DE1619595A1 - Process for multicolor dyeing of textile goods made from acrylic synthetic fibers - Google Patents

Description

PATE NTAN WKi. ι c DR M0LLER-BOR £ - DIPL-ING. GRALF§

DR. MANiTZ ■ DR. DEUFEL 1 β 1

MONCHENa ^ ROBERT-KOCH-STR.! IUi

DR.MANiTZ D. 8MONCHENa ^ ROBERT-KOCH-STR.!

TELEPHONE 225110

July 27, 1967

D / hr - J 313

JAPAN EXLAN COMPANY LIMITED ₉ Osaka / Japan

Process for multicolor dyeing of textile goods made of acrylic synthetic fiber

Priority: Japan of July 2, 1966, No. ₀ 4958V66 and Japan of February 15, 1967, No. ₀ 9997/67

The invention relates to a method for multicolored dyeing of acrylic textile material. In particular concerns the Invention of a method for multicolored dyeing of textiles material made from fibers of acrylic polymer which contains acidic groups (and hereinafter sometimes referred to as acrylicnthesis fiber without basic groups

00 9852/2 001

is), and consists in first coloring a part of the fiber material in dark shading with a front « metallized acid dye of type 1s2, which is an excellent To carry out, and after the fiber material dyed in this way is mixed, mixed, or mixed with the other, opposite fiber material Mixed in this way, the resulting textile material is cross-dyed to be carried out with another dye of different color

In cross-dyeing, where one textile material consists of two similar or the same fibers with identical functional groups to a different one When color swatches are dyed, it is common practice to do a first To dye that part of the textile material β, which is to be colored in a dark shade, and then a second coloring (cross coloring) of the entire arrangement to perform with a dye belonging to the class of Colors that match the one used in the first coloring Dye form a contrast · “.

However, if a textile material made of acrylic fiber with acidic groups but no basic groups and dyed in a dark shade with a dye _F dar katloni-

009852/2001 BAR

This shows behavior in the dye liquor (hereinafter referred to as cationic dye), mixed with an undyed textile material and subjected to a second dyeing with another cationic dye of different colors in order to obtain a multicolored product, the one on the tends to part of the material dyed in the first dyeing for bleeding in cross dyeing or second dyeing, with the result that the ^{other fiber or opposite fiber to be dyed in the second 1} dyeing is tinted, and accordingly the two-color effect is lost

You acrylic textilmater lallen which of the present invention are subjected to, consist of aoryl polymerizates, which contain acidic groups but no basic groups. In the process of producing the acrylic polymer or acrylic polymer, strongly acidic groups, such as Sulfate or sulfonate groups, in the terminal steeps of the molecules through the use of persosulphuric acid, sehulphuric Acid, sulfuric acid or oleum or their salts are introduced as a polymerization initiator * or there are alternatively acidic groups by interpolymerization with

009852/2001

unsaturated monomers introduced, which sulfonate groups contain, such as styrenesulphonic acid, yinylsulphonate, AHyI-sulphonic acid, methallylsulphonic acid, and their salts, or with unsaturated monomers which contain carboxylic acids, such as acrylic acid, methacrylic acid and itaconic acid and their Salts ο This makes the acrylic fiber obtained, which contains acidic groups but no basic groups, receptive to cationic dyes

Cationic dyes, like disperse dyes, are widely used for the coloring of hydrophobic ones Synthetic fibers are used, and the dyeing of an acrylic synthetic fiber with a cationic dye is apparently based on the reversible ion exchange reaction which schematisoh can be reproduced as follows »

(Fiber-4 - SO ₃ TYes ⁺ + (dye) ⁺ Cl ~

(Paser -4 SO ^ dye) * +

It can be seen that when a large one is freshly added Amount of selective on the acidic groups of the fiber too

00985 2/2001 _mmM _

adsorbing bationic substance for the dyeing device Reaction proceeds from right to left, and accordingly becomes the dye which is already bound to the fiber is released because it exchanges with the freshly exposed cationic substance suffers. This phenomenon becomes a practical problem when solo changes are made like changes in pH due to the addition of acid or alkali, or the addition of inorganic salts * & · | λ-. cationic dye of undersole coloring, the to be used in the cross-dyeing bath or the second liquor, and the cationic retarder used in the second Bath should be applied so that when bleeding dee in of the first liquor used dark dye on the cross color the fiber cannot be dyed satisfactorily in the second dyeing o this phenomenon is itself pronounced in the case of the cationic dyes found in the Japanese Industry Standards (JIS) as satisfactory can be referred to in terms of the numeral · Hence such a dyeing process cannot be used satisfactorily for practical purposes

With disperse dyes !! iat from the Journal of the Society of Fiber Science and Technology, Japan, Volume 21

Si 1 '- *.

