JP2009084765A - Tape - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a product generating no imperfect dyeing and have excellent deep color and appearance quality, and high fastness, in the product produced by dyeing a tape by an acid dye homochromy test, measuring color of a polyurethane elastic fiber and an acid dye dyeable fiber, respectively, to specify K/S and ΔE* and degree of contamination, and performing finish dyeing under a product dyeing condition, and provide the tape using a polyurethane elastic fiber having high fastness. <P>SOLUTION: The tape is prepared by interlacingly knitting the polyurethane fiber and an acid dye-dyeable fiber. In the tape, the difference of K/S of the polyurethane elastic fiber and that of the acid dye dyeable type fiber is 10 or less, ΔE* of the polyurethane elastic fiber and that of the acid dye dyeable type fiber are 30 or less and the degree of contamination is 3.5 degree or more, when the tape is colored by the acid dye homochromy test and measured the color of the polyurethane elastic fiber and the acid dye dyeable fiber, respectively. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a tape using polyurethane elastic fibers. More specifically, a tape obtained by using a composite yarn combining polyurethane elastic fiber and acid dyeable fiber, or a tape combining polyurethane fiber alone and acid dyeable fiber, or polyurethane elastic fiber and acid dye. When a polyurethane elastic fiber is exposed in a tape combined with a composite yarn combined with a dyeable fiber and other fibers, or a tape combined with a polyurethane fiber alone, an acid dyeable fiber and another fiber, the color becomes uneven. The present invention relates to a tape having excellent color fastness and appearance quality, and further having high fastness.

  As a result of improving the feeling of wear by imparting stretch properties to the tape, the number of products in which polyurethane fibers are combined with the tape is increasing, and some products are becoming essential. However, polyurethane elastic fibers are acid dye-dyeable fibers because there are no effective dyeing seats for acid dyes in the constituent polyurethane polymer or polyurethane urea polymer (hereinafter referred to as polyurethane polymer) molecules. When dyeing a tape knitted with acid dyes, it is not possible to ensure the same level of dyeing as acid dye-dyeable fibers, and when the fabric is stretched and the polyurethane elastic fibers are exposed, the mottle is different There was a problem that blindness was visible. Further, since the polyurethane elastic fiber is only contaminated at the time of dyeing, it is liable to be discolored by washing or the like, which ultimately causes the product quality to deteriorate. In particular, this tendency is prominent in dark products such as black, which has been a big problem.

In order to solve these problems, a method of incorporating a tertiary nitrogen atom in the molecular chain of the polyurethane polymer is known (see Patent Documents 1 to 4 and Non-Patent Document 1). In addition, it is difficult not only to achieve the same deep dyeing property as that of the polyamide fiber, but also there is a problem that the physical properties of the polyurethane elastic fiber are lowered in some cases.
On the other hand, although a method for mixing a dyeability improver that binds to an acid dye with a polyurethane polymer has been proposed (see Patent Documents 5 to 7), it is possible to obtain a material that achieves deep dyeing and high wash fastness in a tape. It is not done.
In addition, so-called original yarns in which the polyurethane itself is colored have been developed (see Patent Document 8), but they cannot deal with various hues and have limited uses.

Furthermore, a method for improving the deep dyeing property by adding a polymer containing a maleimide structure having tertiary nitrogen as a dyeing improver has been developed (see Patent Document 9). One unreacted component of diamine may remain in the polymer, and the polyurethane elastic fiber to which this polymer is added loses its fastness and becomes stained with nylon after being dyed and washed with a nylon blanket It was found to cause. It was also found that this agent may cause coloring and gelation due to aging. This coloring and gelation affect the color of the fiber and the spinning stability.
Japanese Examined Patent Publication No. 39-23097 Japanese Examined Patent Publication No. 47-51645 Japanese Patent Publication No.59-12789 Japanese Examined Patent Publication No. 61-7212 JP-A 64-52889 JP 2000-313802 A JP 2001-40587 A Japanese Patent Laid-Open No. 2004-60062 Japanese Patent Publication No. 3-6177 Journal of Japanese Society of Rheology, 2001, Vol. 29, P191

  In view of the problems of the prior art, the object of the present invention is to use a polyurethane elastic fiber. The present invention also provides a tape having excellent appearance quality and higher fastness.

As a result of intensive studies on the above problems, the present inventor has dyed the tape production machine with a specific acid dye, and measured the polyurethane elastic fiber and the acid dye-dyeable fiber, respectively. By specifying the K / S difference and ΔE ^* of dye-dyeable fibers and setting the degree of contamination to be 3.5 or higher, there is no discoloration in the dyed product, and deep color In addition, the present inventors have found that a tape having excellent appearance quality and higher fastness can be obtained.

