JPH0236263A - Polyamide dyed article having excellent light-fastness - Google Patents

Abstract

PURPOSE:To provide a polyamide dyed article having excellent light-fastness by comprising a polyamide containing zeolite particles in a dispersed state and a metal complex dye. CONSTITUTION:A polyamide containing >=0.03wt.%, preferably >=1wt.%, of zeolite particles having a specific area of >=150m<2>/g, a SiO2/Al2O3mol ratio of <=14, preferably <=11 and an average particle size of >=10mu is dyed with a metal complex dye. The zeolite particles hold a metal having a lager ionization tendency than that of the central metal of the metal complex dye and the amount of the metal held in the zeolite particles is >=0.005wt.% based on the polyamide shaped article.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention relates to the production of polyamide dyeings with soaked lightfastness (
(dyed polyamide fibers, dyed polyamide fiber structures, and molded products).

(Problems to be solved by the prior art and the invention) Polyamides, especially nylon 6 and nylon 66, have excellent high strength and durability, so they are widely used in the form of yarn for clothing, interior decoration, and industrial materials. However, a major drawback of polyamide is that it is susceptible to discoloration due to photodegradation when exposed outdoors for a long time after dyeing.

In order to improve the light deterioration resistance of dyed polyamide products, various studies have been carried out for a long time at the yarn manufacturing stage or dyeing processing stage.

At the yarn manufacturing stage, for example, there is a method of adding copper or a copper salt to the polyamide. It has been known for a long time that steel has an effect on the heat oxidation resistance and light oxidation resistance of polyamide (French Patent No. 906893,
British patent 652947 @ Seikichi, German patent 8836
Specification No. 44). However, copper compounds alone cannot produce satisfactory effects, and even when added in small amounts to melt processing methods such as spinning and molding, there is a drawback that metallic copper precipitates.

Therefore, in order to enhance the stabilizing effect of copper compounds,
- There is a method of using a copper compound, iodine, and an iodine compound, as proposed in Tan Publication No. 10956 and Publication No. 48-7700. However, in either case, although the strength and elongation retention rate of the dyed polyamide is high, there is little effect on discoloration and fading due to photodegradation of the dyed polyamide, and a satisfactory product has not been obtained. This is the reality.

As a method for dyeing 7JO step, polyamide'4
In order to obtain excellent light fastness of J& fibers or fiber structures, it is common to use metal complex dyes. However, this alone is still insufficient, and as a method to further improve the light fastness of dyed products, for example, a method of using copper salts such as copper sulfate during dyeing is known. -(1980)
1, 8 on pages 19 and 20. Reference is made to the IIANEs paper.

However, depending on the use of polyamide fibers, it is not uncommon for polyamide fibers to be required to have light fastness that far exceeds normal color fastness, and the above method is still insufficient for such uses. For example, kind of car seat, carpet like polyr
For products lined with fluorophore 4-mem, stricter standards are set than for general clothing light resistance group Q (63 DEG C. Cl2O - 40 hour phase meter measurement). For example, when evaluating using a fade meter measurement at 83°C for 200 hours as such a standard, it was found that milling dye,
When dyed with a leveling dye or the like, it was grade 1 according to the gray scale method of JIS-0842. In addition, when polyamide fibers are dyed with metal complex dyes, the light fastness is 1 to 1.
It was 2nd class. Even if a copper salt is used in combination with a metal complex dye in order to improve light fastness, the light fastness will only improve to grade 3 at most.

The object of the present invention is to provide a dyed polyamide, W4 fiber, which has super light fastness even under the above-mentioned severe standards, for example, has a light fastness of grade 4 or higher.

(Means for Solving the Problems) The polyamide dyed product of the present invention that achieves the above object is a polyamide dyed product containing a polyamide and a metal complex dye, wherein the polyamide contains dispersed biolite particles. I'll buy something.

