AU427409B2 - Process for producing multi-colour dyed acrylonitrile textile products - Google Patents

Description

i. invention relates to a process for produclneg multi-color dyed acrylonitrile textile products having two or more different shades and more particularly to a process for producing multi-color dyed acrylic textile products having two, three, four or more different shades very remarkable in the tone-on-tone effect and/or multi-color contrasting effect by multi color-dyeing in one step in one bath a textile product containing treated fibers obtained by treating with an anionic active agent acrylonitrile synthetic fibers (hereinafter referred to as "basic group- containing acrylonitrile fibers") consisting of an acrylonitrile copolymer made by copolymerizing a basic ethylenically unsaturated monomer having a basic nitrogen atom with acrylonitrilt and untreated above mentioned basic group-containing

acrylonitrile fibers, in a.dyeing bath containing anionic dyes.

Prior to the present invention, there have been proposed various methods for producing multi-colored textile products. For example, there has been proposed a method wherein two fibers previously dyed in respectively different colors are blended and spun into a multi-colored yarn, which is then woven, knitted or otherwise organized into a multi-colored textile product. Another known method comprises the steps of blending a' dyed fiber and undyed fiber, spinning the resulting blend into a yarn, then dyeing the undyed fiber, prior to or subseuqent 1 to fabrication into a textile product, with a dye different in color from that employed for the previously dyed fiber. In still another method, fibers with different dyeing properties are blended, the blend is spun into a yarn, and then the yar or an article made therefrom is dyed taking advantage of the different dyeing properties to yield a multi-colored textile product. 2 4274 2 427409-

J

However, in a process for producing

multi-color dyed textile products by using fibers of the same

dye-ability, that is, dyeable with the same kinds of dyes,

it has been difficult to vary the dyeability of said

fibers with an after-treatment so that it has been dif-

ficult to develop a multi-color or ton-on-tone effect

between said fibers of the same dyeability by dyeing in

one bath and further it has been very difficult to produce

a multi-color dyed product by combining such fibers dye-

able with the same kinds of dyes with various other fibers.

Therefore, a main. object of the present invention

is to obtain a multi-color dyed acrylonitrile textile

product having two or more color shades, excellent in the

tone-on-tone and/or multi-color contrasting effect,

very remarkable in the aesthetical performance and high

in the commodity value.

Another object of the present invention is to

provide a method wherein atone-on-tone and/or

multi-color effect can be developed between basic group-containing

acrylonitrile fibers in a textile product containing the basic

group-containing acrylonitrile fibers.

Other objects of the present invention will become

clear from the following description.

The above mentioned objects of the present invention

are attained by one-bath-dyeing (competitively dyeing) a

textile product containing treated fibers obtained by

treating basic group-containing acrylonitrile fibers with an

anionic active agent(anionic aromatic polycondensate

2 n.4 C-c ain :i c fonic -id groups) and (b) untreated basic Group-containing acrylonitrile fibers in a dyeing bath containing anionic dyes.

In the basic group-containing acrylonitrile fibers treated with an anionic active agent in the present in-

vention, the basic groups which constituted dye sites

are blocked with the anionic activeagenso that the

amount of the basic groups which can substantially

bond with an anionic dye is decreased. Therefore, in cases

a textile product containing both of said treated and

untreated basic group-containing acrylonitrile fibers is

dyed (competitively) in one step in one bath with an anionic

dye, due to the difference in the exhaustion and dyeing

rate with the anionic dye, there is developed atone-on

tone and/or multi-color contrasting effect very high in

the aesthetical performance. Particularly, when two or

more anionic dyes are used as mixed a multi-color con-

trasting effect is developed. It is though that diff-

erent shades develop due to the differences of the dyes

in the chemical struc-ture and the affinity with the fiber.

In the; present invention, basic group-containing

acrylonitrile fibers treated with an anionic active agent and

untreated basic group-containing acrylonitrile fibers

are assembled into a textile product by usual spinning,

weaving or knitting operation such as blending, mix-spinning,

mix-plying, blend weaving or blend-knitting together with or

without other fiber (a third component) such as an acrylonitrile

fiber containing dissociable acid groups, polyester fiber,

polyamide fiber or wool. Thus, the "textile product" means

such fiber assembly as spun yarns or knit or woven fabrics

28.1 68 71, and articles made therefrom. Then the textile product is

competitively dyed under general dyeing conditions in a

dyding bath.(to which a dye for dyeing the third component

may be added when necessary) containing an anionic dye,

so that the valuable tone-on-tone and/or multi-color

contrasting effect of the present invention is imparted

to the textile product.