The invention claimed in the present application is as follows.
(1) When a polyurethane elastic fiber and an acid dye-dyeable fiber are used, and the polyurethane elastic fiber and the acid dye-dyeable fiber dyed by an acid dye color matching test are respectively measured The difference in K / S between the polyurethane elastic fiber and the acid dye-dyeable fiber is 10 or less, ΔE ^* between the polyurethane elastic fiber and the acid dye-dyeable fiber is 30 or less, and the degree of contamination is 3 A tape characterized by being grade 5 or higher.
(2) Polyurethane elastic fiber containing 0.2% by weight to 10% by weight of a polymer having a maleimide structure composed of an isobutylene unit represented by the following formula (I) and a maleimide unit represented by the following formula (II) The tape according to (1) above, wherein the tape is used.

(In the formula, R ¹ represents a linear or branched alkylene group having 2 to 6 carbon atoms, and R ² and R ³ may be the same or different, and each linear or branched group having 1 to 6 carbon atoms. Represents an alkyl group)
(3) Polyurethane elastic fibers having a dyeing seat for acid dyes of 7.0 × 10 ⁻³ mmol equivalent or more and 3.5 × 10 ⁻¹ mmol equivalent or less per 1 g of fiber are used ( The tape according to 1) or (2).
(4) The above-mentioned (2), wherein the polymer having a maleimide structure has a weight average molecular weight Mw of 80,000 to 150,000 and Mw / Mn (Mn is a number average molecular weight) of 3.5 or less. The tape described.
(5) The tape according to (2) or (4) above, wherein the 50% dimethylacetamide solution of the polymer having a maleimide structure has a shear viscosity of 80 to 300 poise.

  According to the present invention, there is no discoloration in a tape using a polyurethane elastic fiber and an acid dye-dyeable fiber alone, and a composite tape of a polyurethane elastic fiber and other fibers, and deep color and appearance. A tape having excellent quality and higher fastness can be obtained.

The present invention will be specifically described below.
The tape of the present invention is made of polyurethane elastic fiber and acid dyeable fiber. Examples of acid dyeable fibers include known polyamide fibers such as nylon 6 fibers and nylon 66 fibers, silk, wool, and animal hair. In addition, other materials than the acid dye-dyeable fiber can be further mixed in accordance with the purpose of use. The type, form, and fineness of the multi-material may be selected as appropriate and is not particularly limited. Examples include natural fibers such as cotton and hemp, regenerated cellulose fibers such as cupra rayon and viscose rayon, semi-synthetic fibers such as specific cellulose (trade name Tencel) and acetate rayon, and synthetic fibers such as polyester.

The form of the tape is conventionally known, for example, an assembled tape, a woven tape, a knitted tape, a round tape, a lace tape, or the like.
The tape of the present invention is characterized in that the difference in K / S between a polyurethane elastic fiber and an acid dye-dyeable fiber when dyed by an acid dye color matching test described later is 10 or less. If the difference in K / S exceeds 10, the apparent dyeing density difference between the polyurethane elastic fiber and the acid dyeable fiber is large, and the dyeing density of the polyurethane elastic fiber is low. Absent.
The tape of the present invention is characterized in that ΔE ^* of the polyurethane elastic fiber and the acid dye-dyeable fiber when dyed by the same acid dye color matching test is 30 or less. Preferably it is 20 or less. When ΔE ^* exceeds 30, the hue difference between the polyurethane elastic fiber and the acid dyeable fiber is large, which is not preferable.

Furthermore, the tape of the present invention is characterized in that the degree of contamination due to washing fastness (JIS L0844 A2 method) when it is dyed by the same acid dye color matching test is 3.5 or higher. If it is less than 3.5 grade, it causes contamination of other fabrics due to discoloration during washing, which is not preferable. Here, the contamination degree evaluation refers to the degree of contamination of the acid dye-dyeable fiber.
Such a tape having the characteristics of the present invention can be suitably obtained by using a polyurethane elastic fiber containing a polymer having a maleimide structure.

The polymer having a maleimide structure used in the present invention includes an isobutylene unit represented by the following formula (I) and the following formula (II) (wherein R ¹ is a linear or branched alkylene group having 2 to 6 carbon atoms. R ² and R ³ may be the same or different and each represents a straight or branched alkyl group having 1 to 6 carbon atoms), and is represented by isobutylene. Those in which units and maleimide units are alternately repeated are preferred.

