JPS63165587A - Monobath/one-stage dyeing method of mixture composed of polyester fiber and cellulose fiber dyeable without carrier - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION In the present invention, a fiber material consisting of linear polyester fibers mixed with cellulose fibers is prepared from an aqueous medium by an exhaustion technique using a disperse dye and a reversible dye at the same time. −
The present invention relates to a method for staining in one bath/one step under conditions where the treatment liquid used is approximately the lung density.

A mixture of regular polyester (PK+3) -fRm and cellulose fibers is used as an exhaustive material.
I1. There are a number of practical methods of dyeing using #+gold, each of which is different in terms of texture. Due to the different requirements regarding the categories considered in this case, most of these various methods require multi-equipment configurations and are therefore time-consuming and costly for non-materials, such as fiber mixtures. A two-bath solution is applied in which each component is itself dyed from a separate dye liquor. In the multi-step second method in the above-mentioned length area, f! p [ carried out intermediately in the same downstream bath (-bath method)
(According to I (German Patent Application No. 72158314) and due to the smooth PH-transition from the acidic S form to the alkaline medium during the rX vermilion operation, the a is also reversed (
German patent publications no. 1469750 and no. 1619464) also belong to this category.

Similarly for joint marooning with disperse dyes and reactive dyes of such mixtures consisting of regular PE8-fibers and cellulose dark blue, one bath in which the dyes present simultaneously in the treatment bath are solidified simultaneously on both components of the fiber mixture. / One-stage exhaustion method is also lj! River can. It is for this reason that the process must be carried out in such a special manner, that first of all it is necessary to prepare uniform and advantageous conditions in the exhaustion and solidification steps for the different dyes VC. In the case of reactive dyes, which are limited in terms of a certain chemical composition of the fiber-reactive system (German Patent Application No. 7551466) and which have at least a wide range of pH-constant values during dyeing, A buffer storage is sometimes required (as reported in European Patent Application No. 70021044 and German Patent Application No. 72913718), which is harmful for most disperse dyes, but is not Eliminate the harmful alkaline solid phase of reactive dyes.A similar requirement was addressed by German patent application no. In this method, the pEI-levels generated dynamically in &'Q when reactive dyes are conventionally bath-dissolved in water are made available directly for dyeing benefits - thereby selecting a special 1cQ family. without need - fulfilled by.

PE5-/(6d before the inadequacies regarding the one-bath/single-stage exhaust dyeing of roulose-su fiber mixtures, despite the measures contemplated by the state of the art, the standards deduced in this regard remain unchanged. This leads to numerous staining problems.

If you choose a disperse dye that is long-lasting without compromising the pH value, this often involves coloring agents with poor fastness or extremely thin products that are extremely expensive. Eha Dye C, Technique, Jispers Proof 9 (11345) Father is C0 Technique, Disverse tz7)'' 90 (11117) Also #: ro, 1. Can be renewed in 2 days-spray of 0-66n6 or more Examples are Dye C0, Gisverse Yellow 54, NC, Cispers Red 2.
81 or i0,1. Jisverse Blue 56#:rL/Gular p1! 2t gives only dyeings with low thermal surface 71F fastness on Xs-fibers.

In addition, regular PE5-fibers can be boiled in the exhaustion process with the aid of heating at temperatures up to 106°C and also with the aid of 1HT-strewn 1'FCI at temperatures up to 20-130°C). The choice of disperse dye should be taken into account in the temperature range of the cattle, which must be dyed without any problems. U? -- entails being limited by its transient requirements for staining and its non-damaging rules when using below slightly alkaline pH-values, but on the other hand the reaction in the HT-range. 9 of the best sex dyes possible! In order to achieve color yields large amounts of salt must be used and this large amount of salt is again often used as is known for dispersion dyes - 4Lk for finishing, thereby dyeing on textile materials. - leads to filtration, which causes spots and irregularities in the dyeing;

Moreover, in the work of dyeing textile materials, it is rarely possible to correct the color after theoretical dyeing without adding another amount of dye;
In the T-staining method, f
: To clarify.

In short, polyester-4#! fiber mixture W
A further challenge is to dye dyes using disperse dyes and reactive dyes in a one-bath/one-step exhaustion process in a time and cost saving manner. With this goal setting, the usefulness of the current method, good maroon yield and dyeing taxability, independence of Km of dyeing stripes, and uniformity of the appearance of processing #@vermilion are absolute is necessary.

The object of the present invention is to prepare a PIL fiber material consisting of linear polyester fibers mixed with cellulose fibers from an aqueous medium by an exhaustion technique using disperse dyes and reactive dyes at the same time under neutral pH conditions with a boiling point of approximately By heating the bath to a bath temperature of -bath/in the one-step dyeing method, the dyed product is a mixture of Wt-t-Itaibu with 1 Lulose fiber having polyester fibers which can be dyed without a keyer. pH-adjusting chemical agents from electrolyte-containing dye liquors containing a combination of dissolved dyestuffs and optionally additional dyeing auxiliaries - except for the dyestuffs - of the various types mentioned above. The above dyeing method is patented in that the dyeing is carried out at a pH value in the range of 6 to &5, preferably &5 to 8, and a humidity of qoc to 105C, preferably σ95C to 10DC.

