness with hot melt adhesive without causing clogging of the mouthpiece hole, occurrence of scum and yarn breakage There is an effect that a fiber can be manufactured.

  Hereinafter, examples and the like will be given to make the configuration and effects of the present invention more specific, but the present invention is not limited to these examples. In the following examples and the like, parts indicate parts by mass, and% indicates mass%.

Test category 1 (synthesis of nitrogen-containing compounds of component B)
Synthesis of the nitrogen-containing compound (B-1) represented by Chemical Formula 1 To a 2-liter glass reaction vessel, 100 g of triethylenetetraamine and 863 g of mineral oil were added, and the number average of polybutene moieties was 150 ° C. under a nitrogen stream. 800 g of polybutenyl succinic anhydride having a molecular weight of 1500 was gradually added dropwise and reacted for 2 hours. The temperature was raised to 200 ° C., and unreacted triethylenetetraamine and generated water were removed under reduced pressure. Then, the temperature was lowered to 140 ° C. and filtered to synthesize polybutenyl succinimide. This was made into the nitrogen-containing compound (B-1).

Synthesis of nitrogen-containing compound (B-2), (B-5) to (B-7), (B-10) and (b-2) Nitrogen-containing compound in the same manner as nitrogen-containing compound (B-1) Compounds (B-2), (B-5) to (B-7), (B-10) and (b-2) were synthesized.

Synthesis of nitrogen-containing compound (B-3) represented by Chemical Formula 2 To a 2-liter glass reaction vessel, 47 g of tripropylenetetraamine and 814 g of mineral oil were added, and the number average of polybutene moieties was 150 ° C. under a nitrogen stream. 799 g of polybutenyl succinic anhydride having a molecular weight of 1500 was gradually added dropwise and reacted for 2 hours. After raising the temperature to 200 ° C. and removing the produced water under reduced pressure, the temperature was lowered to 140 ° C. and filtered to synthesize polybutenyl succinimide. This was made into the nitrogen-containing compound (B-3).

-Synthesis of nitrogen-containing compounds (B-4), (B-8) and (B-9) Nitrogen-containing compounds (B-4) and (B-8) in the same manner as nitrogen-containing compounds (B-3) And (B-9) were synthesized.

Synthesis of nitrogen-containing compound (B-11) represented by Chemical formula 3 To a 2-liter glass reactor, 100 g of triethylenetetraamine and 722 g of mineral oil were added, and the number average of polybutene moieties was 120 ° C. under a nitrogen stream. 649 g of polybutenyl succinic anhydride having a molecular weight of 1200 was gradually added dropwise, reacted for 2 hours, and then filtered to synthesize polybutenyl succinic amide. This was made into the nitrogen-containing compound (B-11).

Synthesis of nitrogen-containing compound (B-14), (B-15), (B-17) to (B-20), (b-1) and (b-3) Nitrogen-containing compound (B-11) and Similarly, nitrogen-containing compounds (B-14), (B-15), (B-17) to (B-20), (b-1) and (b-3) were synthesized.

Synthesis of nitrogen-containing compound (B-12) represented by Chemical formula 4 In a 2-liter glass reaction vessel, 775 g of polybutenyl succinic anhydride having a number average molecular weight of 3000 polybutene moiety, 18 g of triethylenetetraamine, and 793 g of mineral oil And reacted for 2 hours at 120 ° C. under a nitrogen stream, followed by filtration to synthesize polybutenyl succinic acid amide. This was made into the nitrogen-containing compound (B-12).

-Synthesis | combination of nitrogen-containing compound (B-13) and (B-16) It carried out similarly to nitrogen-containing compound (B-12), and synthesize | combined nitrogen-containing compound (B-13) and (B-16).

  Table 1 summarizes the contents of the nitrogen-containing compounds of component B synthesized as described above.

Test category 2 (Preparation of modifiers for additive elastic fibers)
Example 1 {Preparation of additive-type elastic fiber modifier (T-1)}
Viscosity at 25 ° C. is ¹⁰ × 10 -6 ^m 2 / s for a mineral oil as the component A (m-1) polydimethylsiloxane 90 parts and a viscosity at 25 ° C. is ^{10 × 10 -6 m 2 / s} (p-1 ) 10 parts of a mixture (a mixture having a viscosity of 10 × 10 ⁻⁶ m ² / s at 25 ° C.) and 5 parts of the nitrogen-containing compound (B-1) described in Table 1 as a B component with respect to 100 parts of the A component Further, 30 parts of magnesium distearate (C-1) as C component is added to 100 parts of the mixture, and the mixture is mixed at a temperature of 20 to 35 ° C. until uniform, and then wet using a horizontal bead mill. The additive type elastic fiber modifier (T-1) was prepared by pulverizing and dispersing colloidal magnesium distearate (C-1).

