DE2120387C3 - Process for the production of multi-colored dyed wool-containing acrylic textile products - Google Patents

Description

CII, CC ■ O ■ (CIL) ,, N
R,

R.

35

where K _{1 is} hydrogen or a methyl group, R ₂ and Rj are each a methyl or ethyl group, η is a whole number from 2 to 4, and 0 to 15 weight percent of at least one neutral, 1110110-ethylenically unsaturated monomer as acrylic fiber.

3. The method according to claim 1, characterized in that that the dyeing with the acid dye is carried out at a pH of 2-5.

4. The method according to claim 1, characterized by the use of a water-soluble Polykoiulensats, that by Frhilzen \ on Bisphcnolsilfon or its derivative and an aromatic sulfonic acid under acidic conditions in the presence from formaldehyde as an anionically active agent.

5. The method according to claim 1, characterized in that * the treatment with your anionic active agent by treating the textile product with an aqueous acidic solution of a pll-Wcrlcs \ on 2 to 7, which are the anionically active Agent in an amount of 0.5 to 10 ", based on the weight of the dry I aser, contains a 'temperature above W) C is carried out.

(>. Process for the production of a multicolored dyed wool-containing acrylic textile products. after Claim I his χ characterized in that daü here a Tcttilprodukl is used, besides the aforementioned lasers still use acrylic fiber !! with dissolvable acid groups (c) and in the! -dye bath, which contains the acid dye, another cationic dye in combination will.

7. The method according to claim 6, characterized by the use of a copolymer with at least 50 percent by weight of acrylonitrile, 0.01 to 5 percent by weight of an unsaturated one Monomers with sulfonic acid groups or carboxyl groups and 0 to 15 percent by weight at least a neutral mono-ethylenically unsaturated monomer made with acrylic fibers acid groups capable of dissociation as additional fiber material (c).

The invention relates to a method of manufacture a multi-colored, wool-containing Acrvl textile product, which is particularly notable for two or more different shades of color with one Multicolored contrast effect distinguishes.

Various methods of making multicolored textile products have been proposed. So was z. B. proposed a method previously mixed in respective different colors of dyed fibers in which two and spun into a multi-colored yarn are that then a multicolored Textilprodiikt is processed by weaving, knitting or in other ways n \. Another known method involves mixing a dyed and undyed fiber, spinning the resulting mixture into a yarn and then dyeing the undyed fiber before or after processing into a textile product with a dye different from the color of the first dyed Fiber used is the dye. In a further method, fibers with different dyeing properties are mixed, the mixture is spun into a yarn and the yarn or the product made from it is then dyed using the different dyeing properties in order to obtain a multicolored textile product.

However, it was very difficult to find a multicolored ElTekl by multicolored dyeing of a textile product with different fibers of the same dyeability, d. H. one Tcxlilproduct made from different fibers with one Coloring activity with the same kinds of dyes, with the same kind of dyes to develop. Furthermore, it was difficult to obtain a multi-colored dyed textile product by combining such la scm, which are dyebai with the same kind of dyes are to be made with various other fibers, even if, for example, an active or painful weave with an acrylic fiber and wool containing basic groups in two baths with anionic dyes! with a staining activity towards the two artefacts is colored by fibers in different colors, ν it colors the dye during later dyeing the zuui dyed fibers, on the other hand, the dye seeps through the previously dyed fiber and discolors the later colored I aser. That is why the multicolored koiurasl effect significantly impaired.

The object of the invention is therefore to create a Multi-colored, wool-containing acrylic Texlilpro dukles with two or more different larbci and an excellent multi-color contrast effect

120 387

This ·: Task is the initially described genus solved by dyeing an acrylic fiber, consisting of a copolymer from acrylonitrile and a basic unsaturated monomer with a /) / C /, - \ Vert at 25'C \ on below K, 0 or from a polymer mixture of homo- or copolymers of the aforementioned basic monomers and homo- or copolymers of Acrylonitrile (a) and wool (bj containing textile product in a dye bath at pH Mm 5 to 9 with a direct fiber / um I am the acrylic fiber content, then treating the textile product with an anionically active agent from the group of aromatic polycondensates with sulfonic acid residues and then dyeing the wool in one change. Color in a dye bath in acidic conditions using an acid dye.

Preferably, a basic unsaturated monomer with a / IAV value of 7.5 or below is used \ used.

Furthermore, the dyeing is preferably carried out with the Di lekifarbsloff at a pH of 6 to 8.

The / »AVWcrl of the fiber is determined as follows:

The fiber is dissolved in dimethylformamide, whereupon the solution obtained in this way has a potentiometric Titration using a sodium hydroxide solution is subjected. This gives the potential (ηιΓ) at half the equivalence point.