The method of the present invention for achieving the above object is a method for producing a dyed polyamide product in which polyamide is dyed with a metal complex dye, wherein the polyamide contains zeolite particles, and the zeolite particles are ionized by the central metal of the metal complex dye. The amount of metal retained in the zeolite particles is 0 relative to the polyamide molded body.
．． 0.005% by weight or more.

In the present invention, when dyeing with a metal complex dye, it is presumed that the central metal of the metal complex dye 1 is coordinately bonded to the ion-exchangeable portion of the zeolite. Therefore, its binding force is extremely large, unlike that which is held by adsorbent materials such as activated carbon and alumina simply by physical adsorption. This is understood to be closely related to the fact that the light fastness of the polyamide dyed product provided by the present invention lasts for a very long time.

Zeolites are generally aluminosilicates with a three-dimensionally developed framework structure, generally based on 89203, XlVt2/. O・A, fl 2 O3・Y
It is expressed as St02 7H20.

M represents an ion-exchangeable metal ion, usually a monovalent to divalent metal, and n corresponds to this valence. On the other hand, X and Y represent coefficients of metal oxide and silica, respectively, and Z represents the number of crystallized water.

Many types of zeolites are known, with different composition ratios, pore diameters, specific surface areas, etc.

The specific surface area of the zeolite particles used in the present invention is 150
TIi/g (anhydrous biolite standard) or more, and the zeolite constituent SiO2/A, 12203 molar ratio is 1
It is preferably 4 or less, particularly 11 or less.

It is thought that the amount, exchange rate, accessibility, etc. of exchange groups in zeolite are attributable to the physicochemical behavior during the dyeing step with metal complex dyes.

The metal complex dye can be retained in the zeolite particles by dyeing the polyamide containing the zeolite particles with the metal complex dye. It is important that the zeolite particles retain a metal that has a greater tendency to ionize than the central metal of the metal complex dye used in dyeing. This means that the polyamide dyed product having super light fastness, which is the object of the present invention, can only be obtained by treating polyamide containing such zeolite particles with a metal complex dye. This is because metal complex dyes are
At the same time as it coordinates with the amino group or carboxyl group in the polyamide fiber molecule, the central metal of the metal complex dye undergoes ion exchange with the metal ion held by the biolite, and as mentioned above, it is stably retained by the coordinate bond with the zeolite. Think of it as something that can be done.

As the zeolite material having a S i 02 /Aβ203 molar ratio of 14 or less used in the present invention, any natural or synthetic olide can be used. For example, natural zeolite 1~ is analcime (Analcime:
S i 02 /l 203 = 3.6 to 5.6),
Cbabazite: S i
02 /AN 203-3, 3-6.0 and 6.4-7
．． 6), Clinoptilolite
ite: S i 02 /l 203=8.5~
10.5) Erionite:
S! 02/Aρ2 o3=5.8~1.4), Faujasite: S i 02 /A
N203 = 4.2-4.6), mordenite ()l
ordenite: S i 03 /A, I! ,
203=8.34~10.0), mordenite SiO
/AN203=9-10), and these synthesized olides are suitable as the zeolite material of the present invention. Particularly preferred are synthetic A-zeolides,
X-type zeolides, and Y-type zeolides and synthetic or natural mordenites.

These ion-exchangeable metals are Na (sodium ions), which can be said to be very suitable from the ionization tendency described below. In other words, the ionization tendency of typical metals is listed as K>Na>Ca>Mq>Zn>
Cr＞Fe■＞Cd＞Co＞Ni＞Sn＞Pb＞Fe■
＞(H)＞Cu〉80＞HQ＞A LJ and the metal used in the present invention? 11 The central metal of the salt dye is preferably Co, Or.

Since the metal is either Ni or Cu, it is very convenient that the metal in the zeolite is Na, which has a large tendency to ionize.

The shape of the zeolite is preferably powder particle, and the particle size is as follows:
The thickness is preferably 10μ or less. When the average particle diameter exceeds 10 μm, the texture of the dispersed state tends to become rough, and the light resistance effect becomes poor. When applied to thick denier fibers, it is several microns to 10
μ may be sufficient, but when used for fibers with a one-line denier, the smaller the particle diameter is, the better, from the viewpoint of spinnability, is 5 μ or less, more preferably 2 μ or less.