Examples 2 to 49 and Comparative Examples 1 to 11 {Preparation of Additive Elastic Fiber Modifiers (T-2) to (T-49) and (t-1) to (t-11)}
In the same manner as in the preparation of the additive-type elastic fiber modifier (T-1) in Example 1, the modifiers for additive-type elastic fibers (T-2) in Examples 2 to 49 and Comparative Examples 1 to 11 are used. (T-49) and (t-1) to (t-11) were prepared. However, in the preparation of the additive-type elastic fiber modifier (t-3) of Comparative Example 3, the viscosity increase during the wet pulverization treatment was severe, and the titanium oxide (C-3) could not be dispersed in a colloidal form. It was.

Tables 2 to 5 show the contents of the modifiers (T-1) to (T-49) and (t-1) to (t-11) for each of the added elastic fibers prepared as described above. Shown together.

In Tables 2 to 5,
Kind of modifier: Kind of modifier for additive type elastic fiber * 1: Mass part of B component with respect to 100 parts by mass of A component * 2: Mass part of C component with respect to 100 parts by mass of A component and B component in total m -1: Mineral oil with a viscosity of 10 × 10 ⁻⁶ m ² / s at 25 ° C. m-2: Mineral oil with a viscosity of 20 × 10 ⁻⁶ m ² / s at 25 ° C. m-3: Viscosity at 25 ° C. Mineral oil of 5 × 10 ⁻⁶ m ² / s m-4: Mineral oil having a viscosity at 25 ° C. of 220 × 10 ⁻⁶ m ² / s m-5: Viscosity at 25 ° C. of 220 × 10 ⁻⁶ m ² / Mineral oil of s p-1: polydimethylsiloxane having a viscosity of 10 × 10 ⁻⁶ m ² / s at 25 ° C. p-2: polydimethylsiloxane having a viscosity of 20 × 10 ⁻⁶ m ² / s at 25 ° C. p- 3: Poly with a viscosity at 25 ° C. of 5 × 10 ⁻⁶ m ² / s Dimethylsiloxane p-4: Polydimethylsiloxane having a viscosity of 10,000 × 10 ⁻⁶ m ² / s at 25 ° C. es-1: 2-ethylhexyl stearate es-2: Isotridecyl stearate B-1 to B-20, b-1 to b-3: Component B described in Table 1 C-1: Magnesium distearate C-2: Calcium distearate C-3: Titanium oxide C-4: Zinc oxide C-5: Silicon oxide C-6 : Magnesium oxide

・ Test Category 3 (Manufacture of polyurethane elastic fiber by dry spinning)
-Examples 50-98 and Comparative Examples 12-24
First, an N, N′-dimethylacetamide (hereinafter referred to as DMAc) solution (concentration 35%) of a polyurethane raw material composed of tetramethylene ether glycol having a molecular weight of 2900, bis- (p-isocyanatephenyl) -methane and ethylenediamine is polymerized, A polymer solution (A) was obtained.

  Next, a polyurethane polymer obtained by reacting t-butyldiethanolamine and methylene-bis- (4-cyclohexylisocyanate) (trade name (registered trademark) Metachlor 2462 manufactured by DuPont), and a condensation polymer of p-cresol and divinylbenzene. A DMAc solution (concentration 35%) of a 2-to-1 (mass ratio) mixture with (trade name (registered trademark) Metachlor 2390 manufactured by DuPont) was prepared as an additive solution (B).

  Then, 96 parts of the polymer solution (A) and 4 parts of the additive solution (B) were uniformly mixed to obtain a mixed solution (C). Furthermore, the additive-type elastic fiber is added to the mixed solution (C) so as to be an added part by mass of the modifier described in Tables 6 and 7 with respect to 100 parts by mass of the solid content of the polyurethane in the mixed solution (C). The modifier was uniformly mixed by an injection method using a static mixer to obtain a spinning solution.

  Using the spinning solution prepared as described above, a 560 dtex polyurethane elastic fiber consisting of 56 single yarns is spun by a dry spinning method used in a known spandex, and the following treatment is performed from an oiling roller before winding. The agent was neatly fed with a roller. The roller oiled in this way is wound at a winding speed of 500 m / min using a surface drive winder through a traverse guide giving a winding width of 104 mm to a 115 mm long cylindrical paper tube, and dry spinning. To obtain polyurethane elastic fiber packages (1 kg and 3 kg). In addition, adjustment of the adhesion amount of a processing agent was performed by adjusting the rotation speed of an oiling roller.