1Ϊ09852/2001

Based (March 1965), S _0156-163 and a summary of "proceedings ¹ * of Friihjalireversammlung the Society of Fiber Science and Technology» Japan (1964), "S, 28, known that the coloring mechanism on the Henry see *. Verteilungsgeeetz Duroh dieββ fact and the fact that the diffusion of the dye is increased considerably in the Paser liber 80 ⁰ C is of Diapersionsfarbstoff that is once adsorbed to the fabric would be subject 1st ₉ distributed by the second dye liquor back into the non-colored substrate fiber from the above observation to draw the conclusion that such a way of working cannot be used in practice.

It has now been found that when dyeing an acrylic synthetic fiber with acidic groups, however, without basic groups a pre-metallized acidic dye of the 1: 2 in a liquor which contains at least one water-soluble inorganic salt of monovalent metals, divalent metals or contains an ammonium salt, there is obtained a colored material which is deeply colored and excellent in fastness and in particular has a minimum of dye migration. The present invention is based on this new position.

BATH ORIGINAL

- 009852/2001

The main objective of the invention is to achieve a multicolored colored material without spots and without blurring of the coloring in an acrylic synthesis fiber _{t contains} soft βaurβ diassociable groups, but no basic dissociable groups = this also gives a multicolored acrylic ceramic product of excellent fastness. Further objects and advantages are sub the following description

Ufa's object of the invention can be achieved by first dyeing an aoryl textile material in a dark shade with a pre-metallized acidic dye of the 1t2 type in the presence of. At least one water-soluble inorganic salt of a monovalent metal, a divalent metal "which is carried out by an ammonium salt" The textile material used is pasers, spun yarns and other textile products, which can be woven or knitted, and only from aoryl synthetic fibers, which contain acidic groups but no basic groups , consist _e used. A second dyeing of the other textile material is then carried out with a cationic dye or a bispersion dye of different coloration after the dyed material mentioned above has been used

009852/2001 _BAD

mentioned uncoloured material by mixing, Uischsplnnen, Misoing by fanning (formation of multi-stranded fondness), Weaving or working here, is united. The an swelter The part mentioned will not be used the first time it is stained colored, but only on the second coloring.

The kinetics and equilibrium of the dyeing behavior were investigated with regard to the dyeing of the aryl synthetic fiber, which contains acidic groups but no basic groups, with a pre-metallized acidic dye of the type 1s2 and it was found that the diffusion of both the cationic dyes and the disperse dyes increases strongly when the temperature of the ^{dye liquor reaches 70 to 90 0} O, but the diffusion of the pre-metallized acidic dyes of type 1 β2 is low because of their large molecular volume, and when the temperature of the dye liquor increases to more than 100 to 11O ⁰ O, the microbrown 'sohe movement of Paser mole kill θ is excited so that the diffusion thereof is substantially increased and a BU t Ad sorb ions isothermal leads _p that is substantially as Henry ¹ ULTRASONIC Verteilungsgeeeta can be shown. In addition, when one of the aforementioned inorganic salts is added to the dye liquor, this sale increases the distribution of the

BATH

00985 2/2001

pre-metallized acidic dye of the type 1: 2 on the fiber considerably and thereby enables the achievement of a dark tint which is assumed to be particularly difficult to achieve pre-metallized acidic dye of the type 1t2 can be achieved by treating the material with a dye liquor containing 0.5 wt. or more of the salt of a divalent metal or 1.0 wt. or more of the salt of a monovalent metal or ammonium salt a coloring ^{temperature of 100 0} C or more _{o In} other words, the use of temperatures of at least 100 ⁰ C, preferably 100 to 150 ⁰ Cj to achieve a "having good diffusion of this dye is a large molecular volume is required in the fiber, and each fleet temperature below 100 ⁰ C leads to a beträehtliehen reduction in dyeability of the fiber" A temperature above 130 ⁰ C., preferably nioht because the acrylic fiber at a as long as it is damaged at high temperatures.

The addition of an inorganic salt to the liquor is essential if there is an increased distribution of the dye Fiber can be achieved aoll. So the presence of 1.0 wt.

00-9852 / - '20O-1

το -. '

i » or more. Salt of a monovalent metal or ammonium salt, or 0.5 wt _o - # of a divalent metal salt in the dye liquor much, and no satisfactory coloration praktisoh be expected when the concentration of said inorganic salt is smaller than mentioned above. Preferably, however, the amount of inorganic salt or inorganic salts up to 5 wt _a - #, since the presence of an amount üb reduce unwanted gensets Government of the dye may cause "

Monovalent metal or ammonium salts that can be effectively used in accordance with the invention include the halides ,. Sulphates and phosphates of the alkali metals (Sodium, potassium and the like) and ammonium, and particularly preferred are those salts which are neutral in aqueous solutions. Specific examples of such salts are Sodium sulfate, sodium chloride, ammonium chloride, ammonium sulfate, potassium sulfate and the like. Of course, these salts can be used individually or in combination,

Examples of water-soluble salts of divalent metals are calcium chloride, barium chloride, zinc chloride, magnesium chloride

BATH ORIGINAL 003852/2001

1619585

ti -: - ■■■ - - ■;

Cadmiumehlorid, at Zinkeulf, magnesium sulfate, zinc nitrate _f Oadmiumnitrat, Calciunrbhiocyanat and the like, and mixtures of two or more of these · Another Torteil using a splehea salt of divalent metals "is that the divalent metal ion, ζ · _Β β Ca ⁺ " ¹ *, Ba ⁺ *, Zn ⁺ *, combines with the acidic groups in the fiber and the attachment sites for cationic. Dye blocks so that in the subsequent dyeing with a cationic dye, the formation of flakes or over-dyeing of the fiber dyed first with the second dye (cationic dye) is prevented.

