JP4667059B2 - Treatment agent for elastic fiber with less scattering and its elastic fiber - Google Patents

Description

  The present invention relates to a treatment agent for elastic fibers with less scattering and an elastic fiber treated with the treatment agent.

Japanese Unexamined Patent Publication (Kokai) No. 57-128276 describes an oil agent for polyurethane elastic fibers comprising polydiorganosiloxane and polyether-modified silicone. Japanese Patent Application Laid-Open No. 61-97471 describes an elastic agent for polyurethane elastic fibers comprising mineral oil or polydiorganosiloxane and amino-modified silicone.
JP-A-57-128276 JP 61-97471 A

Problems to be solved by the invention

Silicone oils, mineral oils, ester oils, and the like are used as base components for elastic fiber oils. Recently, the spinning speed for producing elastic fibers has been increased. For this reason, there is a problem that the amount of scattering of the oil agent increases as the spinning speed increases during oiling or in subsequent steps.
In addition, because of the recent demand for elastic fibers, the finer De has been developed, and there is a problem that threads are taken off by rollers and nozzles during oiling. To solve this problem, an oil agent component having a low viscosity is used. Also, the amount of oil spraying is increased.
Furthermore, when the oil agent viscosity decreases, the oil agent is likely to shift in Cheese, the difference in the amount of oil agent attached to the outer layer and the inner layer of the Cheese over time increases, and the smoothness of the thread changes in the Cheese inner and outer layers, When a knitted fabric is created, there is a problem that the knitted article position changes between the outer layer and the inner layer.

Means for solving the problem

The present invention relates to a styrene butadiene rubber, a butadiene rubber, an isoprene rubber, an EPM, an EPDM, an acrylonitrile butadiene rubber, a chloroprene rubber, a butyl rubber, a silicone rubber, and an olefin elastomer with respect to a base component composed of silicone oil, mineral oil and / or ester oil. , A processing agent for elastic fibers composed of 0.001 to 10% by weight of at least one selected from urethane elastomers, polyester elastomers, and polyamide elastomers. Preferably, it is a treatment agent for elastic fibers constituted by using 0.05 to 1% by weight.
Further, the elastic fiber of the present invention is characterized in that 0.1 to 15% by weight of the treatment agent is applied.

In the present invention, the base component is selected from ester oil, mineral oil, and silicone oil, and at least the following styrene butadiene rubber, butadiene rubber, isoprene rubber, EPM, EPDM, acrylonitrile butadiene rubber, chloroprene rubber, butyl rubber, acrylic rubber, silicone rubber (Silicon raw rubber, silicone rubber, amino silicone raw rubber, amino silicone rubber, etc.), rubbers such as fluorine rubber, and one or more thermoplastic elastomers such as olefin elastomer, urethane elastomer, polyester elastomer, polyamide elastomer It is necessary to contain.
The rubber and elastomer used in the present invention preferably have an average molecular weight in the range of 1,000 to 1,000,000, preferably 10,000 to 500,000.
The rubber and the elastomer may or may not have an active group such as a vinyl group, amino group, carboxyl group, or hydroxyl group at the terminal or side difference. The rubber and elastomer used in the present invention may be raw rubber or raw rubber obtained by cross-linking using a general cross-linking agent such as benzoyl peroxide. Further, the rubber and the elastomer referred to in the present invention are a metal catalyst or an organometallic catalyst containing elements such as Co, Ni, Al, Li, V, Zn, Mg, Pb, and Ti generally used for each polymer. Etc., a polymerization initiator, a polymerization accelerator, a polymerization inhibitor, a polymerization terminator, etc. may be used and synthesized by a general method such as emulsion polymerization or solution polymerization, or natural rubber may be used. Further, among the rubbers and elastomers referred to in the present invention, the composition ratio of those composed of a plurality of monomers is arbitrary.
The oil agent of the present invention preferably has a viscosity at 30 ° C. of ² to 50 mm ² / s, more preferably 5 to 15 mm ² / s. If the viscosity is less than 2 mm ² / s, volatilization of the oil agent may be a problem, and if it is greater than 50 mm ² / s, the wettability of the elastic fiber to the surface may be deteriorated.
When the treatment agent of the present invention is used, the scattering amount of the oil agent is reduced by 20% by weight or more, preferably 50% by weight or more. In addition, the difference in the amount of oil applied to the outer layer and inner layer of Cheese over time can be reduced, and the smoothness of the elastic fibers does not change due to the difference between the inner and outer layers of Cheese. Can be suppressed.

