JPH07119036A - Polyester fiber of improved light fastness - Google Patents

Abstract

PURPOSE:To obtain cationic dye-dyeable polyester fiber which can be deeply and brightly dyed with high light fastness. CONSTITUTION:The polyester fiber is dyed with at least one of cationic dyes and contains more than 0.01%, based on the fiber weight, of at least one of organic nickel complexes selected from the group of nickel p-toluenesulfonate, nickel dibutyldithiocarbamate, and nickel bis(thiobenzyl) and of an ultraviolet absorber, respectively.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to polyester fibers having improved lightfastness.

[0002]

2. Description of the Related Art Although polyester fibers have been expanded in their applications due to their excellent properties, the problems to be overcome are also increasing. For example, among sports applications, when there are many opportunities to wear it outdoors such as ski wear, marine wear, or caddy wear, UV-A light in the sunlight or UV-
It is known that the fading of the dye is much larger than in normal applications, because the B light reflects off snow or water and directly hits the fabric.

Further, the fading color tends to be more noticeable as the blended vivid color such as purple, which has recently become popular, and a fabric obtained by dyeing an ordinary polyester dyeable polyester fiber with a cationic dye cannot meet these needs at all. is the current situation.

In order to solve such a problem, Japanese Patent Laid-Open No. 60-
Japanese Patent No. 252785 discloses a method of adsorbing a light resistance improving agent such as an ultraviolet absorber or an antioxidant on a polyester fiber. However, since the light resistance improving agent has a large molecular structure, There is a problem that the diffusion is insufficient and the agent is likely to drop off.

On the other hand, when dyeing a polyester dyeable polyester fiber with a cationic dye by adding a nickel complex of 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, it is reported that the light fastness is improved ( Textile Research Journal, 8, P.697 ~ 703 (196
However, since the nickel complex has a bulky molecular structure, there is a problem that the hue is dull and the original sharpness of the cationic dye is lost.

[0006]

SUMMARY OF THE INVENTION The object of the present invention is to eliminate the above-mentioned problems of the prior art and to provide a cation which is dyed in a dark and vivid color and has a good fastness to light even when dyed with a blended vivid color. It is to provide a dye-dyeable polyester fiber.

[0007]

Means for Solving the Problems As a result of intensive studies conducted by the present inventors in order to achieve the above object, the cationic dyeable polyester fiber dyed with a cationic dye has an organic nickel having a compact molecular structure. It has been clarified that when the complex and the ultraviolet absorber are blended, a polyester fiber which is dyed clearly and has excellent fastness to light can be obtained.

Thus, according to the invention, a cationic dye-dyeable polyester fiber dyed with at least one cationic dye, consisting of nickel paratoluenesulfonate, nickel dibutyldithiocarbamate and nickel bisthiobenzyl. Provided is a polyester fiber having an improved light fastness, which comprises at least 0.01% of an organic nickel complex selected from the group and an ultraviolet absorber in an amount of 0.01% or more based on the weight of the fiber. It

The structure of the present invention will be described in detail below. The cationic dye-dyeable polyester fiber in the present invention comprises terephthalic acid as a main acid component and at least one glycol, preferably at least one alkylene glycol selected from ethylene glycol, trimethylene glycol and tetramethylene glycol. Polyester as the main glycol component, for isophthalic acid component containing a sulfonic acid metal base, for example, 5-sodium sulfoisophthalic acid or 5-tetrabutylphosphonium sulfoisophthalic acid copolymerized by a known method Stabilizers, antioxidants, flame retardants, antistatic agents, fluorescent colorants, catalysts, colorants, inorganic fine particles and the like may be added within a range that does not impair the object of the invention.

The shape of polyester fiber is filament,
Woolly processed yarn, spun yarn, and if necessary, polyester fibers other than cationic dye-dyeable polyester fibers or natural fibers such as cotton and wool, recycled fibers such as rayon, and polyethylene terephthalate polyester as hard segments, It may be used in the form of interwoven, interwoven, mixed fiber, mixed spinning, etc. with block copolymerized polyetherester elastic fibers having polyoxybutylene glycol-based polyester as a soft segment and other synthetic fibers.