  The polymer having a maleimide structure in the present invention includes a polymer comprising an isobutylene unit represented by the following formula (I) and a maleic anhydride unit represented by the following formula (III), and a diamine represented by the following formula (IV). Can be easily obtained by a dehydration condensation reaction. Polymers consisting of isobutylene and maleic anhydride can be produced in different ratios depending on the polymerization method and the monomer ratio, but the ratio of the two is alternately 1 from the viewpoint of ease of production and cost. Copolymerized polymers are preferred, and examples include Isoban 04 (manufactured by Kuraray Co., Ltd.).

  The diamine used in forming the maleimide may be any diamine that satisfies the above formula (II), for example, 2-dimethylaminoethylamine, 2-diethylaminoethylamine, 2-di-n-. Propylaminoethylamine, 2-diisopropylaminoethylamine, 2-di-n-butylaminoethylamine, 2-diisobutylaminoethylamine, 2-di-tert-butylaminoethylamine, 2-di-n-pentylaminoethylamine, 2-di- n-hexylaminoethylamine, 3-dimethylaminopropylamine, 3-diethylaminopropylamine, 3-di-n-propylaminopropylamine, 3-diisopropylaminopropylamine, 3-di-n-butylaminopropylamine, 3- Diiso Tylaminopropylamine, 3-di-tert-butylaminopropylamine, 3-di-n-pentylaminopropylamine, 3-di-n-hexylaminopropylamine, 4-dimethylaminobutylamine, 4-diethylaminobutylamine, 4 -Di-n-propylaminobutylamine, 4-diisopropylaminobutylamine, 4-di-n-butylaminobutylamine, 4-diisobutylaminobutylamine, 4-di-tert-butylaminobutylamine, 4-di-n-pentylaminobutylamine 4-di-n-hexylaminobutylamine, 2-dimethylamino-2-methylpropylamine, 2-diethylamino-2-methylpropylamine, 2-di-n-propylamino-2-methylpropylamine, 2-diisopropyl Ami 2-methylpropylamine, 2-di-n-butylamino-2-methylpropylamine, 2-diisobutylamino-2-methylpropylamine, 2-di-tert-butylamino-2-methylpropylamine, 2- Di-n-pentylamino-2-methylpropylamine, 2-di-n-hexylamino-2-methylpropylamine, 2-dimethylamino-1,1-dimethylethylamine, 2-diethylamino-1,1-dimethylethylamine 2-di-n-propylamino-1,1-dimethylethylamine, 2-diisopropylamino-1,1-dimethylethylamine, 2-di-n-butylamino-1,1-dimethylethylamine, 2-diisobutylamino- 1,1-dimethylethylamine, 2-di-tert-butylamino-1,1-dimethyl Ruethylamine, 2-di-n-pentylamino-1,1-dimethylethylamine, 2-di-n-hexylamino-1,1-dimethylethylamine, 5-dimethylaminopentylamine, 5-diethylaminopentylamine, 5- Di-n-propylaminopentylamine, 5-diisopropylaminopentylamine, 5-di-n-butylaminopentylamine, 5-diisobutylaminopentylamine, 5-di-tert-butylaminopentylamine, 5-di-n -Pentylaminopentylamine, 5-di-n-hexylaminopentylamine, 3-dimethylamino-2,2-dimethylpropylamine, 3-diethylamino-2,2-dimethylpropylamine, 3-di-n-propylamino -2,2-dimethylpropylamine, 3-diisopropyl Pyramino-2,2-dimethylpropylamine, 3-di-n-butylamino-2,2-dimethylpropylamine, 3-diisobutylamino-2,2-dimethylpropylamine, 3-di-tert-butylamino-2 , 2-dimethylpropylamine, 3-di-n-pentylamino-2,2-dimethylpropylamine, 3-di-n-hexylamino-2,2-dimethylpropylamine, 6-dimethylaminohexylamine, 6- Diethylaminohexylamine, 6-di-n-propylaminohexylamine, 6-diisopropylaminohexylamine, 6-di-n-butylaminohexylamine, 6-diisobutylaminohexylamine, 6-di-tert-butylaminohexylamine 6-di-n-pentylaminohexylamine, 6-di n- hexylamino-hexylamine or mixtures thereof and the like are preferable, among them, 2-diethylaminoethyl amine, 3-dibutyl aminopropyl amine or 3-diethylamino-propylamine is particularly preferred.