As can be seen from the aforementioned fact that the dyeing behavior of the pre-metallized acidic dye of the 1: 2 type relative to aoryl synthetic fiber practically follows the Henry's distribution law, it is necessary that the dye concentration of the liquor be high when the fiber becomes too unified dark shade is to be dyed «For this purpose, the initial concentration of the dye in the dye liquor should be 0.2 öew _e = $> or more _o For economic reasons, the upper limit of the dye concentration is around 1 &>

OO9852 / 20U1

The pre-metallized acidic dye of the 1: 2 type is a Dye j in which two dye st off component enmole küle in Ko ^ ordinate bond with a single metal atom exist ^ as this is typically represented by the following formula:

In this formula, Me means a metal atom, such as chromium _g cobalt _P copper and the like, and R ¹ , R ", R"'and R ^M "

& AD ORIGINAL

OO 9 GG 2 f 2 O OΠ

are the substituents "which the dyes usually have" The structure of the dye formed in this way is anionic o A typical blessing ion is Z ₀ B ₀ the sodium ion The following are mentioned as examples of pre-metallized acidic dyes of type 1 »2:>

C = I ₀ Aoid Blaok 7, CIo Aoid Blaok 60, Col »Acid Black 62, CcIo Aoid Black 64» CIo Acid Black 108, CIo Acid Blaok 114, CI ₀ Acid Black 131, CnI ₀ Acid Black 148, Col »Acid Blue 127, C ₁₁ Io Aoid Bluo 165, CIo Acid Blue 167, CI. Acid Blue 171, Colo Aoid Blue 184, CIo Acid Blue 187, CoI * Aoid Blue 214, C ₀ Io Acid Blue 209, CoI. Acid Violet 46,

Colo Aoid C ₆ Io Aoid C ₀ I ₈ Aoid Cole Aoid Colo Acid Col * Aoid Colo Acid CoI. Acid CoI. Acid CoI, Acid CI. Acid CI. Acid Cl. Acid CI, Acid CI. Acid CI. Acid CI Aoid

Black 58 "Blaok 61 ₉ Black 63" Black 107o Black 113 ". Black 115, Black 132, Blue 7O ₉ Blue 151, Blue 166, Blue 168 j, Blue 183, Blue 186, Blue 188, Blue 215 »Blue 219, Violet 66,

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OI Acid Violet 68 ,, CI. Acid Violet 71, Col »Acid Violet 74, C ₀ I ₀ Acid Violet 78, Colo Aoid Violet 88, C.Io Acid Violet 99, C ₄ Io Acid Violet 101, C ₀ I, Acid Red 30, Colo Acid Bed 182 ₉ Colo Acid Bed 211, Colo Aoid Bed 215, Colo Aoid Bed 217, do Aoid Bed 219 “CoI. Acid Bed 221, Colo Aoid Bed 226, CI. Acid Bed 228, Colo Aoid Bed 252, CI. Aoid Red 258, CI. Acid Bed 261, CJ ₄ Acid Red 265, GoI. Aoid Bed 296, CI. Aoid Brown 21, CI. Aoid Brown 33 "CoI. Acid Violet 70, Cl. Acid Violet 73 * CIo Acid Violet 75 C ₀ Io Aoid Violet 87 "Colo Acid Violet 98, CIo Acid Violet 1OO _P Colo Acid Bed 28. Col" Aoid Bed 178, Colo Acid Red 209 ₉ Colo Acid Bed 213 "Colo Acid Bed 216 , CoI, Acid Bed 218, Colo Acid Red 220, CoI. Acid Red 225 ₉ CIo Aoid Red 227, CoI. Acid Red 251, CIo Acid Red 253, CIo Aoid Red 259, Colo Acid Red 262 »Cl. Acid Red 295 »CI. Aoid Brown 19 »CIo Aoid Brown 29, CoI. Acid Brown 44 »

009852/2001

BATH ORIGINAL

C ₁ Ic acid Brown 45s CI ₀ acid Brown 47 p CIo acid Brown 5O _f CIo acid Brown 225 _S. Colo acid Brown 227? Cold acid Brown 255, Colo acid Brown 257, Col » acid Brown 285, CIo acid Green 43, Colo acid Green 56, Colo acid Green 58, Colo acid Orange 39 » acid Orange 64, C.I. acid Orange 82, CoIc acid Orange 86 ₉ Colo acid Orange 88, Colo
Colo acid
Acid" Orange 94,
Yellow ''59 » O.I, acid Yellow 112, CoI. Ac \ d Yellow 114, CI, Acia Yellow 118, Colo acid Yellow Ί24f CoI. acid Yellow 128,