PE8- which can be dyed without KiV-su with uninvented X taste
Due to the special modification of the basic l&fibric acid components in the fibers, they can be dyed with disperse dyes at boiling humidity without the addition of carriers (dyeing accelerators) and in this case regular PE day-fibers. (Non-modified PK8 - fiber type, which can be dyed "normally") □ Adding a carrier to this at boiling temperature gives a good result similar to 1 (T - which must be dyed under the stripes). It is the meaning of such hydrophobic, synthetic fibers that exhibit vermilion potential.This type of modified frame, the strength of the single-fiber structure of the polymer, to polyester, which is conveniently used as the base polymer. It involves the internal condensation of a member consisting of a trifunctional ester-forming monomer compound that relaxes.
P) Incorporation of other polymerizable compounds such as aliphatic dicarboxylic acids or hydroxycarboxylic acids or well-known diols such as polyethylene oxide or polypropylene oxide into the block polymer cedar rci1
can be achieved.

px'rp - Polybutylene terephthalate fibers (FB'rP) which have been found to be useful by this method for fibers with structurally different properties compared to block polymers.
It is. Ethylene terephthalate and I! Copolymers consisting of comonomers having fi also belong to the class of pgs-fibers which can be dyed without carrier. In addition therein, furthermore, difunctional phosphinic acid derivatives are disclosed in German Patent No. 2.
Carboxyphosphine l! according to No. 546787!
11 PEEI with incorporated nine phosphorus-containing sea breams, which has been rendered flame-resistant by copolymerization of a phosphorus-organic compound to a linear phthalate ester, and which is at the same time dyeable at low temperatures. -To which the fiber type belongs.

The special PH, B as defined above, according to the invention as an oni fraction together with the fiber base fraction (l!
The nine cottons are treated with resizing, as well as other natural fibers with lulose, linen and lulose.

With respect to the physical composition of the fiber material to be dyed by the method according to the invention, the mixing ratio of carrier-free dyeable PKS-fibers to cellulose fibers can be varied within a wide range and, in terms of weight, from 5:95 to 95:5 preferably 5o near.

The ratio can be between 70:30 and 100 parts of the total mixture in each case, with the proportions of the different meat fiber components being supplemented in each case. Furthermore, in the case of the basic single fiber component, there can also be a mixture of a number of separate tanks of pzs and/or σ cellulose fibers.

The invention is applicable in principle to the preparation of cedar (in the processed state), for example to the dyeing of said [miscellaneous mixtures] as woven, knitted, non-woven yarns, rough fabrics or tops. Or it can be a substrate consisting of different fibers according to the warp and weft.

said n1. with disperse dyes and reactive dyes according to the special conditions of the process according to the invention. It is carried out by the exhaustion technique customary for dyeing miscellaneous mixtures. All dyeing devices suitable for exhaust dyeing come into consideration for this purpose.

The aqueous dyeing baths conveniently used for this purpose according to the invention only contain pH-sensitive chemical agents, such as organic acids or classes of chemical compounds which are aliphatically or aromatically treated. A water-bathable organic compound consisting of a dicarboxylic or dicarboxylic acid or a dicarboxylic acid or a dicarboxylic acid or a dicarboxylic acid or an alkali- or alkaline-earth hydroxide or a mixture of these compounds with or without the aid of a buffer. 〜a5 preferably a&5〜8
The pH value is adjusted to .

Among the neutral salts present as electrolytes in the exhaust dye solution, sodium chloride (common salt, sea salt, rock [)] and crystalline or anhydrous disodium sulfate (mirabilite), as well as phosphates, acetates, borates, and carboxylic salts, are present as electrolytes. !!At the same time, other salts such as Natori 9m Matage Kaliwam are also available.In the case of table salt and mirabilite, the appropriate amount for this purpose should be 10 to 100 f/, preferably σ20 to 8°t.
It is 7t.

Is the concept of “boiling and 5i2! degree range” a thorn in the present invention? )
90 to 105 C, preferably in the metering range of t' The above-mentioned requirements regarding humidity control in the exhaustion process are related to the final dyeing temperature, i.e. the dyeing is usually started at a low temperature (e.g. 20C to 60C), and then the above-mentioned dyeing 22 !Heat to 50°C.

-Bath/1st stage 5! ! ! ! The method according to the invention for implementing the color process is such that disperse dyes, reactive dyes, pigments, etc.
6. Including the addition of dyestuffs, neutral salts, and optionally dispersants and other dyeing aids (excluding carriers).6. 6. Vermilion time at final temperature is 10 minutes to 3 hours, preferably C50 minutes to 2 hours.

After completion of the final dyeing step, the bath is optionally cooled together with the cloth material present therein. Lightly dyed fiber material gold surfactant was added to the oven, rinsed with water without adding it, boiled in hot water, stirred for 9 minutes, and washed with water.
Finished with a + degree of scrubbing. Intermittent # by a-phase steam
Rinsing with hot and cold water or #''1rrPn water is also considered for finishing.

Further VC post-treatment of the vermilion color with a cationic post-treatment which is common in practice is advantageous.

The method according to the invention makes it possible to reshape multicolored patterns on a nine-sided fiber-mix component, making it possible to double-cross.

The summer-ready disperse dye thorns according to the invention are meant to be products which are known in principle for the vermillion color of pEs-11N fibers which can be dyed without a carrier. The majority of these types of dyestuffs, depending on their structure, belong to the group of compounds, acytraquinone, nitro- or quinoatarline, and in particular do not contain carboxyl- and/or σ-sulfonic acid groups, and in the case of azo dyes, gold It can exist as a complex compound.

In this respect, "C0LOUR Engineering II) EXJ73 version (197
1) and Addenda 1975 and 1982], the oak species name (0, I, generic name) C0 construction, disperse yellow 5.7.23.42.5
4.56.58.60.64.70゜79.100.1
04.114.122.146.165.201.20
4,218, ○, Engineering, Jispers Orange 1, 3.20, 23, 2
9.30.32.35.38.45.55.54.61
．． 66.76.130, C0 construction, Jispers Red 4
3.50.54.54:1.60.65.75.75.
86.88.91.92.122.132.135.1
45.150.152.153.154.159.16
7.167:1.169.177.182.183.1
84.191.194.200.202.206.20
7.210.225.258.2.81.512.31
9.525.524.558.545.558, c,
I, Dysperse Violet 26.27.28.63
．． 77&bc, 1. Jispers Blue 55.55.56.60
．． 75.81.87.143.183.185.198
It is advantageous to use disperse dyes such as those shown under No. 1, 333, 545.