The proportion of zeolite particles in polyamide is 0.0
3,000% or more (anhydrous biolite standard).

If it is less than 0.033 times, it is difficult to retain enough metal complex dye to have super light fastness. From this point of view, the content is preferably 0.05% by weight or more, more preferably 0.10% by weight or more.

In addition, the amount of zeolide particles added to the polyamide is 0.03% by weight or more as described above, but the amount of metal ions retained by the zeolite particles relative to the polyamide is adjusted to be approximately 0.005% by weight. Must. In other words, the biolite particles are 0% relative to the polyamide.
．． Metals that can be ion-exchanged even if added at 3% by weight or more,
If the amount is less than 0.005% by weight, the metal complex dye cannot be retained sufficiently to have super light fastness. From this point of view, the content is preferably 0.007% by weight or more, more preferably 0.01% by weight or more.

The polyamide of the present invention includes nylon 6, nylon 66,
It is a polyamide with excellent fiber-forming properties made of nylon 11, nylon 12, various lactams, diamines, dicarboxylic acids, etc. The timing and method of adding and mixing the zeolite particles to the polyamide are not particularly limited. For example, a method of adding and mixing to raw materials and then polymerizing, a method of adding and mixing to a reaction intermediate, a method of adding and mixing to a polymer at the end of polymerization, a method of adding and mixing to polymer pellets and molding, a method of adding and mixing to a spinning dope. There are ways to do this. For the sake of simplicity, these methods will hereinafter be simply referred to as "additional mixing to polyamide." In short, the most suitable method may be adopted depending on the properties of the polyamide to be used, the characteristics of the process, etc. (The method of adding and mixing immediately before molding is usually suitable.

The metal complex dye used in the present invention has a central metal that is
It is a metal complex dye that is any of Co, Cr, Ni, or Cu, and includes mordant dyes, acid mordant dyes, metal-containing acid dyes, copper-containing direct dyes, etc., but the metal complex dyes used in the present invention include It is necessary that the metal atom has a coordinate bond with the dye molecule in advance, and metal-containing acid dyes and copper-containing direct dyes are preferred. The use of a dyeing double dichromate treatment such as acid mordant dyes, the so-called chromium post-treatment method, is not suitable for the present invention.

Metal-containing acid dyes include 1:1 metal complex dyes and 1:2 metal complex dyes, but in the present invention, 1:2 metal complex dyes that can be dyed in a neutral or weakly acidic dye bath are particularly preferred. . Examples of dyes of this type include Irqalan (commercial, manufactured by Ciba Geigy), Lanasyn (trademark,
Manufactured by Leand, Mitsubishi Kasei), Lanyl (trademark,
Sumitomo Chemical ■), Ayakalan (trademark, Japanese Herbal Medicine U'l), Aizen Flosan (trademark,
Examples include Hodogaya Chemical (Kyu'!A).

In addition, as copper-containing direct dyes, for example, c, ■, oirec
tRed 83, C, 1, Direct Brown
95, C,1,D+rectBltje 90, etc.

The dyeing method and amount of the metal complex dye used in the present invention are not particularly limited, and may be selected as appropriate depending on the desired color and density. The method for dyeing polyamide fibers and fiber materials may be carried out by conventionally known methods, and the dyeing bath contains, in addition to water and dyes, an antifoaming agent, a leveling agent, a twill dyeing agent, and salt as a pH adjusting agent. To give the grain a slight color tone, other dyes such as acid dyes and disperse dyes are used. Further, from the viewpoint of light resistance, the amount of the metal complex dye used is preferably 0.01% by weight or more, and usually 0.01 to 2.0% by weight based on the fibers to be treated. In order to roughly improve the light fastness, a copper salt may be used in combination with the metal complex dye.