In addition, the treatment agent of the present invention includes conventionally known modified silicones (amino-modified silicones, alkyl-modified silicones, ester-modified silicones, polyether-modified silicones, carbites) in order to enhance smoothness, unwinding properties and antistatic effects. Nord modified silicone, carboxy modified silicone, mercapto modified silicone, phosphoric acid modified silicone, epoxy modified silicone,
Formula: R ₁ R ₂ R ₃ SiO _1/2 (wherein R ₁ , R ₂ , R ₃ are monovalent hydrocarbon groups)
An organopolysiloxane resin comprising a siloxane unit represented by formula: and a siloxane unit represented by formula: SiO ₂ , a formula: R ₁ R ₂ R ₃ SiO _1/2 (wherein R ₁ , R ₂ and R ₃ are monovalent) And a siloxane unit represented by the formula: SiO ₂ and a formula: R ₄ SiO _3/2 (wherein R ₄ is a monovalent hydrocarbon group.)
An organopolysiloxane resin composed of a siloxane unit represented by formula: R ₄ SiO _3/2 (wherein R ₄ is a monovalent hydrocarbon group), an organopolysiloxane resin composed of a siloxane unit represented by the formula: Ingredients usually used as a treatment agent for elastic fibers, such as a binder, an antistatic agent, an antioxidant, and an ultraviolet absorber, can be blended. In addition, the treatment agent of the present invention includes a higher fatty acid metal soap, a neutralized organic carboxylic acid organic amine, and an organic phosphate ester of an amino-modified silicone in order to enhance the smoothness, unwinding property and antistatic effect. Japanese, N, N′-substituted fatty acid bisamide, N, N′-substituted fatty acid diamide, and N-substituted fatty acid amide may be added in an amount of 0.01 to 5 parts by weight. As the higher fatty acid metal soap, known ones conventionally used for elastic fibers can be used, and Ca stearate, Mg stearate, Al stearate, Ba stearate, Zn stearate and the like are preferable.
The styrene butadiene rubber referred to in the present invention is a random copolymer of styrene and butadiene. Butadiene rubber is a polymer of butadiene. Isoprene rubber is a polymer of isoprene. EPM is a copolymer of ethylene and propylene. EPDM is a terpolymer of ethylene, propylene and diene. The acrylonitrile butadiene rubber is a copolymer of butadiene and acrylonitrile rubber, and may be a hydrogenated nitrile rubber in which only the double bond portion existing in the butadiene portion is selectively hydrogenated. Chloroprene rubber is a polymer of chloroprene. Butyl rubber is a polymer of isobutylene, and may be halogenated butyl rubber halogenated with chlorine, bromine or the like. The silicone rubber may be a cross-linked polydiorganosiloxane, or a raw silicone rubber that is not cross-linked. The olefin elastomer is a copolymer using polypropylene or polyethylene for the hard segment and ethylene, propylene rubber, butyl rubber or the like for the soft segment. The urethane elastomer is a polymer containing a urethane group, and is obtained by reacting a general diisocyanate such as 4,4′-diphenylmethane diisocyanate and a general glycol such as poly (oxyethylene) glycol. The polyester elastomer is a copolymer using an aromatic polyester as a hard segment and an aliphatic polyester, an aliphatic polyether or the like as a soft segment. The polyamide-based elastomer is a copolymer using polyamide for the hard segment and aliphatic polyester, aliphatic polyether or the like for the soft segment.

The treatment agent of the present invention is usually applied in an amount of 0.1 to 15% by weight with respect to the elastic fiber. If it is less than 0.1% by weight, the effect of the present invention is not sufficient, and if it exceeds 15% by weight, it is uneconomical. The elastic fiber of the present invention is a fiber having an elongation of 300% or more composed of polyurethane elastomer, polyurethane urea elastomer, polyetherester elastomer, polyethylene elastomer and the like.

The present invention will be specifically described below with reference to examples.
In addition, the characteristic of each oil agent in a specific example was evaluated according to the following method.

viscosity:
Using a Canon Fenceke viscometer, the kinematic viscosity of the sample solution at 30 ° C. was determined.

Roller static electricity:
In FIG. 1, the fiber cheese (1) to which the treatment agent is applied is set on the unwinding side of the unwinding speed ratio measuring machine, rotated at a peripheral speed of 50 m / min, and at 2 cm above the cheese, the Kasuga potential difference With the measuring device (2), the generated static electricity 1 hour after the start of rotation is measured.

Knitting tension:
In FIG. 2, the roller (9) attached to the U gauge (8) with the elastic yarn (4) vertically taken from the cheese (3) through the compensator (5), the roller (6), and the knitting needle (7). And connected to a speedometer (10) and a take-up roller (11). The rotational speed of the take-up roller is adjusted so that the traveling speed of the speedometer (10) becomes a constant speed (for example, 10 m / min, 100 m / min), and the knitting tension at that time is taken up by the take-up roller. Is measured with a U gauge (8), and the friction (g) between the fibers / knitting needles is measured. The generated static electricity is measured with a Kasuga-type potentiometer (12) at a distance of 1 cm from the running yarn.