CpI ₀ acid Brown 46 _P Col. Acid Brown 48, CIo acid Brown 224, CoI. acid Brown. 226 ₉ CoI. acid Brown 254, CoI. acid Brown 256, CoI. acid Brown 275 _t Col "Acid Green 40, CI. acid Green 46, CoI ₀ acid Green 5T ₉ Colo Acid Green 6O ₉ Colo Acid Orange 6O ₉ CIo acid Orange 8O ₉ C _e Io Acid Orange 85 » Col. Acid Orange 87, CI. acid Orange 89, CI. acid Orange 113, CI. Acid, Yellow 111, CoI. acid Yellow 113, Col. ': Acid Yellow 116, CoI. acid -Yellow 119, Cl. acid Yeiiow * 127, Col | acid Yellow 129,

098B2 / 20Ö1 BATH

.16 -.

Col "AeId Yellow 149, C-I. Acid Yellow 150 *

C »I _{; e} AoId Yellow 151» "and the like"

In general, the first coloring is done with a pre-metallized acidic parking of the type 1: 2 with a flow! Capability ratio from 1i8 to 1i50 for a period of about 1 to 3 hours with a ρΉ value of 5 to 9 ο

The textile material dyed in this way is then carried out with undyed !! textile material made of a similar or the same acrylic polymer? However, the acidic group does not contain any basic groups, for example by mixing the staple fibers, conventional blending, MiBöhspinnen, mixing twisting ₉ MIb ohweben ₅ mixed knitting and the like dye or Diiepersionsfarbstoff with a Pärbung _f from that of the pre-metallized acid dye mentioned above, different from the type 1t2 1st subjected. The two staining can be carried out in the usual way. Thus iwird Z ₀ as the second dye in a fleet performed _# melehe 0.1 to 3.0 - ^ ₁ sbezogen weight dee

SAD

Ö098S2 / 2QÜ

Material has a dye, namely at a pH of 2.5 to T ₉ Oe a with a liquid ratio of 1 to 30 to 1: 100,

Examples of cationic dyes »those for the second coloration are the following:

C ₉ I ₀
C ₀ Io
Colo CoIe Colo
C ₀ Io
Col »
Col.
CI «.

Col

CI.

Basio

Basio

basic

Basio

basic

basic

basic

Basio Basio Basic Basio Basio Basio Basio Basio Basio

Blue 1, Blue 4, Blue Blue 30, Blue 32, Blue 36, Blue 40, Blue 42, Blue 45 »Blue 47, Blue 50, Blue 53f Yellow 11, Yellow 13, Yellow 15, Yellow 17, C ₀ Io Basio Col Basic CI Basic CIo Basic C ₀ I. Basic CI ₀ Basle CI. Basio CI. Basio CI. Basio CoI. Basio CoI. Basio Cd. Basio CI. Basic CI. Basio CI. Basio CoI. Basio

Blue 3, Blue 5, Blue 22, Blue 3V Blue 35, Blue 37, Blue 41, Blue 44 »Blue 46» Blue 49, Blue 51, Blue 54, Yellow 12, Yellow 14, Yellow 16, Yellow 18,

009852/2001 BAD

Colo Basic Colo Basic CI Basic C ₀ Io Basic Colo Basic Colo Basic Colo Basic CoI. Basic Colo Basic CoXo Basic CoI _n Basio CI, Basic CoI. Basic CoI. Basio CI Basic C ₀ I. Basio CoI ₀ Basic CI · Basic CoI. Basic CoI. Basio CI Basic CoI. basic

Yellow 19, Yellow 21, Yellow 23, Yellow 28 »Orange 21, Orange 24, Orange 26, Orange 28, Orange 30, Violet 15, Violet 17, Violet 20, Violet 22, Red 14, Red 16, Red 18, Red 20 , Red 23, Red 25, Red 27, Green 1, Green 6, and Colo Basic Yellow 20, CI Basie Yellow 22 _t CIo Basic Yellow 24, CI. Basic Yellow 29, CoI. Basic Orange 22, Col. Basic Orange 25, CI Basio Orange 27, CIo Basic Orange 29, Col »Basio Violet 7, GoI. Basic Violet 16, CI. Basic Violet 19 »Cl, Basio Violet 21, CI * Basic Red 13 * CoI. Basic Red 15, Cl. Basic Red 17, CI. Basio Red 19, CI. Basic Red 22, CI. Basic Red 24, CI. Basio Red 26, CI Basic Red 29, CI. Basic Q / TQsn 3 · the like.