The basic group-containing acrylonitrile fibers

to be used in the present invention are those to which an

*iionic dye-dyeability is imparted by introducing into the

acrylonitrile copolymer (forming said fiber) basic nitrogen-

containing comonomer(s) such as vinylpyridine or alkyl

substituted vinylpyridine, e.g. 2-vinylpyridine, 3-vinyl

pyridine, 2-vinyl-3-methylpyridine or

pyridine; n-vinyl substituents of a nitrogen-containing

heterocyclic compound or derivatives thereof, e.g. N-

vinylimidazole compound, N-vinylpyr6lidone, N-vinylmorph-

olinone or N-vinyloxalidinone; or other basic ethylenically

unsaturated monomers having a basic nitrogen atom such as

an ethylenically unsaturated monomer represented by the

following general formula

0 R i 2 CH C C -0 (CH2 N (I) R 3

wherein R i represents hydrogen or a methyl group, each of

and n R 2 and R 3 represents a methyl or ethyl group

represents an integer of 2 to 4 or the general formula (II) 0

c C 0 R5 X- (II) 2 I R4

wherein R 4 represents hydrogen or a methyl group, R

281 68/71 represents an alkylene group of 2 to 4 carbon atoms,

hydroxy-alkylene group or (-CH 2 CH2 OCH 2 CH-_ group, each of/ R7 and R represents a methyl, ethyl or propyl group and X represents an anion.

Further, in order to improve the properties of

said fiber, the fiber forming polymer may also contain

any one or more neutral monoethylenically unsaturated

monomers such as methyl, ethyl, propyl and butyl'esters

of acrylic acid and methacrylic acid; vinyl esters of

carboxylic acids (vinyl formate and vinyl acetate);

acrylamide and methacrylamide and their derivatives; vinyl or vinylidene halides (vinyl chloride, vinyl bromide

and vinylidene chloride); styrene and cyanostyrene and

the like.

When a basic group-containing acrylonitrile

fiber consisting of an acrylonitrile copolymer containing

a basic ethylenically unsaturated monomer represented by the

above mentioned general formula is used, the multi-color

containing effect is further elevated and an excellent

multi-color dyed product high in the commodity value is

made. However, if an acid ethylenically unsaturated

monomer containing acid dissociable group such as sulfonic

acid group or carboxyl group is copolymerized in the acrylonitrile

copolymer forming the above mentioned basic group-containing

acrylonitrile fiber, the effect of the present invention

will be reduced. Therefore, the use of such acid monomer

should be avoided.

However, when persulfate, sulfite or bisulfite is

used in the polymerization initiator system in producing said copolymer, a slight amount of such dissociable acid

2 8.1 8 /71 group as sulfuric acid group or sulfonic acid group will be introduced into the terminal of the above mentioned basic group-containing acrylic fiber-forming polymer but this will have no influence on the effect of the present invention. Further, the basic group-containing acrylonitrile fibers to be used in the present invention may well be fibers obtained from a composition prepared by blending a homopoly- mer of the above mentioned basic ethylenically unsaturated monomer or a copolymer of the same with acrylonitrile and/or a neutral monoethylenically unsaturated monomer and an acryl- onitrile polymer (an acrylonitrile homopolymer or copolymer with the above mentioned neutral monoethylenically unsatur- ated monomer).

It is preferable that the copolymer or polymer blend for forming the basic group-containing acrylonitrile fibers contains at least 75% by weight of acrylonitrile, 0.5 by weight.of the basic ethylenically unsaturated monomer(s) and 0 15% by weight of the neutral monoethylenically unsat- urated monomer(s).