Treatment agent: In Examples 50 to 98 and Comparative Examples 12 to 23, 10 × 10 ⁻⁶ m ² / s mineral oil was used at 25 ° C., and in Comparative Example 24, a polypropylene glycol polyol having an average molecular weight of 400 was used. It was.

Tables 6 and 7 summarize the additive elastic fiber modifiers used in the production of the polyurethane elastic fibers and the amounts used.

In Table 6 and Table 7,
Kind of modifier: Kind of modifier for additive type elastic fiber Addition part by mass of modifier: of modifier for additive type elastic fiber with respect to 100 parts by mass of polyurethane in the mixed solution (C) Additive parts by mass Comparative Examples 12 and 24: Example in which the additive elastic fiber modifier was not added Comparative Example 15: The additive elastic fiber modifier (t-3) was uniformly mixed because the viscosity was too high It was not possible to produce polyurethane elastic fibers.
T-1 to T-49, t-1 to t-11: Additive elastic fiber modifiers described in Tables 2 to 5

Test category 4 (Evaluation of manufactured polyurethane elastic fibers)
The polyurethane-based elastic fiber package obtained by dry spinning obtained in Test Category 3 was subjected to the following measurements and evaluations, and the results are summarized in Tables 8 and 9.

-Evaluation of mixability with spinning stock solution The dispersion state of the modifier for additive-type elastic fibers in the spinning solution prepared in Test Category 3 was evaluated according to the following criteria.
◎: Additive elastic fiber modifier is uniformly dispersed in the spinning solution, and there is no non-uniform portion. ○: Additive elastic fiber modifier is dispersed almost uniformly in the spinning solution. However, some non-uniform portions are observed. Δ: Additive elastic fiber modifier is dispersed non-uniformly in the spinning solution. X: Additive elastic fiber modifier is almost dispersed in the spinning solution. Not

-Evaluation of spinnability The yarn breakage frequency during spinning and winding in Test Category 3 was measured, the winding distance per yarn breakage was calculated, and the spinnability was evaluated according to the following criteria.
◎: The winding distance per thread break is 5000 km or more. ○: The winding distance per thread break is 4500 km or more and less than 5000 km. Δ: The winding distance per thread break is 4000 km or more and less than 4500 km. Winding distance per turn is less than 4000 km

・ Evaluation of winding shape For the package (1 kg winding), the maximum value (Wmax) and the minimum width (Wmin) of the winding width are measured, the bulge is obtained from the difference (Wmax−Wmin), and evaluated according to the following criteria. did.
A: Bulge is less than 4 mm B: Bulge is 4-6 mm
Δ: Bulge is 6-7mm
×: Bulge is over 7mm

・ Evaluation of unraveling property The first drive roller on one side and the first free roller that is always in contact with the first feed roller constitute the feed section, and the opposite side is wound up by the second drive roller and the second free roller that is always in contact with this. The winding part was installed 20 cm apart in the horizontal direction with respect to the delivery part. The same package (3 kg winding) as the above was mounted on the first driving roller, and was unwound until the thickness of the bobbin became 2 mm and wound around the second driving roller. While fixing the feed speed of the polyurethane elastic fiber from the first driving roller at 50 m / min, the winding speed of the polyurethane elastic fiber to the second driving roller is gradually increased from 50 m / min to increase the polyurethane elastic fiber. Was forcibly resolved from the package. At the time of this forced unwinding, the winding speed V (m / min) when the polyurethane elastic fiber no longer dances between the sending portion and the winding portion is measured. %) And evaluated according to the following criteria.
A: Less than 120% unsolvability (can be solved stably without any problem)
○: Unwinding property is 120% or more and less than 160% (although there is a slight resistance to pulling out the yarn, there is no yarn breakage and it can be unraveled stably)
Δ: Unwinding property is 160% or more and less than 200% (there is resistance to pulling out the yarn, there is some thread breakage, and there is a slight problem in operation)
×: Unwinding property is 200% or more (high resistance to pulling out yarn, frequent yarn breakage, and a big problem in operation)
Moreover, the unwindability was similarly evaluated about the package left at 25 degreeC for 6 months.