Among the reactive dyes which are preferably more substantive and which are considered for the application of the present invention for dyeing LLOUS fiber components, among them are the reactive dyes which, as fiber-reactive systems, react with the aromatic nucleus of the chromophore. I
- chloro-ethylsulfonyl ring, β-dialkyl-inoethylsulfonyl, ethylacetyl-di-1 optionally substituted with acrylic azide (for example a-bromine monomerically β-tetrafluorosyl, butyl-derivative), Q-ri”
acetic acid-i-do,! -chloro- or di-β-sulfato or β-furkylsulfone-propionic acid-amide or mono-sulfonic acid, monochloro-triazinyl-, dichloro-triazinyl-, monofluor-triazinyl-, cyfluoro-triazinyl-, case Pyridinyl-9-mutriazinyl, monochloro-pyrimidinyl-, dichloro-pyrimidinyl-, trichloro-pyrimidinyl-1 monofluor-pyrimidinyl-, difluor-pyrimidinyl-, monochloro-difluor-pyrimidinyl-, methylsulfonyl-chloro- Methyl-pyrimidinyl-, fluoro-chloro-methyl-pyrimidinyl-, monochloro-pyridazinyl-, dichloro-pyridazinyl-, monofluor-pyridazinyl-, difluoro-pyridazinyl-, monochloro-quinoxalinyl-, dichloro-quinoxalinyl-, monofluor-quinoxalinyl- , difluoro-7talazinyl, cyclo-7talazinyl, or difluoro-7talazinyl group □ optionally having C14 property □ in one palindrome a number of times and various reactive groups, this If a precursor (which forms such a unique group during the red color process) or a reactive substituent group (which is easily removable and leaves behind an electrophilic residue) is present, the addition By the mechanism and by the HIE function, the organic compound with dye properties can react with the OH-Fund V component of the fiber molecule and thus incorporate the covalent bond at the same time. Advantageously, for these types of dyes "0OLO17FI IN
DKXJ75th edition (1971) Addendum (1975 and 1
982) in “C0 engineering, FI@acC1 vs D
It is called y5lil J, and it is peripheral.

The color-forming substrates of these water-bathable dyes having reactive groups are particularly suitable for substrates consisting of the series of azo, anthraquinone and phthalocyanine compounds, even if the azo and thalocyanine family does not contain metals. May contain metal.

Sulfone 1 has 1 more Fi in the above-mentioned reactive dyes! I! i (in addition to the case of reactive groups of the 9N family) in the molecule, which can optionally be separated via a chromophore, but especially bound to its aromatic residues. are doing.

From the above examples of V-selected reactive residues according to the present invention, it can be seen that the tetranitrogen atom as a substituted group is attached to a cyclic ammonium residue - for example, in the following structurally represented state (formula 8-triazinyl group derived from nicotinic acid or its functional derivative (especially amide), which corresponds to an aqueous or alkali metal (preferably meaning sodium hydroxide or calicum), is bonded with a cedar. It should be particularly emphasized that in these fiber-reactive dyes, in addition to at least one substituted 8-triazinyl group of the formula (1)-type or of the σ-type (■)-type, the same molecule 74 ammonium moiety bonded to a 9-retrotriazinyl residue, in which further chemical structures, in particular at least one further reactive group of the pi=z-sulfone type, may be present. Furthermore, in addition to the dyes containing Pyridinium S described in German Patent Application Publication No. 73314663, there are
No. 181374, No. 60-181576 and 6O-18
It is stated in the t577 newsletter.

The disperse dyes and reactive dyes selected according to the invention can be used alone or in combination (multicolor) within the scope of the dyes.

The disperse dyes and reactive dyes contemplated for dyeing according to the present invention can also be premixed as a solid and then used in the premixed cedar.

In this case, these premixes can be used as a powder bed or as a liquid fraction.

Cow? IJ? - PH1 which can be dyed at boiling humidity without concomitant use - Exhaustive dyeing of fibers Vc Commercially available disperse dyes are finely dispersed from an aqueous medium. I'm afraid that I'll get angry <rim de n
(r chssmtsrassr(1/1sxctl
-1ndoscrisJ 26/78 (1976
) 9 years old 550-556 pages and 27/79 (15'7
7), pages 336-339jL & 452-454 and r Melliand TextLlbsr
ichCe J 62 (1981), 7795-8
See page 00].

Furthermore, studies have shown that the dyeing behavior of this particular type of fil, axis, is dependent on a specific comonomer that is responsible for the modification of the underlying fiber material ([Oh @mL
sfaaern &+ TsxC1lLndo8Cr
te Jso/82 (M; 18o), pp. 758-45]. It should be taught! Regarding dye selection, the molecular size and polarity of the dye used are important.

In this case, there is a limit from the dye side for reasons of dispersibility and fastness, as well as the possibility of improving the dye build-up.

Therefore, efforts to improve certain retrieval properties of vermilion produced using conventional disperse dyes continue to be focused on optimizing the vermilion process. Based on the fiber protection 1C that occurs in the case of high temperature wires, VC without carrier can be produced in pms.
- Processing of fiber type with accompanying temperature sensitive fibers is provided as a field of application. Indeed, according to the state of the art, such a fiber mixture has a 1! However, the solid maroon color of both fiber fractions is not specifically indicated in the literature.