By ion-exchanging the ion-exchangeable metal (sodium ion) of biolite with another metal, it is possible not only to improve the light resistance but also to provide a completely different function. For example, copper ions, silver ions, zinc ions, etc. are known to have antibacterial properties, and polyamides containing Biolye 1~ in which sodium ions (Na>) are partially substituted with these metals are dyed with metal complex dyes. This makes it possible to obtain a polyamide dyed product that not only has excellent side-light dyeing fastness but also has antibacterial activity.

For example, by dyeing polyamide containing zeolite in which sodium ions (Na+) have been partially replaced with copper ions (CLJ") with metal complex dyes, it not only has excellent side light dyeing fastness but also resists photodeterioration. It is also possible to obtain a polyamide dyed product in which the decrease in strength and elongation caused by the dyeing process is greatly improved.

(Example) Examples of the present invention will be described below, but the present invention is not limited to these examples unless the gist thereof is exceeded.

The light fastness, strength retention, and antibacterial activity in Examples were measured by the following test methods.

(Light fastness measurement method) Cut the processed sample into 7 cm x 7 crn, cut polyurethane foam with a thickness of 10 cm into the same size, apply it to the surface, load it into a fade meter, and keep the inside at 83 ° C for 20 days.
After exposure for 0 hours, the degree of discoloration was determined on a gray scale.

(Strength and elongation retention rate) The yarn sample was loaded into a fade meter, and the strength retention rate was measured after exposure for 200 hours while maintaining the inside of the vessel at 83°C.

(Anti-bacterial power) Measured by the bacterial killing rate shown below.

(Measurement of bacterial killing rate) ESC CheriChia coli or 5taph
Using a suspension of S. y+ococcusaureus, the test bacteria solution was diluted to a concentration of 2 to 4 x 10'' cells/ml.

0.2 d of this test bacterial solution was dropped onto the molded body and allowed to act at 37° C. for 18 hours while keeping the molded body still. After 18 hours, the molded body was washed with physiological saline and the whole body was rated at 10 (7), then 1
1 nl was dispersed on an agar medium, maintained at 37°C for 24 hours, and the number of surviving cells was measured to calculate the mortality rate.

Examples 1 to 4 Natural and synthetic zeolite particles used in the examples of the present invention were crushed and classified to obtain zeolites 71 to Z4 having an average particle size of 0.6 to 2.0 μm. The theoretical content of Na contained in Biolite Z1, Z2, Z3 and Z4 is 15.7wt%, respectively, based on no hopiolite as shown in Table 1.
14.4 wt%, 11, 2 wt%, and 6.0 wt%
Met.

These zeolites were dried under reduced pressure at 200°C for 7 hours. Relative viscosity (η, .1.) measured in 95% sulfuric acid2.
A zeolite of any one of Suko Z1 to Z4 was added and mixed in a proportion of 2% by weight to 3-6 nylon chips, melt-spun, and then drawn to obtain a drawn yarn of 70 denier/24 filaments. At this time Zl.

Z2. Samples ■ and ■ of drawn yarns containing Z3 and Z4, respectively.
, ■ and ■. The Na content of these samples was as shown in Table 2.

These samples ① to ② were made into a nylon tricot fabric using a conventional method and were treated with metal complex dyes (center metal - Co).

After dyeing using Cr) under the following dye bath composition and conditions, the light fastness was measured. The measurement results are shown in Table 2.

Dyeing bath 1 (metal-containing dye) Lanasin Yellow 2RL (trademark, manufactured by Sandoz Co.) 0
．． 103% ovf Metal-containing dye (center metal Co) Lanasin Bordeaux RL (trademark, manufactured by Sandoz Co.) 0.
0185%owf Metal-containing dye (center metal Co) Lanasin Black BRL (trademark, Sandoz Co., Ltd.) 0.0
6%owf Metal-containing dye (center metal Cr) Ammonium sulfate 0.5g/Ω
Neogen S-20 (trademark, manufactured by Daiichi Kogyo) 2.0% ov
f Seropol DR-80 (trademark, manufactured by Sanyo Chemical) 0.6%o
wf bath ratio: 30 times bath temperature: Dyeing was carried out while raising the temperature to 30 to 90°C over 60 minutes, and then dyeing was carried out at that temperature for 45 minutes.