The fineness of the polyester fiber is not particularly limited, but the effect of the present invention can be remarkably exhibited when applied to ultrafine fibers having a single fiber fineness of 0.5 denier or less.

The cationic dye used in the present invention is one that is soluble in water and is used for dyeing synthetic fibers such as cationic dye-dyeable polyester fibers and acrylic fibers, and is classified into the following two structural types. ing. Conjugate type cationic dyes Methine type, polymethine type, azamethine type, azo type, triazole azo type, thiazole azo type, benzothiazole azo type, triphenyl methane type, etc. Insulation type cationic dye azo type, anthraquinone type, etc.

The cationic dye has a pigment base molecular weight of 2
It is preferable to use one of 50 to 500. If the molecular weight is less than 250, thermal decomposition tends to occur, while if it exceeds 500, it becomes poorly soluble in water and stains are likely to occur.

Further, the thermal decomposition resistance of the cationic dye is
The residual dye ratio after treatment at 130 ° C for 60 minutes is at least 90.
% Or more is preferable. If the residual ratio of the dye is less than 90%, problems such as unclear hue occur.

In the present invention, at the time of dyeing a cationic dye dyeable polyester fiber with the above cationic dye, at least one selected from the group consisting of nickel paratoluenesulfonate, nickel dibutyldithiocarbamate and nickel bisthiobenzyl. It is necessary to use a combination of the organic nickel complex and the ultraviolet absorber together with the cationic dye-dyeable polyester fiber.

The contents of the organic nickel complex and the ultraviolet absorber should be 0.01% or more, preferably 0.1% or more, based on the weight of the fiber.

When the content is less than 0.01%, a sufficient effect of improving the light resistance cannot be seen, but the effect is saturated even if the amount is increased, so it is desirable to limit the content to 2.0% at most.

The weight ratio of the organic nickel complex to the ultraviolet absorber is preferably 1: 1 to 1:10.

Furthermore, two or more kinds of the above-mentioned organic nickel complex and ultraviolet absorber may be used in combination.

The UV absorber used in the present invention has an effect of absorbing UV rays and internally converting the energy into heat energy to prevent photodecomposition of the dye, and is a benzophenone-based or benzotriazole-based UV absorber. The agent is preferably exemplified, and a benzotriazole-based ultraviolet absorber which causes less yellowing is particularly preferably exemplified.

In dyeing, the usual dyeing conditions for polyester fibers can be directly used. For example, the dyeing temperature is
The dye, the organic nickel complex and the UV absorber are sufficiently adsorbed, and the dye does not decompose or deteriorate.
~ 140 ° C is preferred.

If necessary, a pH adjusting agent at the time of dyeing,
There is no problem even if a dispersion leveling agent, an inorganic salt (sodium sulfate, sodium nitrate) or the like is added.

The cationic dye-dyeable polyester fiber thus obtained has a light discoloration resistance ΔE * of 4 or less after irradiation with a fade odometer for 20 hours, and a difference Δa *, Δb in the chromaticness index between the base cloth and the light irradiation cloth. * Is preferably -3 to 3, respectively.

When ΔE * exceeds 4, fading due to light irradiation is too large, and the difference in chromaticness index Δa
When * and Δb * are less than -3 or more than 3, the hue change may be too large to be put to practical use depending on the application.

[0025]

According to the study by the present inventors, the photobleaching of the cationic dye is caused by the highly reactive singlet oxygen oxidizing the dye and decomposing the dye, so that the generation of singlet oxygen is prevented as much as possible. At the same time, it is necessary to immediately return the generated singlet oxygen to the original state.

In the present invention, although the detailed mechanism thereof is unknown, an organonickel complex having a compact molecular structure selected from the group consisting of nickel paratoluenesulfonate, nickel dibutyldithiocarbamate and nickel bisthiobenzyl is used. , Exhibits the action of adsorbing singlet oxygen to the surface of nickel very easily and at the same time returning it to the original oxygen, and the action is extremely remarkably exhibited when the above organic nickel complex and an ultraviolet absorber are used in combination, and the light resistance is improved. It is presumed that a cationic dye-dyeable polyester fiber with dramatically improved fastness can be obtained.

Therefore, the fade odometer 20 is usually used.
Even with polyester fibers having a light discoloration resistance ΔE * close to 10 after irradiation with time, ΔE * can be improved to 4 or less.