SAD

00985 2/2

Ess textile material; which "becomes" in the second dyeing shows no signs of Aushlutenei from the fiber dyed first, i.e. no pleekeri formation or over-dyeing the last colored laser «Uaher shows what has been preserved ISaterial an attractive two-tone effect «

Under the expression Aerylsynthef aser * which, acidic groups however does not contain Taasiselien groups, and according to the Invention is applied is an acrylic fiber of acrylonitrile polymer © äer to an acrylonitrile copolymer understand which one is free of itiseh polymer components, which contain basic srupia "

Hie here verwenäete Albkürzüng tJ »X _n! Means Color" index to Auf3jage ₉ 1956s Tuad supplement 1963 * published by the Society of I) yers and 0olourists _f Bradfordsi England and the American Association of Textile Chemists and Colourists, Powell, Massachusetts' US "A"

The following examples show some typical embodiments of the invention "" All percentages -and parts are as β Gewicirfr 1> ez © gen _s unless otherwise specified "

_BATH

The Ams ^ mcfc aF ₀ means percent, based on weight

the Jiaser »-. -.

For 97.7 ropes of a dye liquor, 0.3 ropes of a pre-metallized acidic dye of the 1: 2 type are added. Acid HLue 187 "-mid given 2.0 parts of sodium sulfate, and Exlan L fiber C J Japan Eslan Company latä", laser from a mixed polymer; For © m acrylonitrile C90) / lle-taiyl acrylate (10), with 2OmMoI acidic lipstick / kg fiber) a coloring temperature of 12O ¹⁹ C! two hours of dyeing. At the end of this side span, the dyed fiber is removed. Hach the soap will be. Dyed fiber washed three times, each time with 50 times the amount of water, based on the fiber. The fiber is @eSalted and then dried. 20 ropes of the above-gurbed fiber are spun with 80 ropes of an undyed Exlan fiber to form a white and blue yarn. 2 parts of this yarn are dipped in 98 ropes of a dye liquor , the ame 0.01 $ cationic dye CI Basic Yellow 11, 0 _f 0S | 6 acetic acid, 0 ₉ 1 i » Matriumeralfat, 0.04 $> retarder üevegäl PAN (Farbenfabriken Bayer AG, üei ^ artesen) and 99» 79 | 6 there is water, and / with a

- 009852/2001 bad original

21 -,. . ■■. "· - ■. ■ ■■: -

, Colored temperature is increased from 6O ⁰ G to about 10O ⁰ O for 60 minutes, it is further colored ° east for an additional 30 minutes at about 10Ö;

The different colored yarn obtained shows no signs of * signs of a bleeding from the previously colored paser, i.e. no flaking of the last dyed fiber, which in this way takes on a light yellow tint. The result is an attractive mixed yarn of yellow and blue «

In contrast, the same yarn made of fibers shows one of which Part with a first dye liquor of the cationic dye CIo Basic Blue 1 and the other part of the fibers then colored in different shades, marked signs of staining on the last colored Fiber by bleeding out of the dye from the first dyed fiber, whereby the entire yarn takes on a greenish color. The expected effect of a multicolor so is not achieved *

EXAMPLE 2
Exlan DE fiber (Japan Exlan Company Ltd., Paser a »Hieoh-

000852/2001

polymer of acrylonitrile (91) / methyl acrylate (8 _f 8) / allylsulfonic acid (0.2), since it contains 43 mHol acid groups / kg fiber) is dyed in a bobbin dyeing device under the following conditions: 5 # aF «,, pre-metallized dye of type 1 : 2CI. Aeid Black 131 * 20 $> aF «, sodium chloride, liquid ratio 1/20, dyeing temperature 120 ° 0, 2 hours. The dyed fiber is soaped C for 20 minutes from the Spulenffärbevorrichtunggenommen and with 0.5 g / l Ho.igen HC (Daiichi Kogyo Co Seiyafcu <>, Ltd. ") at 60 ⁰ _o Then, the fiber is washed three times, in each case with 50 times the amount

will

Water on a fiber basis. The fiber is oiled and then dried. 20 parts of the fiber dyed in this way are mixed with 20 parts of undyed Exlan VK fiber to produce a mixed yarn which is dyed under the following conditions: cationic dye CI Basic Blue 1, 0.1 £ a " ? ·. Acetic acid 1 i> a «F ·, sodium sulfate 10 $> aF«, Tersögerer LAH (EoI. Du Font de Nemours, USA) 3 # a _or F., liquid ratio 1/50, the temperature of the dye liquor gradually increasing from 60 on. about 100 ⁰ C is increased within one hour, followed by further staining at about 100 ⁰ G follows for 7ieitere 30 Hinuten. The pleasure obtained does not show any signs of bleeding from the fiber dyed first, whereby the

BATH ORIGINAL

0O98S2 / 2ÖO1

1619535

cross-dyed bases have a brilliant pale bluish tint assumes ο It will be a very satisfactory cross-stitched one Sam. obtain·

If, on the other hand, the same fiber is first produced in a bobbin dyeing device under the following conditions: cationic dye Sumiacryl Black FFP (Sumiaerylsehwarz FET from Suinitomo Chemical Co., Ltd., Japan), 5 Io aoP ", sodium acetate 1 $> a ₀ F" , Leakage ratio 1/20 ρ with one? Flotteatemperatur that gradually increases from 60 to about 100 ⁰ C * -imd swar- is within a span of 40 minutes, and daan "feel about 100 ⁰ C for another 90 minutes ge =" · colored and then the colored Paser like Up Further