Comparative Examples 1 to 3 Polyamide containing no zeolite (sample ■) was dyed in dye bath 1.
The light fastness was measured for samples dyed with the following dye bath composition and conditions using a leveling type acid dye that is not a metal complex dye, and sample (1) and sample (2) containing zeolite Z3 using a leveling type acid dye that is not a metal complex dye. The measurement results are shown in Table 2.

Dye bath 2 (leveling type acid dye) Kayanol Yellow NFG (trademark, manufactured by Nippon Kayaku) 0
．． 12%owf Chikarayanol Phloxine NK (trademark, manufactured by Nippon Kayaku) 0
．． 1%ovf Aminyl Blue E-2GL (trademark, manufactured by Sumitomo Chemical) 0
．． 092%owf Acetic Acid 0.5g/ΩNeogen 5-20 2.0%owf Seropol DR-800, 6%owf Bath temperature and bath ratio: Same as Example 1 Based on the results, samples ■ to ■ containing zeolite were Lightfastness 4 for samples of the invention dyed with metal complex dyes
However, for the polyamide sample that does not contain zeolite, the light fastness was 1 to 2 and good results could not be obtained even when dyed with a metal complex dye. Ta. Furthermore, when sample (2) containing zeolite and sample (2) not containing zeolite were dyed with a leveling type dye different from the metal complex dye, the light fastness was grade 1 in both cases, which was still poor.

That is, it can be seen that the dyed product obtained by dyeing the polyamide fiber mixed with the zeolite of the present invention with a metal complex dye has excellent light fastness.

Examples 5-1 to 5-3 and Comparative Example 4 The amount of zeolite z3 used in Example 3 added to polyamide was O, O12, 0,045, 9,0, and 13.0.
Nylon tricot raised fabrics obtained according to Example 1 with different wt% were used as samples ① to ②, respectively. The Na content in this polyamide fiber was as shown in Table 3. These samples ① to ② were dyed with the metal complex dye of Example 1 (Dye Bath 1), and the light fastness was measured. The measurement results are shown in Table 3.

From these results, the Na content retained by zeolite is
At 0.002vt% based on the entire polyamide, the light fastness is class 2 and the effect is insufficient, but at 0.005vt%
For those containing t%, the light fastness was grade 4, and a very good effect was confirmed. This means that the proportion of polyamide in the entire polyamide in the present invention is approximately 0.005w.
This means that it is preferably t% or more. In addition, the Na content relative to the entire polyamide is 1.0 wt%,
Even when 1.5 wt% was added, the light fastness was 4 to 5 grade, which was very good, but when 1.5 wt% was added, yarn breakage occurred frequently during spinning, making spinning difficult. From this, it can be said that it is preferable that the amount of zeolite added to the entire polyamide is less than 9vt%, taking spinnability into consideration.

Example 6 and Comparative Example 5 1/20 to 250 g of dried fine powder of Z3 shown in Table 1
Ion exchange treatment was repeated four times by adding 1 g of M copper sulfate aqueous solution, stirring at room temperature for 5 hours, and then filtering. The copper-zeolide obtained by this ion exchange method was washed with water to remove excess copper ions attached thereto. The water-washed copper-zeolide was dried at 100 to 105°C and then ground to obtain a fine powder of copper-zeolide. The copper content and specific surface area of the obtained dry copper-zeolide product were as shown in Table 3.

Polyamide fibers were obtained in the same manner as in Example 1 using this copper-zeolide. The theoretical metal content in polyamide fibers is Na -0, 184 wt%, Cu -0,
It becomes 055wt%. A tricot raised fabric was made from the obtained polyamide fiber in the same manner as in Example 1, and this was used as a sample [
phase].