  The weight average molecular weight Mw of the polymer having a maleimide structure contained in the polyurethane elastic fiber used in the tape of the present invention is preferably 80,000 to 150,000, and Mw / Mn (Mn is the number average molecular weight) is 3. .5 or less is preferable. More preferably, Mw is 90,000 to 120,000, and Mw / Mn is 3.0 or less. If the molecular weight is too low, the polymer will bleed out to the surface and will easily fall off. Conversely, if the molecular weight is too high, the polymer will be difficult to uniformly disperse in the spinning dope. Even when the molecular weight distribution is too wide, a phenomenon similar to the above may occur due to some low molecular weight components or high molecular weight components. Although the molecular weight described here will be described in detail later, it is a molecular weight in terms of PMMA and can be determined by GPC (gel permeation chromatography).

  The shear viscosity of the polymer having a maleimide structure in the present invention is preferably in the range of 80 to 300 poises, more preferably in the range of 90 to 200 poises when converted to a 50% dimethylacetamide solution. If the shear viscosity is within this range, gelation does not occur, so the resulting knitted fabric is excellent in fastness, and contamination of the white fabric when washed with an acid dye-dyed fiber white fabric after dyeing is suppressed. The In addition, there is little influence on the color change and spinning stability of the fiber due to coloring and gelation due to changes in the agent over time. The polymer having a maleimide structure having such shear viscosity is obtained by reducing the molar equivalent of the diamine, which is another raw material, to the polymer consisting of the raw material, isobutylene and maleic anhydride, Can be suitably obtained by reducing the diamine residue of the raw material by improving the solvent by distilling it off under reduced pressure. Although the shear viscosity described here will be described in detail later, it can be measured with an E-type viscometer.

By adding 0.2% to 10% by weight of the polymer containing the maleimide structure to the polyurethane polymer, the dyeability and fastness of the polyurethane elastic fiber can be increased. More preferably, it is 0.5 to 10% by weight. If the amount is less than 0.2% by weight, sufficient dyeing performance is not exhibited, and if it exceeds 10% by weight, the overdyeing is excessively caused, resulting in the occurrence of blinding and further deterioration of fastness.
In addition, the polyurethane elastic fiber used in the tape of the present invention contains a polymer having a specific maleimide structure obtained by reducing the diamine residue derived from the raw material by improving the reaction conditions and the processing conditions as described above. Therefore, it maintains a sufficient darkness even after washing and is excellent in fastness to washing.

The polyurethane elastic fiber used in the tape of the present invention has a dyeing seat for acid dyes by adding a polymer containing a maleimide structure. The number of dyed seats is preferably 7.0 × 10 ⁻³ mmol equivalent or more and 3.5 × 10 ⁻¹ mmol equivalent or less per 1 g of polyurethane elastic fiber. The dyeing seat in this case is synonymous with an amine moiety having basicity that can be titrated with an acid such as hydrochloric acid.

  The polyurethane polymer used in the present invention, for example, reacts a polymer glycol having a number average molecular weight of 600 to 5000 with an organic diisocyanate to synthesize a urethane intermediate polymer that becomes a soft segment, and then forms a hard segment with a chain extender. It can manufacture by using well-known techniques, such as superposing | polymerizing and terminal-blocking with a terminal stopper. When a low molecular diol is used as a chain extender, a polyurethane polymer whose hard segment is a urethane bond can be obtained, and when a bifunctional amine is used, a polyurethane polymer whose hard segment is a urea bond can be obtained.

  Examples of the polymer glycol include, for example, homopolyether diols such as polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol and polyoxypentamethylene glycol, and two or more oxyalkylenes having 2 to 6 carbon atoms. Copolymerized polyether diol, adipic acid, sebacic acid, maleic acid, itaconic acid, azelaic acid and malonic acid and one or more dibasic acids and ethylene glycol, 1,2-propylene glycol, 1,3 -Propylene glycol, 2,2-dimethyl-1,3-propanediol, 1,4-butanediol, 1,3-butanediol, hexamethylene glycol, diethylene glycol, 1,10-decanediol, 1,3-dimethylol Polylactone diols such as polyester diol, polyester amide diol, polyester ether diol, poly-ε-caprolactone diol and polyvalerolactone diol obtained from one or more of glycols such as rhohexane and 1,4-dimethylolcyclohexane , Polycarbonate diol, polyacryl diol, polythioether diol, polythioester diol, or a copolymer or mixture of these diols.