The acrylonitrile fiber containing dissociable acid groups to be blended, mix-twisted, blend-woven or blend- knitted, as required, together with a basic group-containing acrylonitrile fiber treated with an anionic active agent and an untreated basic group-containing acrylonitrile fiber is a fiber dyeable with a cationic dye. The fiber containing dissociable acid groups is formed from an acrylonitrile homo- polymer or copolymer into whose molecular terminal such dis- sociable strong acid groups as a sulfuric acid group and sulfonic acid group are introduced by using persulfate, sul- fite or bisulfite in the polymerization initiator system 7 427409 which is a step in producing an acrylonitrile homopolymer or copolymer. The acrylonitrile fiber containing dissoc- iable acid groups is also formed from an acrylonitrile co- polymer made by copolymerizing acrylonitrile with an ethyl- enically unsaturated monomer containing a sulfonic acid group such as styrenesulfonic acid, vinylsulfonic acid, allylsulfonic acid and methallylsulfonic acid or their salts or a carboxylic acid group such as acrylic acid, methacrylic acid and itaconic acid or their salts. The above described basic unsaturated monomer is not contained, as copolymerized, in said fiber forming polymer.

It is preferable that the copolymer for forming the

acrylonitrile fibers containing dissociable acid groups con-

tains at least 80% by weight of acrylonitrile, 0.01 5% by weight of said ethylenically unsaturated monomer containing sulfonic acid groups or carboxylic acid groups and 0

by weight of at least one neutral monoethylenically unsatur-

ated monomer. The anionic active agent to be used in the present invention is essesntally anionic aromatic polycondensate

containing dissociable aeid g-oup auh as a sulfonic acid group. Examples of such anionic active agent are a naphthal- enesulfonic acid-formaldehyde condensate represented by the

chemical formula:

427 409

2 8. 168 /71

NaO 13---3Na

water-soluble products obtained by reacting a formaldehyde

condensate of a polyhydric phenol or polyhydric phenol

carboxylic acid with a sulfite (Japanese Patent Publication

1 t

No. 7044/1968); sulfomethylate of a condensation

product of di(4-hydroxyphenyl) sulfone and a lower aliphatic aldehyde (Japanese Patent Publication No. 24205/1968); water-soluble polycondonsate obtained by

heating bisphenol sulfone or its derivative and an aro- matic sulfonic acid in an acidic "endition'in -tje pre- ,sence :of formaldehyde (Japanpese Patent -Publication No. -9424/'1966); p aequ ousolution of an alkali salt or ammonium salt of a condensation product of a lower ali- phatic aldehyde and a sulfonic acid of dioxydiphenyl sulfone (Japanese Patent Publication No. 24231/1965); reaction product of 2,2'-bis(hydroxyphenyl) sulfone and pxymethane sulfonic acid (French Patent No. 1,274,939); bi st4,4'-dihydrpxyphenyl)-sulfone as sulfonated and con- 4gnsed with formaldehyde (British Patent No. 975,307) or trimethylol monomethane-sulfonic acid compound of.4,4'- diphenyl-dimethylmethane Patent No. 2,522,569). In the as of treating anaaesyfe synthetic fiber consisting of an acrylonitrile copolymer containing the above mentioned basic group-containing unsaurated monomer with a treating solution containing at least one of such anionic active agents as are described above, proper values of the: mount of use of the treating agent and the treating conditions (such as the pH and temperature) are to be determined depending on the kind of the treating agent and it is difficult to directly limit the ranges. However, generally, in order that the treating solution containing an anionic active agent may be kept under an acidity (preferably, pH 2.0 7.0) and the treating effect of the treating agent may be accelerated, it is necessary