Inter-fiber friction coefficient (F / Fμs):
In FIG. 3, a monofilament of elastic fiber to which a treatment agent has been applied is taken about 50 to 60 cm, a load T1 (13) is suspended at one end, and the other is attached to the U gauge (15) via a roller (14). The ends are pulled at a constant speed (for example, 3 cm / min), the secondary tension T2 at that time is measured with a U gauge (15), and the inter-fiber friction coefficient is obtained by Equation 1.
Coefficient of friction between fibers (F / F μs) = 1 / θ · ln (T2 / T1) Equation 1
(In Equation 1, θ = 2π, ln = natural logarithm, T1 is 1 g per 22 dtex)

Unwinding speed ratio:
In FIG. 4, the fiber cheese (16) to which the treatment agent is applied is set on the unwinding side of the unwinding speed ratio measuring machine, and the paper tube (17) is set on the winding side. After setting the winding speed to a constant speed, the rollers (18) and (19) are activated simultaneously. In this state, there is almost no tension on the yarn (20), so the yarn is stuck on the cheese and does not leave, so the unwinding point (21) is in the state shown in FIG. By changing the unwinding speed, the unwinding point (21) of the yarn (20) from the cheese changes, so the unwinding speed is set so that this point coincides with the contact point (22) between the cheese and the roller. The unraveling speed ratio is obtained by Equation 2. The smaller this value is, the better the unpacking property is.
Unwinding speed ratio (%) = (winding speed−unwinding speed) ÷ unwinding speed × 100 Equation 2

Measurement of the amount of oil attached Cheese is left in a temperature-controlled room at 20 ° C. and 65% RH for 3 months, 5 g of yarn is precisely weighed from the outer and inner layers, the oil is extracted with hexane, the yarn is dried and weighed accurately, and the weight We ask from decrease. The smaller the difference between the outer layer and the inner layer, the smaller the transfer of the oil agent in Cheese.

Oil dispersion measurement:
In FIG. 5, the scattered oil agent collector (25) has a spinning side diameter of 15 cm, a winding side diameter of 5 cm, and a length in the running yarn direction of 20 cm. The distance from the oiling nozzle (24) to the conical scattered oil collector (25) is 15 cm. The spun yarn (23) is passed through the oiling nozzle (24), passed through the scattered oil agent collector (25) and wound up. In this state, spinning was performed at a speed of 500 m / min while applying 6% by weight of the oil to 77 dtex fibers, and the weight of the oil collected in the scattered oil collector (25) after 10 minutes was precisely adjusted. Weigh. The weight at this time is defined as the amount of oil dispersion, and the smaller this value, the less oil dispersion.

Preparation of spinning dope:
A polytetramethylene ether glycol having a number average molecular weight of 1800 and 4,4′-diphenylmethane diisocyanate are reacted at a molar ratio of 1: 2, and then chain-extended using a 1,2-diaminopropane solution in dimethylformamide to obtain a polymer concentration of 27%. Of dimethylformamide was obtained. The concentration at 30 ° C. was 1700 mPaS.

Examples 1-10 and Comparative Examples 1-3
The polyurethane spinning dope was discharged into a N ₂ stream at 230 ° C. and dry-spun. While measuring the amount of scattering of the oil agent using the oil agent scattering measuring method described in FIG. 6% by weight was applied to a bobbin at a speed of 600 m / min to obtain 44 dtex monofilament cheese (wound amount 400 g), and the resulting cheese was left in an atmosphere of 35 ° C. and 50% RH for 48 hours. In addition, as an accelerated deterioration test, the obtained cheese was left in an atmosphere of 60 ° C. and 80% RH for 10 days, and then left in an atmosphere of 20 ° C. and 45% RH for 48 hours. These results are shown in Table 1.

The invention's effect

  By using the treatment agent of the present invention, the amount of splashing oil during or after oiling is maintained while maintaining stable antistaticity, good unwinding property and good smoothness to the elastic fiber. Can be reduced. In addition, after the manufacture of Cheese, it is possible to suppress the migration of the oil in Cheese with time.

  The schematic diagram explaining the measuring method of roller static electricity generation amount.   The schematic diagram explaining the measuring method of knitting tension | tensile_strength, and the measuring method of the amount of static electricity generation.   The schematic diagram explaining the measuring method of the friction coefficient between fibers.   The schematic diagram explaining the measuring method of unwinding speed ratio.   The schematic diagram explaining the measuring method of oil agent scattering amount at the time of oiling.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Cheese of elastic fiber 2 Kasuga type potential difference measuring device 3 Cheese of elastic fiber 4 Yarn 5 Compensation sweater 6 Roller 7 Knitting needle 8 U gauge 9 Roller 10 Speedometer 11 Take-up roller 12 Kasuga type potentiometer 13 Load 14 Roller 15 U gauge 16 Cheese 17 Winding paper tube 18 Roller 19 Roller 20 Traveling yarn 21 Unwinding point 22 Contact point of cheese and roller 23 Traveling yarn (spinning tower side)
24 Oiling nozzle 25 Scattering oil agent collector (conical type)
26 Traveling yarn (winding side)

Claims (2)

At least one base component selected from silicone oil, mineral oil and ester oil;
At least one selected from styrene butadiene rubber, butadiene rubber, isoprene rubber, EPM, EPDM, acrylonitrile butadiene rubber, chloroprene rubber, butyl rubber, olefin elastomer, urethane elastomer, polyester elastomer and polyamide elastomer with respect to the base component. An elastic fiber treatment agent containing 0.001 to 10% by weight.   An elastic fiber to which 0.1 to 15% by weight of the treatment agent according to claim 1 is applied.

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