  Examples of the organic diisocyanate include methylene-bis (4-phenylisocyanate), methylene-bis (3-methyl-4-phenylisocyanate), 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m- and p-xylylene diisocyanate, α, α, α ′, α′-tetramethyl-xylylene diisocyanate, m- and p-phenylene diisocyanate, 4,4′-dimethyl-1,3-xylylene diisocyanate, 1-alkylphenylene -2,4 and 2,6-diisocyanate, 3- (α-isocyanatoethyl) phenyl isocyanate, 2,6-diethylphenylene-1,4-diisocyanate, diphenyl-dimethylmethane-4,4-diisocyanate, diphenyl ether-4, 4'-Diisocy Anate, naphthylene-1,5-diisocyanate, 1,6-hexamethylene diisocyanate, methylene-bis (4-cyclohexylisocyanate), 1,3- and 1,4-cyclohexylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, penta Examples include methylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, or a mixture thereof.

  Examples of the chain extender having a polyfunctional active hydrogen atom include, for example, hydrazine, polyhydrazine, an amino group having a straight or branched aliphatic, alicyclic or aromatic active hydrogen having 2 to 10 carbon atoms. Diamines such as ethylenediamine, 1,2-propylenediamine and diamines having a urea group described in JP-A-5-155841, hydroxylamine, water, and low molecular weight glycols such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 2,2-dimethyl-1,3-propanediol, 1,4-butanediol, 1,3-butanediol, hexamethylene glycol, diethylene glycol, 1,10 -Decanediol, 1,3-dimethylolcyclohexane Beauty 1,4-dimethylol cyclohexane, and the like can be used. Preferred are ethylenediamine and 1,2-propylenediamine.

Examples of the terminal terminator having a monofunctional active hydrogen atom include dialkylamines such as diethylamine and alkyl alcohols such as ethanol. These chain extenders and end terminators may be used alone or in combination of two or more.
In addition to the polymer containing the maleimide structure of the present invention, this polyurethane-based polymer includes other compounds usually used for polyurethane elastic fibers, such as ultraviolet absorbers, antioxidants, light stabilizers, chlorine embrittlers, Gas stabilizers, colorants, matting agents and fillers may be added.
The polyurethane polymer thus obtained can be formed into a fiber shape by known dry spinning, wet spinning or melt spinning to produce polyurethane elastic fibers.

  Polyurethane elastic fiber obtained, polydimethylsiloxane, polyester-modified silicon, polyether-modified silicon, amino-modified silicon, mineral oil, mineral fine particles such as silica, colloidal alumina and talc, higher fatty acid metal salt powder such as stearic acid Oils such as solid waxes at room temperature such as magnesium and calcium stearate, higher aliphatic carboxylic acids, higher aliphatic alcohols, paraffin and polyethylene may be applied singly or optionally in combination.

  When the tape of the present invention is dyed with an acid dye, it has good color developability and fastness to washing, and can prevent eye peeling. The acid dye-dyeable fiber and the polyurethane elastic fiber can be mixed using either a polyurethane elastic fiber as a bare yarn, a method of mixing with an acid dye-dyeable fiber, or a method of using it as a composite yarn such as a coated elastic fiber. good. In addition, other materials that are further mixed in addition to the acid dyeable fiber can also be used as a yarn as it is or as a composite yarn with an elastic fiber.

The form of the acid dye-dyeable fiber and other fibers may be either a filament yarn or a spun yarn. Known yarn processing such as false twisted yarn and combined yarn processing may be performed, or a composite of these may be used. Examples of the composite method of polyurethane elastic fibers include aligning yarn, air covering, covering, combined yarn twisting, and the like. The composite may be not only one type of method but also a plurality of combinations. The number of twists and the like may be the setting of the number of twists usually performed.
The presetting conditions, sewing conditions, dyeing finishing conditions, and final setting conditions of the tape of the present invention are not particularly limited and may be appropriately selected. At the dyeing stage, functional processing such as antibacterial processing, deodorization processing, and ultraviolet absorption processing, and resin processing or the like as post-processing can be applied as necessary.

The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. The measured values in Examples and the like are determined by the following measurement methods.
(1) Acid Dye Same Color Test A tape in which the polyurethane elastic fiber of the present invention and the acid dye dyeable fiber were mixed was dyed and set under the following dyeing conditions using a rubber tape continuous dyeing machine. First, the tape was dyed with 1% owf of raw acid half-milling dye (Telon BLUE A2R; manufactured by DyStar), leveling agent (SeraGalN-FS; manufactured by DyStar) 0.6% owf, and ammonium sulfate 4.0% owf. After impregnating with the liquid, it was padded, steamed (100 ° C. × 4 minutes), passed through four washing layers, and then dried with a hot roller.