・ Evaluation of smoothness Using a friction measurement meter (trade name SAMPLE Friction Unit Model TB-1 manufactured by Eiko Sokki Co., Ltd.), a chrome-plated satin pin with a surface roughness of 2S and a diameter of 1 cm is placed between two free rollers. The contact angle of the polyurethane elastic fiber drawn out from the package (1 kg roll) with respect to the chrome plated satin pin was set to 90 degrees. Under the condition of 60% RH at 25 ° C., 5 g of initial tension (T ₁ ) was applied on the inlet side, and the secondary tension (T ₂ ) on the outlet side when running at a speed of 100 m / min was measured. The friction coefficient was calculated from the following formula 2 and evaluated according to the following criteria.
A: Friction coefficient is 0.150 or more and less than 0.220 B: Friction coefficient is 0.220 or more and less than 0.260 Δ: Friction coefficient is 0.260 or more and less than 0.300 ×: Friction coefficient is 0.300 or more

Evaluation of anti-scum property Ten of the above-mentioned packages (1 kg roll) were prepared on a miniature warping machine imitating a warping machine, and wound at 500 km at a yarn speed of 100 m / min in an atmosphere of 25 ° C. × 65% RH. At this time, the dropout and accumulation state of the scum in the comb guide of the miniature warping machine was visually observed and evaluated according to the following criteria.
A: Almost no scum adhered.
○: Scum slightly adhered, but there was no problem in stable running of the yarn.
Δ: There was much adhesion and accumulation of scum, and there was a slight problem in stable running of the yarn.
X: Adhesion and accumulation of scum were remarkably large, and there was a big problem in stable running of the yarn.

・ Evaluation of adhesion A rubber-based hot melt adhesive mainly composed of a styrene butadiene styrene block copolymer heated and melted at 145 ° C. is uniformly applied with a roller on a spunbond nonwoven fabric made of polypropylene, and cut into 40 mm. Two pieces having a size of 20 mm were prepared. Between the adhesive application surfaces of the two cut pieces, 10 mm of a polyurethane elastic fiber having a length of 40 mm drawn from the package (1 kg roll) is sandwiched, a processing temperature of 160 ° C., and a load of 9 g / cm. ² for 30 seconds to prepare a sample. Fix the polypropylene spunbond nonwoven part of this sample to the upper sample gripping part of a tensile testing machine (trade name, Autograph AGS, manufactured by Shimadzu Corporation), and fix the polyurethane elastic fiber to the lower sample gripping part, The tensile strength required to pull out the polyurethane elastic fiber from the polypropylene spunbond nonwoven fabric was measured at a speed of 100 mm / min, and evaluated according to the following criteria.
A: Strength is 35 g or more (Strong hot melt adhesion, enabling stable operation)
○: Strength is 30 g or more and less than 35 g (practical hot melt adhesion, no problem occurs in operation)
Δ: Strength is 25 g or more and less than 30 g (There is a slight problem with hot-melt adhesion, and problems may occur during operation)
X: Strength is less than 25 g (Hot melt adhesion is weak and there is a big problem in operation)

Evaluation of scourability Fabrics were produced from the polyurethane elastic fiber package (1 kg roll) and nylon yarn by knitting. Two pieces of 5 cm square were cut from this woven fabric, and the adhesion amount OPU ₁ (mass%) of the additive-type elastic fiber modifier and the above-mentioned treatment agent was measured for one of them. The remaining one uses a product name pitch run manufactured by Nikka Chemical Co., Ltd. as a scouring agent. OPU ₂ (% by mass) was measured in the same manner. The measurement of the adhesion amount (OPU ₁ and OPU ₂₎ is a method based on JIS-L1073 (Synthetic Fiber Filament Yarn Test Methods), was measured using n-hexane as an extraction solvent. The oil agent residual ratio was calculated from the following number 3 and evaluated according to the following criteria.
◎: Oil agent residual ratio is less than 30% ○: Oil agent residual ratio is 30% or more and less than 40% △: Oil agent residual ratio is 40% or more and less than 50% ×: Oil agent residual ratio is 50% or more

In Table 9,
Comparative Example 15: Same as test category 3

  As is apparent from the results of Tables 8 and 9, the modifier of the present invention has a good mixing property with the spinning dope, has very little scum accumulated in the production process, and has a good spinnability. A high-quality elastic fiber having excellent twisted shape, unwinding property, smoothness, hot-melt adhesiveness and refinability can be produced.