In view of the more or less unfavorable experience in exhaustion vermilion in one bath/in one stage of mixtures with lullose fibers containing regular PE5-fibers in combinations consisting of disperse dyes and reactive dyes, this study has been made. Depending on the vendor, these! ! Based on the characteristics of both dyes of 4 types, the unique dyeing φ in a common dye solution! This method of carrying out this study involves such a mixture containing PF3 fibers that can be dyed without
It could not have been foreseen that it would be possible to convert it to a proboscis and incorporate the processing strips according to the present invention to bring it together with respect to a wide range of M foundations at the same time.

Due to these results, many disperse dyes are neutral! 4i! It was not as expected that N was unstable when staining under HT-streaks from the solution. It has been found that the dye according to the present invention is completely stable at boiling temperatures. Again regarding this,
In this case, by the vermilion method according to the present invention, pH-
In the value, otherwise [1IT - pH for maroon -
It is possible to dye reliably, accurately and with complete dyeing yields even with disperse dyes which are considered sensitive (i.e. sensitive at pi (-value > 6)). ．．
Have a taste.

In particular, these disperse dyes, which are known to be pH-sensitive, are used during the dyeing of the above fiber mixtures according to the invention with carrier-free VC-colorable PF3-, which are not mixed in the M method.
The maroon color of the fibers (i.e. without the simultaneous presence of lulose fibers, reactive dyes and salts) is significantly less sensitive to pH than when used in the summer.

Furthermore, using the reactive dyes which are used under the boiling temperature conditions of the present invention during the entire dyeing time under the maroon operation of the multi-stage dyeing process, these dyes are It is noteworthy that a significantly higher dyeing yield is achieved than when using the corresponding HT-East 1 color Vc length.

In exactly the same way, using the method according to the invention, the fiber mixtures used according to the invention were compared with fiber materials containing regular PKS fibers as a mixture component of 54i!
It was expected by those skilled in the art that better fastness properties (wet-1 rub, chemical wash fastness) would be obtained for all 7'C dyeings made in this manner than when dyeing. Quantitative benefits correspond to modified nine PE8-#J1 fibers and roulose-su components.

Taken as a whole, the method according to the invention shows that the method according to the invention allows for accurate and redusting of exhaust dyeing of mixtures consisting of modified PE5 and cellulose fibers in the shortest possible time and processing outlays and at the lowest possible dye costs. Possibilities are advancements in knowledge and skill regarding Sugino.

The following examples provide a detailed explanation of the invention. In these descriptions, unless otherwise specified, parts and percentages mean heavy weight parts and weight percentages.

There are commercially available products of cedar spindle type, dyes and auxiliaries. CoLoa BINDEX J
It is clear from the 75th edition (1971) and the addendum.

Example 1 Polyethylene Tele7 tarley modified using polypropylene cryol in a laboratory-scale dyeing apparatus (PK
PP5 capable of staining without the type of enzyme TP)
- 1 oi of yarn consisting of 5 ml of a complete mixture of 5 ml of fiber and 5 ml of cotton was mixed with 4 oc of dye C0, DiSverse Blue 55 5 oz. Commercially available formulation of 1 ml color reactive dye represented by the following formula @ 60 q 1 Glauber's salt 10 f, lignin sulfonate Aqueous dyebath 2DO containing dispersed Oki Ju2f of the type - and crystalline dibasic phosphate 1f and with an H-value of Q7.51C54 due to acetic acid.
TnliC 4 people. Under sufficient shaking of the thread, 2
The yarn is heated to 28-10D DEG C. for 0 minutes and then dyed at the treatment temperature thus adjusted under the action of the dyeing mixture for 45 minutes. Subsequently, the exhausted bath together with the yarn was cooled to VC70-80C, and then the dyed yarn was soaked with water for 10 each of Yuzusa and 2 (B).
Temperature at boiling temperature in aqueous medium for up to 1 minute.
Rinse again with water. By mixing, a blue dyeing with good two-color dyeing and excellent fastness against non-H colors is achieved.

EXAMPLE 2 The dyeing operation is carried out as described in Example 1, except that the specific modified PETP fibers (processed as a mixed component in the warp yarn) and cotton (processed as a mixed component in the warp yarn) and cotton (processed as a mixed component in the warp yarn) are used as described therein. Example 1
If we use the backstriped disperse dye 1519 described therein and the evening color reactive dye 135η given by the formula therein, a blue two-tone dyeing with good fastness properties on mixed fibers as well as on valvewood is obtained. It will be done.

EXAMPLE 3 The dyeing operation is carried out as described in Example 1, but with a strand consisting of a mixture 'a' of polyethylene terephthalate fibers 7f modified with the block copolymer cedar with viscose 1QF and polyethylene glycol. 10F and in the bath otherwise identical process conditions 4C as in Example 1, dye C was used instead of the dye described therein.
．． I. By using a commercially available formulation of yellow reactive dye 500 η and 500 η of a yellow reactive dye represented by
! A kI/2 yellow staining is obtained.

Example 4 A complete mixture of cotton flock 10f & polybutylene terre 7 tallate (PBTP) - fibers was placed in an experimental apparatus for dyeing textile materials in a pack system loaded with Wk at 2DC as shown by the following formula: A commercially available formulation of a red reactive dye containing 1!140 cape and dye C0 technology, Gisbur Rez)''5440~, plus 2'l of common salt, phosphorus containing ninatrichum Q, 8f & phosphoric acid-sodium 0.2f and pH - Charge an aqueous dye bath 200- with a value of 7.4. Heat this exhaust dye bath to 95 C within 20 minutes under circulation and then dye in this way for 40 minutes at a processing concentration of 1 liter. Subject to the action of the mixture.