The tape was disassembled into polyurethane elastic fibers and acid dyeable fibers, and the surface dyeing concentrations K / S and ΔE ^* of the respective fibers were measured by the following methods. Separately, the degree of contamination of the dyed tape was measured by a washing fastness evaluation method according to JIS L0844 A2. Here, as a white cloth used for evaluation of the degree of contamination, a cloth made of polyamide which is an acid dye-dyeable fiber was used.

K / S: With a spectrophotometer COLOR-EYE 7000A manufactured by Gretag Macbeth Co., the color of polyurethane elastic fiber and acid dyeable fiber is measured, and the respective surface dyeing density K / S is obtained, and the difference in K / S Was determined by the following formula.
K / S difference = (K / S of acid dyeable fiber) − (K / S of polyurethane elastic fiber)
ΔE ^* : Polyurethane elastic fibers and acid dye-dyeable fibers were measured with a spectroscopic color difference meter SQ-2000 (standard light source C, 2-degree visual field) manufactured by Nippon Denshoku Industries Co., Ltd. The lightness index L ^* and chromaticness indices a ^* and b ^* were determined using the CIELAB color system. The lightness index and chromaticness index of polyurethane elastic fiber and acid dyeable fiber are (L ₁ ^* , a ₁ ^* , b ₁ ^* ) and (L ₂ ^* , a ₂ ^* , b ₂ ^* ), respectively. ΔE ^* was determined by the following formula (V).
ΔE ^* = √ ((L ₂ ^* −L ₁ ^* ) ² + (a ₂ ^* −a ₁ ^* ) ² + (b ₂ ^* −b ₁ ^* ) ² ) (V)

(2) Measurement of dyeing seat Approximately 200 mg of a 50% dimethylacetamide solution of a polymer having a maleimide structure is accurately weighed and dissolved in 10 mL of dimethylacetamide, and bromphenol blue is used as an indicator to prepare a hydrochloric acid-methanol solution (0.16 mol). / L), neutralization titration was performed, and the amine value in 1 g of the polymer was measured. The number of dyed seats per gram of polyurethane elastic fiber was calculated from the amount of polymer having a maleimide structure in the spun polymer and the amine value.

(3) Measurement of weight average molecular weight and molecular weight distribution Using an eluent in which LiBr was dissolved in dimethylacetamide so as to have a concentration of 10 mmol / L, a polymer having a maleimide structure was adjusted to 1.0 mg / mL. Measurement was performed by GPC as a sample.
Measurement conditions Data processing Tosoh GPC-8020
Two columns TSKgel α-M (7.8 mm x 30 cm) Oven 60 ° C
Eluent Dimethylacetamide (LiBr 10mmol / L) 1.0m L / min
Sample volume 200μL
Detector RI
Calibration curve PMMA

(4) Measurement of shear viscosity The shear viscosity was measured with an E-type viscometer (RE105U manufactured by Toki Sangyo Co., Ltd.).
Measurement conditions Temperature 30 ℃
Sample volume 0.5mL
Rotor 3 ° × R14
10 rpm

(5) Opening The tape that had been dyed and finished under the product dyeing conditions was pulled and visually judged to determine the state of openness from grades 1 to 4.
4th grade: Level where dyeing shade difference between polyurethane elastic fiber and acid dyeable fiber is not recognized at all 3rd grade: Polyurethane elastic fiber is sufficiently dyed, but there is little difference in shade from acid dyeable fiber Level 2: Polyurethane elastic fibers are dyed, but there is a large difference in density with acid dyeable fibers, and polyurethane elastic fibers are clearly recognizable. Level 1: Open and clearly visible polyurethane elastic fibers Able to recognize that it is almost unstained

(6) Same color properties of dyed finish tape A tape that had been dyed and finished under product dyeing conditions was pulled and visually judged to determine the hue difference between the polyurethane elastic fiber and the acid dye-dyeable fiber from ○ to ×.
○: Level at which the hue difference between the polyurethane elastic fiber and acid dyeable fiber is not recognized at all ×: Level at which the polyurethane elastic fiber and acid dyeable fiber are clearly different (7) Fastness of the dyed finish tape Product dyeing The fastness to washing according to JIS L0844 A2 method was evaluated for the tape dyed and finished under the conditions. Here, a polyamide white cloth, which is an acid dye-dyeable fiber, was used as the attached white cloth, and the degree of contamination was defined as the fastness to washing.