If you process ₉ you get a cross-dyed sara, but the last dyed paser is spotted to a large extent, which leads to a yarn that is hardly marketable . . ■■; ■. '-. . ' . "-

EXAMPLE 5

Exlan BK Fiber CJapan Exlan Company Iitd.) Comes with a pre-metallized acidic. Type 1: 2 colored dye and never after-treated in the same way in example 2 · you

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24 - '■■■ · .-

Paser is then spun into yarn. 1 part of the dyed yarn is mixed-twisted with 2 parts of yarn consisting of undyed Exlan EK fiber * and the resulting mixed-twisted yarn is machine-knitted. The resulting knitted fabric is dyed under the following conditions: cationic dye Sumiacryl Brilliant Yellow 5G (Sumiacryl Brilliant Yellow 5G Sumitomo Chemical Co ·, ltd., Japan) ₉ O ₉ 5 $ aF _"t acetic acid" 3 $> a "F., sodium acetate 1 # a" F. _t Retarder! Levegal PAN (Farbenfabriken Bayer AG., Leverkusen) 2.9 i ° aF _e , bath ratio 1 / 2O _? at a plot · * tent door empera j which gradually from 60 ⁰ C to about ⁰ C TOO increases within a time span of 40 minutes, and "closing further coloring at about 100 ⁰ C for a further 45 s Minufc"

They received cross-dyed fabric has an attractive schwars dotted pattern and shows no signs of Ausblut ens of the dye d _{o o} no Fleokenbildung the last dyed yarn "

If, on the other hand, a yarn is used »the one with the cationi— see dye Sumiacryl Black FFP (Sumiacryl black PPP)

.BAD ORIGINAL 009852/2001

is colored, leads to the bleeding of the dye from the yarn dyed first leads to extensive flaking on the yarn dyed last. You entire merchandise takes a gray one Tint on and the desired effect of cross-staining completely missing

EXAMPLE 4

Exlan DK fiber (Japan Exlan Company Ltd ₉ ') by means of a coil forming apparatus under the following conditions gefärbts pre-metallised acid dye from! Type 1s2 ₉ C »I * Acid Green 43 ₉ 8 $> a" F. ₉ potassium sulfate 20 $> a "F _e> fluid" ratio 1/20 »liquor temperature 12O ⁰ C ₉ 2 hours» The dyed fiber is processed in the same manner as in Example 2 for producing a colored yarn, the colored yarn ί leil is twisted with 5 / ropes of yarn ", which consists of an undyed Exlan DK fiber, and to increase the whiteness of the undyed yarn, the mixed yarn is dyed under the following conditions" cationic optical brightener Daitöphour ÄH (Daito Ghemieal Co., Ltd., Japan) 0.8 a F _{o of} Watriumsulfat 10 5έ SeF., acetic acid 1 ^ a _o P _e, Flttßeigkeitsverhältnis 1/100, at a emperature Flott ent "the gradually from 60 to about 100 ⁰ C within a time *

00015271001

span of 40 minutes increases, followed followed by further staining at about 10O ⁰ C ^ for 40 minutes. The cross-dyed yarn of the yarn obtained shows no sign of fleok formation and the yarn is highly marketable.

Instead of dyeing with a pre-metallized acidic dye of the Ts2 type, the fiber which is to be dyed first is treated under the following conditions. Cationic dye C * I _e Basic Yellow 21 0.5 $> a _o P _e , 0 "I _e Basic Blue 45 1 _t 5 # aF, sodium sulfate 10 Ji aF _t acetic acid 1 # ad?". " Retarder JLevegal PAU (Farbenfabriken Bayer AG. _F Leverkusen) 1.8 ° a »F, ₉ liquid ratio 1 / 20p with the liquor temperature rising gradually from 60 to 85 ° C within a period of 40 minutes, whereupon another dyeing at 85 ° follows C for another 10 minutes and then within 20 minutes, the temperature of 85 ° 0 is increased to about 100 ⁰ C, whereupon follows a further staining for 30 minutes at about 100 ⁰ C. If the yarn obtained is treated further as above, the beneficial effect of cross-dyeing is not obtained, since the dye from the yarn dyed first bleeds to a large extent and stains in the yarn dyed last and the entire product takes on a smooth greenish tint.

BAD ORiGiNAL

009 8 52/2001

EXAMPLE 5

To 1OD .Seilen a dyeing liquor 0 »3 parts 6" I · Acid Black 131 be given, and a Exlan DK fiber (Japan Exlan Company ütd ,,. _T Japan) is dyed under conditions shown in Table I for 2 hours "The soaps the colored

Fiber wjbrd M * 1 g / l iJoigen HC (Daiichi Kogyo Seiyaka. Co., Ltd., Japan) "at a liquor ratio of 1/20, a Seiiperatur of 6O ⁰ C for 30 minutes conducted long · The fiber nird flrelmal washed and in each case with 50 times the ifeage of water, based on the fiber. Finally, the fiber is oiled and dried. The results of the above hardening are summarized in Table I _o .