Hereinafter, the present invention will be described more specifically with reference to examples. The evaluation methods used in the examples are as follows.

(1) Light Irradiation Conditions In accordance with JIS L0842-71, the dyed cloth was irradiated with a fade odometer at 63 ° C. for 20 hours.

(2) Photochromic resistance ΔE * Macbeth Color-Eye Model M-
Light source D6 using 2020 (Kolmogen, USA)
Measure the diffuse reflectance of the original cloth and the light irradiation cloth in the field of view of 5 and 10 degrees,
Lightness index L *, chromaticness index a
After calculating * and b *, ΔE * was calculated from the following equation according to JIS Z8730-1980. ΔE * = {(ΔL *) ² + (Δa *) ² + (Δb *) ² } ^{1/2 If} ΔE * is 4 or less, discoloration due to light irradiation is small, and even in vivid colors such as purple, It can be said that it has good light fastness.

Further, the difference in chromaticness index Δa *, Δ
When b * is less than -3 or more than 3, the hue change is too large and it cannot be put to practical use depending on the application.

[0032]

Examples 1 to 3 By a known method, 1.7 mol% of tetra-n-butylsulfonium 3,5-dicarboxybenzenesulfonate was copolymerized with dimethyl terephthalate,
Melt spinning a polyethylene terephthalate chip with tetramethylammonium hydroxide added at 50 mmol%,
A cationic dye dyeable polyester multifilament of 75 denier / 36 filament was obtained.

Then, a plain woven fabric is woven using the multifilament as a background and scouring, relaxing, and
It was dried and preset.

Then, the organic nickel complex and the ultraviolet absorber shown in Table 1 were added to the following dyeing bath, and dyeing was carried out at 130 ° C. for 60 minutes at a bath ratio of 1:50. CI Basic Violet 11 (molecular weight 471) 5.5% owf CI Basic Blue 75 (molecular weight 394) 0.5% owf acetic acid 0.4 g / l sodium sulfate 6.0 g / l

After dyeing, in order to remove the dye adhering to the fiber surface, reduction washing was carried out in the following bath at 80 ° C. for 20 minutes. NaOH flakes 1 g / l hydrosulfite 1 g / l amylazine D (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 1 g / l After reduction cleaning, sufficient washing with water, drying, and curing.

[0036]

Example 4 In place of tetra-n-butylsulfonium 3,5-dicarboxybenzene sulfonate in Example 1, a 5-sodium sulfoisophthalic acid component was added to 2.
The same procedure as in Example 1 was carried out except that 6 mol% was copolymerized.

[0037]

Comparative Example 1 The procedure of Example 1 was repeated except that the organic nickel complex and the ultraviolet absorber were not used.

[0038]

Comparative Example 2 The procedure of Example 1 was repeated, except that the ultraviolet absorber was not used.

[0039]

Comparative Example 3 The procedure of Example 1 was repeated except that the organonickel complex was not used.

Table 1 shows the light discoloration resistance ΔE * of the obtained woven fabric and the differences Δa * and Δb * between the chromaticness indexes of the base fabric and the light irradiation fabric.

[0041]

[Table 1]

[0042]

EFFECTS OF THE INVENTION According to the present invention, a polyester fiber which is deeply colored and vividly dyed and whose light fastness is dramatically improved can be obtained, and the polyester fiber can be applied to the field of outdoor sports textiles. It will be possible.

Claims (3)

[Claims] 1. A cationic dye dyeable polyester fiber dyed with at least one cationic dye, selected from the group consisting of nickel paratoluene sulfonate, nickel dibutyldithiocarbamate and nickel bisthiobenzyl. A polyester fiber having improved light fastness, which comprises at least one organic nickel complex and an ultraviolet absorber in an amount of 0.01% or more based on the weight of the fiber. 2. The polyester fiber according to claim 1, wherein the ultraviolet absorber is a benzotriazole type ultraviolet absorber. 3. The light fastness according to claim 1 or 2, wherein the light fastness to color change ΔE * is 4 or less, and the differences Δa * and Δb * between the chromaticness indexes of the base cloth and the light irradiation cloth are -3 to 3, respectively. Improved polyester fiber.