[Example 1]
40 g of alternating isobutylene-maleic anhydride copolymer (Kuraray Isoban 04) having an average molecular weight of about 60,000, 33.8 g of diethylaminopropylamine, and 160 g of dimethylacetamide were mixed at 50 ° C. under a nitrogen atmosphere. The mixture was stirred for 1 hour and at 100 ° C. for 1 hour, and then heated for 4 hours while distilling off the water formed under reflux at 180 ° C. Residual volatiles were distilled off under reduced pressure, and the resulting polymer was dissolved in dimethylacetamide to give a 50% solution. The obtained polymer had a weight average molecular weight Mw = 1.0 × 10 ⁵ and a molecular weight distribution Mw / Mn = 2.7.

A polyurethane prepolymer having isocyanate groups at both ends is reacted with 1,500 g of polytetramethylene ether glycol having an average molecular weight of 1,800 and 312 g of 4,4′-diphenylmethane diisocyanate while stirring at 60 ° C. for 90 minutes in a nitrogen gas stream. A polymer was obtained. Next, after cooling to room temperature, 2,700 g of dimethylacetamide was added and dissolved to prepare a polyurethane prepolymer solution.
23.4 g of ethylenediamine and 3.7 g of diethylamine were dissolved in 1,570 g of dry dimethylacetamide and added to the prepolymer solution at room temperature to obtain a polyurethane polymer solution having a viscosity of 2,200 poise (30 ° C.). .

In this polyurethane polymer solution, 1.0% by weight of an isobutylene adduct of a polyaddition product of p-cresol and dicyclopentadiene, 0.4% of Sumilizer GA-80 (manufactured by Sumitomo Chemical Co., Ltd.) was added to the polyurethane solid content. Wt%, 2- (2H-benzotriazol-2-yl) -4,6-bis (2-phenylpropan-2-yl) phenol 0.2 wt%, hydrotalcite 5.0 wt% and preparation 1.0% by weight of the polymer having the maleimide structure was mixed to prepare a spinning dope.
This spinning dope was dry-spun at a spinning speed of 500 m / min and a hot air temperature of 325 ° C. to produce 940 dtex / 72 filament polyurethane elastic fiber.

Using the above-obtained polyurethane elastic fiber bare yarn 940 dtex and nylon 6 processed yarn 78 dtex / 24 filament yarn, create a 10 mm wide tape production machine with a Cometz knitting machine, and set with a normal continuous dyeing machine The dyeing finish tape was obtained. Table 1 shows the evaluation results of the tape production machine and the dyed finish tape.
<Dyeing method>
Acid half-milling dye: DyStar
Telon Red A2R; 0.14% owf
Telon Yellow A2R; 0.16% owf
Telon Blue A2R; 0.12% owf
Leveling agent: SeraGalN-FS; 0.5% owf manufactured by DyStar
pH slide agent: ammonium sulfate 4.0% owf
Tape speed 5m / min
Steaming 100 ° C x 4 minutes <Soaping recipe>
Soaping agent: New Sunrex E; 2g / L made by Nikka Chemical
<Fixed recipe>
Fixing agent: HiFix SW-A; Dainippon Pharmaceutical 5% owf
Anti-scum agent: NWH201; Senka Co., Ltd. 1% owf
Adjust to pH 4-5 with sodium carbonate

[Example 2]
Spinning was carried out under the same conditions using the same spinning stock solution as in Example 1 except that the amount of the polymer having a maleimide structure was 2.0% by weight, and a 940 dtex polyurethane elastic fiber was obtained. . A tape production machine was prepared in the same manner as in Example 1, and dyeing and finishing were performed in the same manner to obtain a dyeing finish tape. Table 1 shows the evaluation results of the tape production machine and the dyed finish tape.

[Example 3]
Spinning was performed under the same conditions using the same spinning stock solution as in Example 1 except that the amount of the polymer having a maleimide structure was 4.0% by weight, and a 940 decitex polyurethane elastic fiber was obtained. . A tape production machine was prepared in the same manner as in Example 1, and dyeing and finishing were performed in the same manner to obtain a dyeing finish tape. Table 1 shows the evaluation results of the tape production machine and the dyed finish tape.