009852/2001

TABIILLE

W.
O
ο
i
Z NOo Dyeing conditions Salt ratio 1/15 •
Tint of hue I. I. Bath temperature
( ⁰ O no 1/15
1/15 dyed fiber
Y value pale gray ti
I. ό
ο ■■ ■ ■ III 100 no
1 part sodium
iulphate 1/15 17.8 deep gray
almost sQhwara co
co
cn
Κ » IV 120
120 2 ropes of sodium
sulfate 1/15 4.21
1.42 grabs Bohwarz 001 V
; 120 1 rope calcium
chloride 1.28 deep black 120 1.06

The tint of the colored fibers is expressed as a Y value (#) _? what the tint of a sample means * that relating to the tristimulus values on the basis of the blue-black standard plate (Xs 2.90 #, Y: 2.90 #, Z: 5 »55 #) by means of a color differential meter (Japan Color Machines, Ltdo, model CM 20) is measured: "The sample is practically completely black ^ if its Y-value is less than 1 # 1Ö? S ·

From Table I it can be seen that under the dyeing i _f d _e h "at a Pärbeflottentemperatur voii 100 ⁰ C and in the absence of salt, the fiber is dyed only to a faint tinge, and that at a Flottentemgeratur of 120 ⁰ C as described in the conditions II, the diffusion of the dye is favored even in the absence of the salt, with the result that although the final shade is a dark, rich gray, it is nevertheless impossible to obtain the desired black product. almost black fibers can be obtained when sodium sulfate was added as an alkali salt, as in the case of conditions III and Vi black fiber can be obtained », '

009862/2001

i) 10 parts of the fiber initially dyed under the dyeing conditions Y were mixed-spun with 90 parts of undyed Exlan DK fiber, and the resulting speckled (marble-lined) roving was dyed under the following conditions: cationic dye C ₀ I. Basic Blue 1 O ₉ 2 # avFo , Acetic acid 1 $> a "F" ₍ sodium sulfate 10 £ aF, third-octave storage medium LAlST (Ed. Du Pont de, Nemours, USA) 3 # aF ·, liquid ratio 1/50, the bath temperature gradually increasing from 60 to about 100 ^° C. 60 minutes rose, and the dyeing was continued for a further 30 minutes at about 100 ^° C. The dyed fiber was washed with water and then dried The dye adsorbed first would have bled out, and the second dyed portion of the same fiber took on a glossy pale blue tint, thus creating an extraordinarily beautiful multicolored bevel r can be obtained.

On the other hand, a first dyed fiber was made by an Exlan SE fiber was dyed using a bobbin dyer under the following conditions: more cationic

009 8 52/2001

Dye Snmiacryl black FFP (Sumitomo Chemical Co., Ltd. ·, Japan} 5 i> a * F, _f sodium acetate 1 $> aF _e, Flüssigkeitbverhältnis t / 20, at a liquor temperature that gradually increased from 60 to about 10Q ⁰ C within has exceeded 40 minutes, the coloring -more 90 minutes at about 100 ⁰ C continued ο the above fiber was then mixed with unstained Exlan DK Paser in the same manner as above. It was festgestelltf that the roving obtained by dye from the first colored laser bleeded out, got an unusually strong flake formation and took on a hardly marketable appearance, /

EXAMPLE 6 - '

0.53 part of CibaLan Brilliant Hau (pre-metallized acidic dye type 1: 2 from Ciba Ltd., Schweis) was added to 100 ropes of a dye liquor, and 6.7 parts of Exlan L fiber (Japan Exlan Company, Ltd.) were added to the fleet immersed _β staining was carried out for 2 hours at 120 ⁰ C. In carrying out this dyeing, the various water-soluble inorganic salts of Table IX were added to parts of the liquor mentioned above.

BAD OBKa »NAL

Ö09852 / 2001

• and the coloring results were compared. The tints of the stained samples were compared according to the Eubelka-Munk-IOrmel. The results, in E / S ₈ are shown in Table II.

TABEL II , 2 . 46.4
K / S (mmol) Amount of ,8th 2.0 92.8 Inorganic salt Control rS 2.4 5.2 Sodium chloride 0.5 inorganic salt _S 1 5.8 5.7 Sodium sulfate 0.5 23 , 2 4.4 5.9 Barium chloride O ₉ 5 1 rl ' 4.2 5.2 Zinc chloride 0.5 1 , 0 5.4 4.9 Magnesium chloride 0.5 5 6.0 Calcium chloride 0 * 5 4th 4th 5

The tint of the dyed fiber is represented by the 2 / S value obtained by measuring the reflectance R of the dyed fiber at the wavelength of 580 millimicrons iind is then calculated by the following equation:

E / S - _: (1 - S) ² / 2R

SAD

985 2/2001

If the staining is done without salt, it is done on the fiber merely stains while adding Salt favors the coloring. Next will be regardless of the kind of salt »the fiber is colored thankfully as the amount of salt increases. The use of alkali salts, such as sodium chloride, Sodium sulfate and the like give E / S values ranging from 1.6 to 3 »7, which are pale to medium Color tones correspond to »When adding water-soluble salts of divalent metals are the K / S values of the fiber obtained at least equal to 4.0 or higher, doho that the fibers are darker than are dyed in medium shades (see Table II).