S0 427409 to treat it at a temperature above 600 C. The amount of the treating agent in the treating solution may be about 0.1 20%, preferably 0.4 10% by weight based on the dry weight of the fibers to be treated. In order to adjust the pH of the treating solution, an organic or inorganic acid such as acetic acid, oxalic acid, formic acid, hydrohloric acid, sulfuric acid, nitric acid, etc, may be used. The anionic dyes to be used in this invention are acid dyes (including pre-metallized acid dyes), mordant dyes and directed dyes. More particular examples of such dyes are C.I. Acid Yellow, C,I. Acid Red, C.I. Acid Blue, C.I. Acid Brown, C.I. Acid Orange, C.I. Acid Violet, C.I. Acid Green, C.I. Acid Black, C.I. Mordant Yellow, C.I. Mordant Orange, C.I. Mordant Red, C.I. Mordant Violet, C.I. Mordant Blue, C.I. Mordant Green, C.I. Mordant Brown, C.I.Mordant Black, C.I. Direct Yellow, C.I. Direct Orange, C.I. Direct Red, C.I. Direct Violet, C.I. Direct Blue, C.I. Direct Green, C.I. Direct Brown, C.I. Direct Black, etc. Most preferable are acid dyes. Examples of cationic dyes to be used for dyeing the third component fibers acrylic fibers having dissociable groups) are C.I. Basic Blue, C.I. Basic Orange, C.I. Basic Red, C.I. Basic Brown, C.I. Basic Yellow, C.I. Basic Violet, C.I. Basic Green, etc. The C.I. names as used above and those indicated in the following Examples are those of Colour Index, 2nd Edition, 1956, and Supplement 1963, published by The Society of Dyers and Colourists, Bradford, England, and The American Association of Textile Chemists and Colorists, Lowell, Mass., U.S.A. 1 2740

28 1 '71 The invention will be illustrated in the following Examples wherein all percentages and parts are by weight unless otherwise specified. In these Examples, means weight percentage based on the weight of the dry fiber.

Example 1 265 parts of biophenol sulfone were homogenously mixed with 220 parts of P-naphthalenesulfonic acid, and 2 parts of concentrated sulfuric acid were added to the mixture. Then 105 parts of 30% aqueous solution of form- aldehyde were gradually added thereto, and the mixture was stirred to react at 1100 C. for 2 hours and was neutralized. Then a saturated solution of sodium sulfate was added thereto, the produced polycondensate was salted out, separated and taken and was then dried to be powder. In a treating bath prepared by adjusting 2.5% o.w.f. of the thus obtained polycondensate to be of a pH of 3.0 with sulfuric acid, an undyed basic group-containing acrylic fiber (which is referred to as "fiber A" hereinafter) shaped from an acrylo- nitrile copolymer consisting of 90% acrylonitrile, 7% vinyl acetate and 3% N,N-dimethylaminoethyl methacrylate was heated at a rate of 10 C./min. from 700 C. to about 100 0 C., for 60 minutes and was then quenched. The treated fiber was then washed with water and dried. parts of the thus obtained anionic active agent- treated fiber A, 30 parts of the untreated fiber A and parts of an acrylic fiber (made from an acrylonitrile copolymer consisting of 90% acrylonitrile, 97% methyl- acrylate and 0.3% sodium allyl sulfonate: the fiber will be referred to as fiber B hereinafter) containing dissociable

427 409 r 1 /71 acid groups and dyeable with basic dyes were blended and spun into a yarn and then a coarse knit fabric was made of the yarn. Said knit fabric was multi-color dyed (competitively dyed) in one bath by being heated at a rate of about 10 C./min. from 600 C. to about 100°C. and kept at 100 0 C. for 45 minutes at a prescription of 0.2% o.w.f, C.I. Basic Yellow 28, 0.3% o.w.f. C.I. Basic Yellow 13, 0.4% o.w.f. C.I. Basic Blue 3 and 1% o.w.f, Levenol R (product of Kao Soap Co.) as a retarder on the fiber 1% o.w.f. C.I. Acid Blue 62 on the untreated fiber A, 5% sodium sulfate on the total fiber weight, 1 of a nonionic surface active agent: Noigen ET 170 (product of Daiich. Kogyo Seiyaku Co, Ltd.), a pH of 3.0 (adjusted with H2 SO4 and a liquor ratio of 1/50,. The thus obtained multi-colored knit fabric was a three-different colored product in which deep blue and light blue were present as mixed on a green ground. Sub- stantrally no inter-staining of the different colored fibers forming said fabric wa.s observed and the multi- color contrasting .effect was excellent. -Example 2 The fiber A treated with the anionic synthetic water-soluble polycondensate containing bisphenol sulfone, untreated fiber A and fiber B in Example 1 were respectively blended and spun to make three kinds of blended spun yarns having a single yarn count of 7. Three of each of the obtained three kinds of blended spun yarns were arranged to be an inter-twisted yarn and then the yarn was tufted on a hemp base cloth to make a carpet having looped piles