[Example 4]
The polyurethane elastic fiber bare yarn 940 dt obtained in Example 2 was stretched at Df = 3.5, and a nylon 678 dtex / 24 filament processed yarn was covered at 750 times / m as the warp, and the weft was nylon. Using a 78 dtex / 24 filament processed yarn, a raw tape machine was made by using a Mueller loom and dyeing was performed using a rubber continuous dyeing machine to obtain a dyed finish tape. Table 1 shows the evaluation results of the tape production machine and the dyed finish tape.
<Dyeing method>
Acid half-milling dye: DyStar
Telon Red A2R; 0.14% owf
Telon Yellow A2R; 0.16% owf
Telon Blue A2R; 0.12% owf
Leveling agent: SeraGalN-FS; 0.5% owf manufactured by DyStar
pH slide agent: ammonium sulfate 4.0% owf
Tape speed 5m / min
Steaming 100 ° C x 4 minutes <Soaping recipe>
Soaping agent: New Sunrex E; 2g / L made by Nikka Chemical
<Fixed recipe>
Fixing agent: HiFix SW-A; Dainippon Pharmaceutical 5% owf
Anti-scum agent: NWH201; Senka Co., Ltd. 1% owf
Adjust to pH 4-5 with sodium carbonate

[Comparative Example 1]
Spinning was carried out under the same conditions as in Example 1 except that no polymer having a maleimide structure was added. Spinning was performed under the same conditions as in Example 1 to obtain a 940 dtex polyurethane elastic fiber. A tape production machine was prepared in the same manner as in Example 1, and dyeing and finishing were performed in the same manner to obtain a dyeing finish tape. Table 1 shows the evaluation results of the tape production machine and the dyed finish tape.

[Comparative Example 2]
Spinning was carried out under the same conditions using the same spinning stock solution as in Example 1 except that the amount of the polymer having a maleimide structure was 15% by weight, to obtain a 940 dtex polyurethane elastic fiber. A tape production machine was prepared in the same manner as in Example 1, and dyeing and finishing were performed in the same manner to obtain a dyeing finish tape. Table 1 shows the evaluation results of the tape production machine and the dyed finish tape.

[Comparative Example 3]
Using a black original polyurethane elastic fiber made of Asahi Kasei Spandex Europe Co., Ltd. Dorlastane BL (trademark) 940 dtex, a tape production machine is prepared in the same manner as in Example 1, dyeing and finishing are performed in the same manner, and a dyeing finish tape is prepared. Obtained. Table 1 shows the evaluation results of the tape production machine and the dyed finish tape.

[Comparative Example 4]
Spinning was carried out under the same conditions as in Example 1 except that no polymer having a maleimide structure was added. Spinning was performed under the same conditions as in Example 1 to obtain a 940 dtex polyurethane elastic fiber. In the same manner as in Example 4, a tape production machine was prepared, and dyeing and finishing were performed in the same manner to obtain a dyeing finish tape. Table 1 shows the evaluation results of the tape production machine and the dyed finish tape.
From the results shown in Table 1, it can be seen that the tape of the present invention does not cause discoloration, is excellent in deep color and appearance quality, and has a higher fastness.

  The tape of the present invention has excellent deep color and appearance quality, and further high fastness when the fabric is stretched when worn and the polyurethane elastic fiber is exposed to cause the appearance of speckles with different colors. Have.

Claims (5)

Polyurethane obtained by measuring the color of polyurethane elastic fiber and acid dye-dyeable fiber when dyed by acid dye color matching test, using polyurethane elastic fiber and acid dye-dyeable fiber The difference in K / S between the elastic fiber and the acid dyeable fiber is 10 or less, the ΔE ^* between the polyurethane elastic fiber and the acid dyeable fiber is 30 or less, and the pollution degree is 3.5 grade. A tape characterized by the above. A polyurethane elastic fiber containing 0.2% by weight to 10% by weight of a polymer having a maleimide structure composed of an isobutylene unit represented by the following formula (I) and a maleimide unit represented by the following formula (II) is used. The tape according to claim 1, wherein

(In the formula, R ¹ represents a linear or branched alkylene group having 2 to 6 carbon atoms, and R ² and R ³ may be the same or different, and each linear or branched group having 1 to 6 carbon atoms. Represents an alkyl group) 3. A polyurethane elastic fiber having a dyeing seat for acid dyes of 7.0 × 10 ⁻³ millimole equivalent or more and 3.5 × 10 ⁻¹ millimole equivalent or less per 1 g of fiber is used. The tape described.   The tape according to claim 2, wherein the polymer having a maleimide structure has a weight average molecular weight Mw of 80,000 to 150,000, and Mw / Mn (Mn is a number average molecular weight) of 3.5 or less.   The tape according to claim 2 or 4, wherein the 50% dimethylacetamide solution of the polymer having a maleimide structure has a shear viscosity of 80 to 300 poise.