On the other hand, gate yarns were made by spinning 15 parts each of the dyed fiber prepared as above with 15 parts each of Exlan DK undyed fiber (Japan Exlan Company, Ltd.) *, and the obtained gate yarns were made into knitted fabrics. This knitted fabric was then dyed under the following conditions: the cationic dye Sumiaoryl Orange G (Sumitomo Chemical Go., Ltd., Japan) 0.4 i> aP _ef esaetic acid 1 £ aF ,, liquid ratio 1/50, with gradually increasing temperature Fleet of 60 on

BATH

90 ⁰ O within 30 minutes, the staining continued for a further 60 minutes. The dyed products were then washed and dried. In the case of the final, differently colored knitted fabrics, the invention resulted in better-dyed products with a brilliant multicolored pattern - of blue and orange-yellow.

EXAMPLE 7

Exlan L fiber (Japan Exlan Company, Ltd.) was dyed for 120 minutes using a liquor containing a premetallized acidic dye type 1: 2 and a water-soluble inorganic salt at a liquid ratio of 1: 20 and at a temperature of 120 ⁰ Co the colored in this way fiber bow ie uncolored Exlan L fiber was spun into roving was then added to a single gate yarn mis ohgef eight in which the two components were arranged in a symmetrical pattern. This latter twine was then misoh pied to produce a fiber with a mottled (marbled) pattern. This fiber was then dyed under the following conditions; Sumiaoryl Brilliant Selb 5 G (Sumitomo

BATH

009852/2001

■ fßT9595

OheiBical Go », Ltd *) O ₈ 5 S a <, F. _? Acetic acid $ 1. a * F. »., - Liquid / bit ratio i /? Q0 ₉ at a bath temperature of ₉ the aHmahliea rose within 30 minutes τοη 60 to 9Ö ^Ö C, whereupon it boiled for a further 60 minutes

the · PIeekenMläung des? TorscMeden colored
the Is: are made in the manner described .., "- is summarized in Salselle HI»

the

added salt

concentration
(

concentration

the suerat
colored
Fiber through
2 «staining

Pleckenbiläo

dsr as second gefärM «5a

Saser "flsrek Aupblutea des

! »Dye ,,

fttea E

{BÄSl ¹ }

Bath 219

■ 4

BaCl

BsCl

2'-

BaCl,

20. 20

20th

20 20

-

"4

4 ~ 5

4-5

.3-4 4-5

4 - 5

From Table III it is seen that in all cases, virtually no floc formation takes place by bleeding of the first dye f that, however, the FIeckenbildung the first dyed fiber see through those used in the second coloring katlonl · "dye is alleviated considerably when the water-soluble salt of a divalent Metal is used «

In the above example, the degree of staining was determined as follows: a dyed acrylic fiber and the same undyed fiber were each weighed exactly to 1 g, and both fibers were placed in a flask fitted with a reflux condenser and at a liquid ratio for one hour cooked by 1/50. After this treatment, each of the two fibers was dried at a temperature below 60 ⁰ C. The flocculation of the undyed fiber was evaluated by the AATOC card fOr measuring the transfer of ink or the geometric stain scale, and the values obtained were placed in rows. The value 5 represents the best result, and with falling values the staining becomes high.

BATH ORIGINAL 0098 52/2001

Claims (2)

p AiE sr τ a ir s ph ü c η ε: ■ -.- ■■ - 1 ο method for dyeing textile material made of acrylic synthetic fiber to a multicolor pattern, characterized in that a textile material made of acrylic fiber, which contains acidic groups but no basic groups »with a door-metallized acidic dye of the type 1: 2 in a bath that has at least one water-soluble contains an inorganic salt of a monovalent metal, a divalent metal or an ammonium salt, ^{dyes at a temperature of 100 0} C or more, combines the textile material dyed in this way with an undyed identical or similar textile material, and the composite with a cationic dye for coloring the undyed textile material colors in a conventional way 2. The method according to claim 1, characterized in that that at least one water-soluble inorganic salt is one monovalent metal or an ammonium salt in the first Dye liquor is present in an amount of 1.0 to 5% by weight 3. The method according to claim 1, characterized in that that at least one water-soluble inorganic salt is one Ö0985 2/2001 divalent metal in the first liquor in an amount of 0.5 "to 5s, 0 wt _o - # is present» 4ο method according to claim 2, characterized in that that the inorganic salt used is sodium sulfate, sodium chloride, ammonium chloride, ammonium sulfate or potassium sulfate will" 5ο method according to claim 3 »characterized in that that calcium is the inorganic salt of divalent metals » chloride, barium chloride, zinc chloride, magnesium chloride, Cadmium Chloride, Zinc Sulphate, Magnesium Sulphate, Zinc Nitrate, Oadmium nitrate or calcium thlocyanate is used o 8A0 00985272001