Claims (16)

An additive-type elastic fiber modifier used by adding to a spinning dope for producing elastic fibers, comprising the following A component, B component and C component, and the A component / the B component = 100 / It is contained in a ratio of 0.01 to 100/30 (mass ratio), and is contained in a ratio of the sum of the A component and the B component / the C component = 100 / 0.01 to 100/100 (mass ratio). Wherein the C component is dispersed in a colloidal form, and the average particle size measured by the following average particle size measurement method is 0.01 to 100 μm. Agent.
Component A: containing 50 to 100% by mass of mineral oil and 0 to 50% by mass (total 100% by mass) of silicone oil and / or ester oil, and a viscosity at 25 ° C. of 2 × 10 ⁻⁶ to 1000 × 10 ⁻⁶ m ² / s liquid.
Component B: One or two or more selected from a nitrogen-containing compound represented by the following chemical formula 1, a nitrogen-containing compound represented by the chemical formula 2, a nitrogen-containing compound represented by the chemical formula 3 and a nitrogen-containing compound represented by the chemical formula 4.

{In Chemical Formulas 1 through 4,
R ^{1 to} R ⁶ : a residue obtained by removing one terminal hydrogen atom from a polyolefin having a number average molecular weight of 200 to 8000 X ^{1 to} X ⁴ : an alkylene group having 2 to 6 carbon atoms Y ¹ , Y ² : carbon number 1 -20 alkyl group, alkenyl group having 1-20 carbon atoms, hydroxyalkyl group having 1-20 carbon atoms, or hydrogen atom (however, when p = 0 or r = 0, the hydrogen atom is excluded)
p to s: integer of 0 to 10}
Component C: One or two or more solid fine particles selected from silicon oxide, the following metal atom oxide, the following metal atom carbonate and the following metal atom salt of a fatty acid having 12 to 22 carbon atoms Atom: Sodium, magnesium, calcium, barium, zinc, titanium, aluminum Measuring method of average particle diameter: Polypropylene having a viscosity of 10 × 10 ⁻⁶ m ² / s at 25 ° C. Using a mixed solution of 1/1 (mass ratio) of dimethylsiloxane and mineral oil, dilute so that the concentration of component C in the additive-type elastic fiber modifier is 1000 mg / L. A method of measuring a volume-based average particle diameter by using a laser diffraction particle size distribution measuring apparatus at a liquid temperature of 25 ° C.   The additive type elastic fiber modifier according to claim 1, which is contained at a ratio of A component / B component = 100 / 0.01 to 100/20 (mass ratio).   The additive-type elastic fiber modifier according to claim 1 or 2, which is contained in a ratio of the sum of component A and component B / component C = 100 / 0.01 to 100/50 (mass ratio).   The component A contains 70 to 100% by mass of mineral oil and 0 to 30% by mass (100% by mass in total) of silicone oil and / or ester oil. Additive fiber modifiers according to one of the items. The modifier for additive elastic fibers according to any one of claims 1 to 4, wherein the component A has a viscosity at 25 ° C of 2 x 10 ^{-6 to} 100 x 10 ^-6 m ² / s. B component, of 1 of X ¹ to X ⁴ are additive-type elastic fiber of any one of the preceding of claims 1 to 5 is of the case where an alkylene group having 2 to 4 carbon atoms in the 4 Modifier. When B component is Y ¹ and Y ^{2 in} Chemical Formula 1 and Chemical Formula 3 are an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, a hydroxyalkyl group having 1 to 12 carbon atoms, or a hydrogen atom The additive-type elastic fiber modifier according to any one of claims 1 to 6.   The modifier for additive-type elastic fibers according to any one of claims 1 to 7, wherein the component B is one in which p to s in chemical formulas 1 to 4 are integers of 1 to 6. The component B is ^one in which R ^{1 to} R ^{6 in} Chemical Formula 1 to Chemical Formula 4 are residues obtained by removing one terminal hydrogen atom from a polyolefin having a number average molecular weight of 500 to 5,000. The modifier for additive-type elastic fibers according to any one of the above.   The additive for elastic fibers according to any one of claims 1 to 9, wherein the component B is a nitrogen-containing compound represented by Chemical Formula 1 and / or a nitrogen-containing compound represented by Chemical Formula 2.   The additive elastic fiber modifier according to any one of claims 1 to 10, wherein the component C is a magnesium salt of a fatty acid having 12 to 22 carbon atoms and / or a calcium salt of a fatty acid having 12 to 22 carbon atoms. .   12. The additive elastic fiber modifier according to any one of claims 1 to 11, having an average particle size of 0.1 to 30 [mu] m.   A method for producing an elastic fiber, comprising spinning a spinning solution obtained by adding the modifier for additive type elastic fiber according to any one of claims 1 to 12 to a spinning solution of the elastic fiber.   The method for producing an elastic fiber according to claim 13, wherein the spinning solution is dry-spun.   An elastic fiber obtained by the method for producing an elastic fiber according to claim 13 or 14.   The elastic fiber according to claim 15, wherein the elastic fiber is a polyurethane-based elastic fiber.