13 27 40 9

2 8,1 68 /71 having a gauge of 5/32, 9.5 yarns /25 mm. stitch and a pile height of 10 mm. except the thickness of the base cloth. Then the obtained carpet was multi-color-dyed using the wince dyeing machine in one bath according to the below mentioned recipe. The percentages of the dye and assistant were by weight on the total weight of the carpet. Dyeing recipe Acid dyes: C.I. Acid Yellow 49 0.3 C.I. Acid Red 99 1.3 Catiohic dyes: C.I. Basic Yellow 14 0.03% C.I. Basic Red 39 0.53% C.I. Basic Blue 65 0.008% Cationic retarder: Panalon E (product of Ipposha Oil and Fat Co.) 0.5 Dyeing assistant: Sodium sulfate 10 Noigen ET 170 (nonionic surface active agent) 1 g./l. Dyeing pH (adjusted with pH 3 H2 SO4 Dveing temperatures: From 60 0 C to 90 0 C. elevatsd at a rate of 1 C./min. At 90oC kept for 60 min. From 90 C to about 100°C elevat d at a rate 8 of 1 C./min. At about 1000 C. kept for 60 min. From about 100°C to reduceg at a rate C. of 1 C./min.

The thus obtained multi-colored carpet was a

427 4 0 9

2 81 f 8 ni three-different colored product mostly in a carmine

tone, dyed in light red in the treated fiber A part,

in deep red in the untreated 'fiber A part and in carmine

in the fiber B part, very excellent in the deep and light

multi-color contrasting effect, giving an image of a high

class article. Example 3

In a treating bath containing 10% o.w.f. of an

anionic active agent having the structure of the below mentioned formula CH2

and adjusted to be a pH of 3.5, the fiber A was immersed. 0 The bath was heated to the boiling temperature from 60 C. 0 at a rate of.1 C./min. during 40 minutes and was maintained

at this temperature for 60 Minutes. Then the bath was

quenched, and the fiber was washed with water and then dried.

parts oi the thus obtained treated fiber A,

parts of the untreated fiber A and 60 parts of the basic

dye-dyeable fiber B were blended'and spun to be a spun yarn

and a coarse knit fabric was made of the yarn. Said knit

fabric was multi-color dyed in one bath by being heated 0 0 from 600 C. to 100 C. at a rate of about 1 C/min. and kept

at this temperature for 45 minutes at a dyeing recipe of

0.2% o.w.f. C.I. Basic Yellow 28, 0.3% o.w.f. C.I. Basic

Yellow 13, 0.4% o.w.f. C.I. Basic Blue 3 and 1% o.w.f.

Levenol R on the weight of the fiber B, further 1% o.w.f.

Ir 27' 4 09

2 8.1 68 /71 C.I. Acid Blue 62 on the weight of the untreated fiber A and 10% o.w.f. sodium sulfate and 1 of Noigen

ET 170 on the total weight of the fibers, a pH of (adjusted with H2 SO4 and a bath ratio of 1/50. The

thus obtained multi-colored knit fabric was a three- different-color dyed product in which thick blue and thin blue were present as mixed on a green ground. The

multi-color contrasting effect was excellent. Example 4

A blended spun yarn consisting of 50 parts of the fiber A treated with the anionic active agent and 50 parts A of the untreated fiber/in Example 1 was dyed in one bath with each of various acid dyes shown in Table 1. It was

dyed according to the temperature elevating method in Example 1, at a liquor ratio of 1/100 in a dyeing bath in which 1% o.w.f. of each dye was used on the untreated fiber A and 10% o.w.f. sodium sulfate and 1% o.w.f. acetic acid were added as dyeing assistants. All the thus dyed blended spun yarns were products in which such multi-color or tone-on-tone effects as are shown in Table 1 were imparted, the aesthetical performance was very favorable. Further, it has become clear from Table 1 that, by utilizing the combination of acid dyes, that is, the fact that there is a difference between the affinities of the acid dyes with the fiber A, not only the tone-on-tone effect but also the multi-color effect can be developed. That is to say, when both of a dye low in the affinity and a dye high in the affinity are used, on the treated fiber A, only the dye high in the affinity is deposited and the

427409 shade of said dye is developed, whereas, on the untreated fiber A, both of the dye low in the affinity and the dye high in the affinity are deposited and therefore a mixed color of said two kinds of dyes is developed and thus a multi-color dyed product is obtained.