The dyed fiber material is then dyed according to the method of Example 1 vc
Follow and sickle. A mixed material-70k dyed in light pink by two-color dyeing is obtained.

Example 5a Under the order described in Example 4, ? ＃Processed to A length 9
and 95% polyethylene terephthalate-fiber yarn modified with butylene glycol and Mar-e IJ
The knitted fabric ICM' made of 5% cotton is then dyed. In this way a pink/red colored knitted fabric with good fastness properties is obtained.

Example 5b The dyeing is carried out as in Example 5a, but with the opposite fibers -
Summer use of knit glJ with the mixing ratio results in a pink/red colored knitted fabric with similarly good fastness properties.

Example 6 PZ fiber finished to be flame resistant and modified with phosphorus-organic components & 7t, viscose fiber 2f & cotton 1
．． At 6DC in an autoclave for HT-dyeing 10f of yarn consisting of a complete mixture of 3f, dye C0
Engineering, Gisverse Orange 25 ((3,1,71122
No. 7) Cape 70, a commercially available formulation of an orange-red reactive dye represented by the following formula 45η, anhydrous sulfuric acid 17 QM 4F, a dispersant consisting of a series of cresol-formaldehyde synthesis products 0.2 t&
200 d in an aqueous dyebath 200 containing 1f dipotassium biphosphate and pH-100 million brought to 6 gI41 with acetic acid.
Add inside.

This exhaust dyeing solution was heated to τ03-105C in a closed dyeing container within 20 minutes under sufficient shaking of the yarn, and then the fiber material was heated for 50 minutes under the action of a dye mixing nozzle. Allow to stand at processing temperature. The exhausted bath was then cooled together with the system to about 70 C, the dyed yarn was then rinsed with water, and 1 f/l of nonylphenoxyethylate was added twice, each time at boiling temperature in an aqueous medium. After washing and rinsing as much as possible with warm water and subsequently with cold water, in this way an orange dyeing of the cedar with a mixed color pattern was achieved, which corresponds to a special composition of the mixed yarn, which is excellent in good fastness to the valvewood. Ru.

Example 7 In the dyeing method corresponding to the method described in Example 6, in this case Adipine W is used as the fiber material! Polyethylene terephthalate fiber modified by m2f1 polycyclohexanediol-7 dibate fiber modified by co-condensation of block copolymerization consisting of polyethylene glycol and terephthalic acid 3f and cotton 5f treated with mar1 resizing are used in summer. Correspondingly, orange-dyed threads are obtained, in which case the dyed frame P# exhibits a color mixing effect as a result of the fiber mixture.

Example 8 Kujo Okishita mentioned in Example 1. However, in this case, PIIC modified with polyethylene glycol and a 9-block copolymer.
11 consisting of 50% TP-fiber and 5° linen! The fiber mixture GLJ is dyed and the post-dying treatment is carried out as follows: take out the dye bath and rinse the dyed fiber material in cold water for 1 minute, steam at 102-105 C for 1 minute and rinse in cold water for 1 minute. Rinse, steam at 102-105C for 1 minute, rinse with cold water for 1 minute, steam at 102-105C for 1 minute, followed by rinse with cold water for 1 minute. Is this method better next time? A monochrome dyed yarn with IQ fastness is obtained.

Example 9 P that can be dyed in cotton in the weft and without a key ring in the warp by loading 4000 tons of 60C water.
4'Jk was loaded into a rough strip-shaped fiber material 100 made of PS fibers, and then 400Kt of salt, 2 noodles of wetting agent, and a wrinkle suppressant (lubricant ] 4 Kf, 4 to 4 dispersion wounds, 9 crystalline sodium acetate
Mu8 odor, dye C. I. Gisverse Blue 555 2K
Commercial formulation 94KI of a blue reactive dye having the following formula is added. The pH value of the treatment bath is adjusted to Q8 with acetic acid and it is heated to boiling temperature within 45 minutes. Using this dye liquor, textile materials are dyed at boiling temperature for 90 minutes and then treated with 9M1. Remove the specimen from the pepper material, rinse it with water,
Rinse as usual and rinse again with water. Next, the quality of the cotton used was then dyed on this with a denatured 9 PFB - compared to the dyeing on the m fibers - but the intensity of the color was too dark. A) Troweling with the addition of reactive dyes When a slight density of bronzing exists on cotton, the heating is interrupted in the exhaust dyeing solution and the above reactive dye is added VC0.5 Kf. - dissolved in a little water - is added within 15 minutes. Then the heating material is boiled again within 15 minutes and the textile material is continued to be dyed with it again for 30 minutes. A leather fiber material dyed in a two-tone blue color with uniformity is obtained.

b) If there is too much color strength on sickle-colored rectified cotton with the addition of disperse dyes, add the above disperse dyes to the exhaust dye liquor - 1a, 5KI11f dispersed in a little water.
r: Add. After reprocessing similar to that described under a), a two-tone blue-dyed fiber material with good evenness is obtained.

Example 10 Yarn 1 made of 9pEs-fiber m65X & cotton 55N modified with iron copolymer and dyeable without a keyring
00f with mirabilite 160f and borax toft-2 60
C into 2 L of aqueous dyebath. The pH value of this treatment solution was adjusted to A5 with a little soda, and then the dyeing solution was adjusted to Dye C1, Dysperse Blue 60 If, Dye A
, Z, Disperse Ye''-12211:Mf and 2f of a commercially available formulation of a Turkish blue reactive dye of the following formula are added after making a paste from 50 mK of water.