After dyeing the sample [phase] with a metal complex dye (dye bath 1), the light fastness and strength retention were measured. Copper as a comparative example
Regarding the polyamide sample ■ that does not contain zeolide,
After dyeing with Dye Bath 1, the strength retention rate was measured. sample [phase]
Table 5 shows a comparison of the measurement results for sample ① and sample ①.

From this result, when zeolite retains copper, if it is treated with a metal complex dye, it will not only have a light fastness of grade 4, but also a strength retention rate of 75% due to the effect of Cu in the polyamide fiber.
．． It was 0%. In the case of polyamide that does not contain copper-zeolide, the light fastness is 1st grade and the strength retention rate is 15.0%, so dyeing polyamide containing copper-zeolide with a metal complex dye can improve light fastness against fading. It has been found that it is possible to obtain a polyamide dyed product which not only has excellent properties, but also has significantly improved strength and elongation reduction due to photodeterioration.

Example 7 and Comparative Example 6 Sample ■ containing zeolite Z3 and sample ■ not containing zeolite Z3
were dyed in Dye Bath 3 below in which a copper salt was used in combination, and the light fastness of each was measured. The measurement results are shown in Table 6.

From this result, if polyamide fiber containing zeolite (sample ■) is dyed in dye bath 3, which contains a metal complex dye and a side light improver (copper salt), the light fastness improves from grade 4 to grade 5. However, it has been found that polyamide fibers containing no zeolite can only improve to grade 3 at most.

Example 8 and Comparative Example 7 250 g of dried fine powder of Z3 shown in Table 1 was collected, 1 g of 1/20M silver nitrate aqueous solution was added thereto, and the resulting mixture was kept under stirring at room temperature for 3 hours. Then ion exchange was performed. The silver-zeolide obtained by the ion exchange method was filtered and washed with water to remove excess silver ions. The obtained silver-zeolide was treated with an aqueous copper sulfate solution in the same manner as in Example 3 to obtain silver and copper-zeolide. The copper and silver contents and specific surface areas of the silver and copper-zeolides obtained were as shown in Table 7.

The obtained silver, copper-zeolide was treated in the same manner as in Example 1 to obtain a drawn thread (Sample 11). The metal content in the drawn yarn measured by atomic absorption spectrophotometer and fluorescent X-ray analysis was as shown in Table 8.

Using this sample 11, a tricot raised fabric was prepared in the same manner as in Example 1, and dyed with the following metal complex dye (dye bath 4).

Dye bath temperature and bath ratio: The metal content in the polyamide dyed product obtained in the same manner as in Example 1 was as shown in Table 8. Furthermore, the light fastness, strength retention, and antibacterial activity of this polyamide dyed product were determined.

As a comparative example, sample (2) containing no silver or copper-zeolide was also dyed in the same manner as above and subjected to the same 41 tests. The measurement results are also shown in Table 9.

From the results in Table 8, by dyeing polyamide fibers containing copper and silver-zeolide with metal complex dyes, the content of copper, silver, and silica is almost constant, while only sodium content is 0.053 wt%. It can be seen that the content has decreased to 0.022 wt%. This is true when silver and copper-zeolide-containing polyamide fibers are dyed with metal complex dyes, as in the present invention.

Copper is not ion-exchanged (only sodium is ion-exchanged and the zeolite retains the metal complex dye).

Furthermore, from the results in Table 9, the dyed products made by dyeing polyamide fibers containing silver and copper-zeolide with metal complex dyes have ultra-light fastness with a light fastness of grade 4 and a strength retention rate of 73.5%, and are resistant to fungi. It can be seen that it has 100% super antibacterial activity.

Claims (1)

[Scope of Claims] 1. A polyamide dyed product containing a polyamide and a metal complex dye, characterized in that the polyamide contains zeolite particles dispersed therein. 2. A method for producing a dyed polyamide product in which polyamide is dyed with a metal complex dye, wherein the polyamide contains zeolite particles, the zeolite particles hold a metal having a greater tendency to ionize than the central metal of the metal complex dye, and the zeolite particles A method characterized in that the amount of metal retained in the polyamide molded body is 0.005% by weight or more based on the polyamide molded body.