Table I

Shade

Untreated Treated Acid Dyes Fiber A Fiber A Effect C.I. Acid Yellow 49 Reddish Multi- C.I. Acid Red 133 orange Yellow color effect CI, Acid Red 57 Reddish Multi- C.I. Acid Yellow 42 orange Yellow color effect, C.I. Acid Red 57 3 Deep Light reddish Tone-one C.I. Acid Yellow 49 reddish tone orange orange effect C.I. Acid Blue 23 4 Multi- C.I. Acid Yellow 49t Green, Yellow color effect C.I. Acid Yellow 42 Green Multi- C.I. Acid Blue 62 Blue color effect

6 C.I. Acid Blue 62 Deep Light Tone-on C. 1. Acid Yellow 49 green tone green effect 7. C.I. Acid Blue 62 Purple Multi- C.I. Acid Red 133 Blue color effect Acid Red 57 8' C.I. Acid Blue 23 Purple Red M~ul colorti- effect C.I. Acid Red 57 C.9I. Acid Deep Light Thich- Acid Blue Blue 62 62 purple purple ness effect 4 27 4 0

Claims (1)

1. 28 /71 The claims defining the invention are as follows:-

   1. A process for producing a multi-colour dyed acrylo-

   nitrile textile product characterised by the fact that an

   acrylonitrile textile product containing treated

   fibers obtained by treating with an anionic active agent,

   selected from Q-e&t y anionic aromatic polycondensates

   containing sulfonic acid groups, acrylonitrile fibers con-

   sisting of an acrylonitrile copolymer made by copolymeriz-

   ing a basic ethylenically unsaturated monomer, having a

   basic nitrogen atom, with acrylonitrile and untreated

   acrylonitrile fibers as defined in is dyed in a single

   bath containing an anionic dye.

   2. A process as claimed in Claim 1 wherein the acrylo-

   nitrile fibers are prepared from a copolymer comprising

   at least 75% by weight of acrylonitrile, 0.5 10% by

   weight of at least one compound of the formula: 0

   SR 3 1 3

   (wherein R1 is hydrogen or methyl group, each of R 2 and R

   is methyl or ethyl group, n is an integer of 2 to 4 in-

   clusive) and 0 15% by weight of at least one neutral

   monoethylenically unsaturated monomer.

   3. A process as claimed in Claim 1 wherein the anionic dye is selected from the group consisting of acid dyes,

   mordant dyes and direct dyes.

   4. A process as claimed in Claim 1 wherein the anionic

   active agent is a water-soluble polycondensate obtained by

   heating bisphenol sulfone or its derivative and an aromatic

   sulfonic acid under acidic conditions in the presence of formaldehyde. is 4 27409

   2.1 6 71 A process as claimed in Claim 1 wherein the treatment with the anionic active agent is conducted with an aqueous solution of pH 2 7 containing the said anionic active agent in an amount of 0.1 20% based on the weight of the dry fiber at a temperature above

   6. A process as claimed in Claim I wherein a textile product containing the acrylonitrile fibers treated with an anionic active agent selected from eeis ily an- ionie aromatic polycondensates containing sulfonic acid groups, the untreated acrylonitrile fibers and (c) acrylonitrile homopolymers or copolymers having disscociable acid groups, is dyed in a single bath containing an anionic dye and cationic dye.

   7. A process as claimed in Claim 6 wherein the acrylo- nitrile copolymers containing dissociable acid groups comprise at least 80% by weight of acrylonitrile, 0.01 by weight of an ethylenically unsaturated monomer con- taining sulfonic acid groups or carboxylic acid groups and 15% by weight of at least one neutral monoethylenically unsaturated monomer.

   Dated this 25th day of July, 1972

   JAPAN EXLAN COMPANY LIMITED By their Patent ttorney:

   of GRIFFITH, HASSEL &.FRAZER

   42 7 a4 0 9