This exhaust dye solution is heated to 98 to 100 c and used to dye the yarn for 60 minutes. After this treatment, the yarn is rinsed with water, washed under boiling in an aqueous medium, rinsed again with water, and finally treated with a cationic post-treatment agent 2f for 15 minutes at 40 crc in a new aqueous bath. Attach to. After rinsing the yarn again with water, a turquoise yarn is obtained which has very good wet-1 rub and chemical wash fastnesses.

EXAMPLE 11 Exhaust Dyeing At the ninth stage, a liquid formulation consisting of 50 parts of the blue reactive dye given by the formula in Example 1, 20 parts of the blue disperse dye described in Example 1 and 150 parts of water was prepared, This is 6
- Adjust the pH slightly. If this dye mixture 52 is applied thereon according to the method of Example 10 and on a mixed yarn of the following composition, an intense navy blue dyeing with excellent fastness properties is obtained thereon after finishing.

Example 12 The advantages that can be achieved when carrying out the method according to the invention with respect to the disperse dyes used - compared to the results with suitable dyeing techniques - can be illustrated by the following tests: a) Implementation according to the state of the art Method Unmodified regular p1ii8-stm50f
and wood #1i50f, a dispersant 1F
and an aqueous dyeing liquor 1 containing 2f of crystalline disodium phosphate and adjusted to a pH of 1S11 to Z5 with diluted sulfuric acid and with the addition of 1t of Dye CO, Diverse Blue 555, was introduced into the solution. do. The bath is heated to 150C in a closed dyeing vessel within 30 minutes and then the fibers are allowed to stand under the action of the dyeing mixture for 60 minutes. ffl# The bath exhausted with the material is cooled and subsequently, after the usual rinsing of the dyeing thus formed, soaping under boiling water, rinsing again and drying, the cotton component of the textile material dyed in this way is By treatment with 855% phosphoric acid at 80C for minutes? Take a bath. As a result of the dyeing, a blue-dyed pzs fiber material remains after rinsing.

b) Method of implementation according to the invention Modified nine-PKB fibers which can be dyed without carrying
Completely mixed glI consisting of 50F and cotton 50F, Th,
a] In addition to the components mentioned under point 1, a further additive is introduced into an aqueous dyebath which additionally contains a commercial formulation of mirabilite 50f & bijika S@2t. The dye liquor is heated to 98-100 C within 30 minutes and the textile material is then left in boiling temperature conditions under the action of the dyeing formulation for 60 minutes. Here, the treatment of the left-over dyeing is then carried out as described in Example 1jla), and the dyeing results are as follows: Example 12a below. py;:s-
A fiber material is obtained.

From the above findings, it can be seen that the tested Friend Dye C1 process, Gisverse Blue 533, is surprisingly much more stable under the conditions of the present invention than by the conventionally practiced exhaustion process (method a). It's obvious.

EXAMPLE 13 In order to appreciate the superiority of the process according to the invention over the customary process with regard to the reactive dyes used, the following are illustrated: a) Process according to the state of the art Unmodified regular pEs-*msc+2 and cotton 50f (meat fiber type as thread in cedar of mixture)'fr
1 Dispersant 1F, Crystalline Phosphoric Acid Dis) 17 '7 Mu2F, Glauber's Salt 50F and a commercially available formulation of a blue reactive dye glJ2F corresponding to the structure shown by the formula in Example 1 and pH
- Aqueous dye liquor 1, whose value has been adjusted to 7.5 K with diluted sulfuric acid, is introduced into it. Run this bath at 13DC within 30 minutes.
and then leave the yarn in the action of the dyeing mixture F) IT-conditions. The exhausted dye liquor and thread are cooled down, the resulting dye is rinsed with soap, soaped under boiling water, rinsed again, and dried. As a result of the dyeing, a blue-dyed cotton component is obtained on the mixed yarn.

b) Regular P used in method a) for carrying out dyeing according to the present invention
E8 - In this case, a thread consisting of modified pis-fibers, which can be dyed without a key, is used for the fiber thread 9, and a dye bath is used.
The composition remains the same as described in test a]. The liquor is heated to 98-100C within 50 minutes and the yarn is then heated for 60 minutes under the action of the mixed formulation and left at a boiling temperature of 90 degrees. After that, the exhausted nine baths are cooled together with the threads contained therein, and the threads thus dyed are rinsed as if they were a suitable material, boiled, dried, and rinsed again. As a result of dyeing on dry υ yarn, a blue-toned cotton fraction is obtained, which has a ps5
It has 14 specific definitions.

From this, for comparison, Vcl! ! Used ratio, example 1
It is concluded that under the conditions according to the invention, the scheelite dyes corresponding to the formula in are reproducible, surprisingly much darker dyeings than the dyeings of the exhaust step according to the conventionally practiced process a).

C) Test method 13a for the fastness of the dyeing formed
] A fastness test of 1 ft. was carried out using textile material specimens containing a blue-toned cotton component which had been prepared and dyed according to the following I) IN-Standard. Measure the following values in accordance with: Specimen 13a) 13b) Waterfastness (severe) (No. DzN754006)
4-5 2 315 3-4 4shio-hikukanshitaishu (
5[]C) (p Kozai No. 54013 3 5
3 315 3-44 sweat'i prison (firi)
CDlN754020) 5 3 31
5 5-a5-a Sweat fastness (Fluka 11 property) CD
1N754020) 5 2-3315 3-4
5-4 A higher robustness rating on this rating scale means a better result in the test. (F = change in tone, C
o = soiled cotton, Wo = soiled wool].

On the basis of the numerical results from the fastness tests, it can be deduced that the dyeings produced according to the invention are significantly more robust than the dyeings obtained by the conventional method.

Example 14 Case of forming dyeing using disperse dyeing feeExample 12a) Or 1
2b) Analogously to the steps described in 2b), but only twice by increasing or decreasing the pH by 5 units, respectively, and adjusting it to match the quality of the individual sample. Based on the reflectance measurements, the following values of color intensity (pEI7.5-
The color yield of Some and Tomoe is rated as being equal to Inu 100.)
can be confirmed on the PK8-textile material dyed in this color in 1r color: pH 7,0L52 1 100 y, s 1oo l to.

ao 64198 These values do not lead to a stable dyeing yield when applying the dyeing method b) #″r disperse dye according to the present invention, but only a slight p-t variation in the conventionally practiced dyeing method a]. Even in the dark, the fc color intensity varies completely, thus leading to a high instability in the dyeing process, which is close to reality with respect to the reproducibility of the results.

Example 15 When forming dyeing 1 using disperse dye Example 13a) and #
: r15 b) Performed analogously to the article described in the text, but both times with the pEI-value increased or decreased by 0.5 units, respectively, in accordance with the quality of the individual samples. Based on this, the next value of color dullness (2
Day 15 - The intensity of the dyeing (each rated equal to 100) can be dyed blue in this way and confirmed on the material: 2 days l mouth 72 1 987.
5 100 1 100 a0 120 1 100 These values lead to a stable dyeing yield when the graystone dye is used in the dyeing method b) according to the present invention, but they do not lead to a stable dyeing yield when the dyeing method b) according to the present invention is used. This means that even slight pH fluctuations in the dye can completely change the intensity of the colorimetry and therefore lead to a high instability under real-time dyeing with respect to the reproducibility of the dyed results.

Examples 16 to 70 The dyeing operations shown in Example 1 are carried out using one or more of the disperse dyes specifically indicated in the following table. If it fluctuates slightly, f
Monochrome and bicolor with excellent color strength, excellent fastness results and high stability of color strength even at 5 pH values.
Staining obtained: 16 Dysperse 0-7 (26090)
Two colors 17 Jisbath Ie C1-42 (1
0338) '18 Jispers Yellow 5619 Jispers Yellow 58 (5624
5) -20 Jispers Yellow 60 (127
12) #21 Jispers Yellow 64
(47023) -22 Jispers Ie o-7Q
(11900) '23 Jispers Ye 0-10024 Jispers Yellow 1222
5 Jispers Yellow 14626 Jispers Yellow 16327 Jispers Yellow 201 Examples Number c, 1. Generic name
Dyeing result 28 Jispers Yellow 204
Two colors 29 Jispers Yellow 21830 Jispers Orange 1 (1
1080) 51 Jispers Orange 13 (2
6080) 32 Jispers Orange 25 (1
1227) 33 Jispers Orange 29 (2
6077) 34 Jispers Orange 30 (1
111<1)35 Jispers Orange 523
6 Jispers Orange 5537 Cisverse Orange 5438 Jispers Orange 6139 Jispers Orange 13040
Jispers Red 4541 Jispers Red 54:142 Jispers Red
60 (60756) 46 Jispers Red
73 (11116) Example No. C0 construction, generic name
Staining result 44 Jispers Red 8
6 (62175) Bicolor 45 Jispers Red 88 46 Jispers Red 91 47 Jispers Red 12248
Jispers Red 13549 Jispers Red 1505o Jispers Red 15351
Jispers Red 16752 Jispers Red 18253 Jispers Red 18354 Jispers Red 20055
Jispers Red 32356 Jispers Red 32457 Jispers Red 558
58 Jispers Red 34559
Jispers Red 358 cases number c, 1. Generic name Staining result 60 Dysverse Violet 26 (62025) Two colors 61
Gisverse Violet 27 (60724)
'62 Jisverse Biojit 6563 Jisverse Blue 55
Single color 64 Gisverse Blue 56
(63285) Light color 65 Jisverse blue 75 (63265) 66 Jisverse blue 8167 Jisverse blue 87
Two-color 68 Gisverse Blue 183 (1107B) Single color 69
Jisverse Blue 3357D Jisverse
Blue 345 Two-color examples 71 to 1
05 Carry out the dyeing operation according to Sumi Kujo as shown in Example 1.
However, if used in the summer with one or more of the reactive dyes specifically shown in the table below, excellent color strength and excellent color strength can be obtained even in the case of slight pH fluctuations. Excellent fastness results and high stability of color intensity. Monochromatic and dichromatic dyeings are obtained having: Example No. Reactive dye 71 (orange) of the formula Example No. Reactive dye 72 (Nagui) 73 (Navy) 74-103 (Turkish blue)

Claims (1)

[Claims] 1. A fiber material consisting of linear polyester fibers mixed with cellulose fibers is brought from an aqueous medium to about the boiling point under approximately neutral pH conditions using a disperse dye and a reactive dye at the same time by an exhaustion technique. In a one-bath/single-step dyeing process by heating to a certain bath temperature, a mixture with cellulose fibers having polyester fibers dyeable without a carrier as the dyed product is used in the above-mentioned variety for both types of fibers. from an electrolyte-containing dye liquor containing a combination of dispersed or dissolved dyestuffs of the type and optionally also the usual dyeing auxiliaries - minus the carrier, in the presence of pH-adjusting chemicals.
5, preferably a pH value in the range from 6.5 to 8 and 90°C.
The dyeing method described above is characterized in that dyeing is carried out at a temperature of from 95°C to 100°C, preferably from 95°C to 100°C. 2. The individual fiber components involved in the production of the fiber mixture are - by weight - 5 to 95 parts, preferably 30 to 70 parts of carrier-free dyeable polyester fibers and preferably 95 to 5 parts for every 100 parts of the total mixture. is 70 to 30
Claim 1 lies in the mixing ratio of cellulose fibers in
The method described in section. 3. The polyester-fiber type which is dyeable without a carrier participating as a component of the fiber mixture is prepared by combining a long-chain diol, preferably consisting of polyethylene oxide or polypropylene oxide, with a hydroxycarboxylic acid or an aliphatic dicarboxylic acid or with a phosphorus-organic diol. A polyethylene terephthalate fiber or a polybutylene terephthalate fiber as modified by copolymerization with a compound preferably based on a difunctional phosphinic acid derivative. Method. 4. According to any one of claims 1 to 3, in which all additives/chemical agents taken into account for the carrying out of the dyeing are present from the beginning in the pre-dye bath which is heated in particular to the dyeing temperature. Method. 5. The method according to any one of claims 1 to 4, wherein after the exhaustion step, the dyed fiber material is subsequently post-treated by intermittent steaming with saturated steam and rinsing with cold or hot water. 6. The method according to any one of claims 1 to 5, wherein the dyed fiber material is subsequently post-treated with a cationically active post-treatment agent after the exhaustion step is completed. 7. As a disperse dye, type name (C.I. general term) C.I. I
．． Jispers Yellow 5, 7, 23, 42, 54, 56
, 58, 60, 64, 70, 79, 100, 104, 1
14, 122, 146, 163, 201, 204, 218, C. I. Jispers Orange 1, 3, 13, 20, 25, 29, 3
0, 32, 33, 38, 45, 53, 54, 61, 66
, 76, 130, C. I. Jisper Red 43, 50
, 54, 54:1, 60, 65, 73, 75, 86, 8
8, 91, 92, 122, 132, 135, 143, 1
50, 152, 153, 154, 159, 167, 16
7:1, 169, 177, 182, 183, 184, 1
91, 194, 200, 202, 206, 207, 21
0, 225, 258, 281, 312, 319, 323
, 324, 338, 343, 358, C. I. Dysperse Violet 26, 27, 28, 63, 77 and C.I. I. Jispers Blue 35, 55, 56, 60, 7
3, 81, 87, 143, 183, 185, 198, 3
At least one of the disperse dyes known under 33,345
7. The method according to any one of claims 1 to 6, wherein seeds are used. 8. Vinylsulfonyl-, β-sulfato-ethylsulfonyl-, β-bonded directly or via short-chain, preferably aliphatic bridge members to the aromatic nucleus of the chromophore as a reactive dye as a fiber-reactive system. Thiosulfatoethylsulfonyl-, β-chloroethylsulfonyl-, β-dialkylaminoethylsulfonyl-, ethylene-imidyl-, optionally substituted acrylamide-, α-chloroacetic acid-amide, β-chloro- or β -sulfato- or β-alkylsulfone-propionic acid-amide or -sulfonamide-, monochloro-triazinyl-, dichloro-triazinyl-, monofluor-triazinyl-, difluoro-triazinyl-, optionally substituted pyridinium-triazinyl-, monochlor -pyrimidinyl-, dichloro-pyrimidinyl-, trichloro-pyrimidinyl-, monofluor-pyrimidinyl-, difluor-pyrimidinyl-, monochloro-difluoro-pyrimidinyl-, methylsulfonyl-chloro-methyl-pyrimidinyl-, fluoro-chloro-methyl-pyrimidinyl-, Monochloro-pyridazinyl-, dichloro-pyridazinyl-, monofluor-pyridazinyl-, difluor-pyridazinyl-, monochloro-quinoxalinyl-, dichloro-quinoxalinyl-, monofluor-quinoxalinyl-, difluoro-quinoxalinyl, dichloro-phthalazinyl- or difluoro-phthalazinyl- group. 7. A method according to any one of claims 1 to 6, characterized in that at least one reactive dye is used which has -, one or more times in the same molecule, with optionally different properties. 9. The reactive dye used as a fiber reactive yarn has the general formula (I) ▲Mathematical formula, chemical formula, table, etc.▼(I) (In the formula, M means hydrogen or an alkali metal, preferably sodium or potassium) 9. A process according to claim 8, containing at least one substituted s-triazinyl group of the type corresponding to . 10. The fiber-reactive dye used contains, as fiber-reactive system, at least one substituted s-triazinyl group of the formula (I) type and also at least one in the same molecule.
10. A method according to claim 9, containing further reactive groups having different chemical structures. 11. The reactive dye used is a fiber-reactive system containing at least one substituted s-triazinyl group of the type corresponding to the general formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) 9. The method according to claim 8, comprising: 12. The fiber-reactive dye used contains, as fiber-reactive system, at least one substituted s-triazinyl group of the formula (II) type and also at least one in the same molecule.
12. A method according to claim 11, containing further reactive groups having different chemical structures. 13. A fibrous material consisting of linear polyester fibers mixed with cellulose fibers is heated from an aqueous medium by an exhaustion technique using disperse dyes and reactive dyes simultaneously to a bath temperature at about the boiling point under approximately neutral pH conditions. Dispersion or dissolution of the various types mentioned above for both types of fibers, preferably in one-bath/one-step dyeing processes, with polyester fibers dyeable without carrier as dyestuffs, with cellulose fibers. 6 to 8 in the presence of pH-adjusting chemicals from an electrolyte-containing dye liquor containing a dye combination and optionally still the usual dyeing auxiliaries - minus the carrier.
．． 5, preferably a pH value in the range from 6.5 to 8 and 90
A textile material consisting of carrier-free dyeable polyester fibers mixed with cellulose fibers, which are dyed at temperatures between 95°C and 100°C, preferably between 95°C and 100°C.