Furthermore, various rabbits, whose ρKi, values are known, are dissolved in dimethylformamide. The solutions obtained in this way are titrated potentiometrically with a sodium hydroxide solution to their half equivalents / points. A diagram is then produced which shows the relationship /. between the / »AV values and the potentials in dimethylformamide. From this diagram the /> / w, value, which corresponds to the first determined potential, is obtained.

To determine the amount of acrylonitrile and the basic monomer / u, proceed as follows:

It becomes the infrared absorption spectrum of the fiber determined to analyze quuutilativ / u, of which Type is the base contained in the fiber, i.e. i.e. whether it is a primary, secondary or tertiary Amine or a quaternary ammonium salt.

The fiber is dissolved in dimethylformamide, whereupon the solution obtained in this way is neutralized is titrated with a sodium hydroxide solution. In this way the amount of basic groups is obtained.

On the other hand, the fiber is analyzed for its nitrogen content. The acrylonitrile content is in the Way determined that the basic nitrogen content is subtracted from the nitrogen content. The basic one The monomer content is determined by subtracting the nitrile content determined from the total salary.

When carrying out the dyeing process according to the invention, only the one basic unsaturated Monomercs with a specific base / itäl containing acrylic fiber with a direct dye underneath dyed a specific condition and the obtained textile product containing dyed fibers with a treated anionically active agent, so that the animal-colored laser can be prevented from being drawn Direklfarhsloff can bleed into the dyebath and also that at the same time an acid dye as a dye in a later dyeing process discolors the dyed fiber, and then only the wool content in the aforementioned textile product in a different color at a specific pH range using of the acid dye is colored.

So, according to your ingenious procedure, according to which a basic group-containing acrylic fiber and wool have activity with the same

ίο type of dye spun into a textile product, knitted or blown, a very excellent multicolor contrast effect in the textile product developed and thereby a new HITekl, as it is according to any known conventional multi-color dyeing process is unthinkable, received. This means that it was considered very difficult a multicolor conflicting effect in fibers that have a dyeing activity with the same kind of dyes show / ti develop. According to the invention, however, it is has become possible, a multi-colored dyed textile product with an excellent multi-color contrast and more favorable aesthetic design / u obtained without discoloration or bleeding to release two types of fibers that have a dyeing activity with the same type of dyes, by an acrylic fiber with a basic, unsaturated monomer with a specific basicity and a specific pre-staining condition, specific treatment of the pre-stained lasers and spe- / mixes Re-staining condition is chosen.

The basic groups-containing acrylic fibers and wool to be used in accordance with the invention such a spinning, knitting or weaving treatment such as blending, mixed spinning, formation of mixed layers,

; I5 blended weaving or blending together with or without other fibers (as a third component) such as For example, subjected to an acrylic fiber with dissociable acid groups or polyester fibers, so that they are processed into a textile product

ίο, such as spun yarn or knitted or woven goods. Then the textile product according to the invention is applied to a non-woven textile product Multi-color dyeing process applied. As pre-coloring or pre-coloring with a direct color pen According to the invention, a generally known dye recipe can be used, except that the pH of the dyebath should be in the range of 5 to 9, preferably between (1 and 8. As a second or Post-dyeing with an acid dye A well-known dye can be used except that the pH of the dyebath is acidic, particularly preferably in a range should be from 2 to 5.

The direct and acid dye (including pre-metallized acid dye) can be any of the commercially available ones. Particular examples of direct dyes are those with CI designations such as CI direct yellow, CI Direktgelb (DirectOrange), C. 1. Direct Red, CI Direktviolet (Direct Violet). CI Direct Blue, CI Direct Green, CI Direct Brown and C.I. Direct Black. Particular examples of acid dyes are those with C.I.- designations such as C. 1. Acid Yellow, CI Acid Red, CI Acid Blue, CI Acid Brown, C. i. Acid Orange, C ". I. Acid Violet, CI Acid Green, CI Acid Black, etc.

[The C.I. designations, as sic above and in the are used in the examples given below, come from the Color Indc <, 2nd edition, 1956, and Supplementary volume, 1963, published by The Society of Dyers and Colourists, Bradford, Fngland and The American Association of Textile Chemists and Colorists, Lowell, Mass., USA.

The basic group-containing acrylic fiber to be used in the present invention is a synthetic one Acrylic fiber produced from an acrylonitrile polymer by a conventional spinning process or -composition (simple polymer or polymer mixture), which is a basic, unsaturated monomer with a / IAVVerl at 25 ° C of less than 8.0, preferably less than 7.5, (^ contains polymerized, such as basic unsaturated Monomer having a basic nitrogen atom as an unsaturated monomer of the following general Formula 1):

CH ₂ -C -CO- (CH ₂ ) ,, - N

(I)

where R _{1 is} hydrogen or a methyl group, R ₂ and R _{: are} each a methyl or ethyl group and 11 is an integer from 2 to 4, or of the general formula (II):

CH ₂ CC - O - R ₅ - NR ₆ R ₇ R ₁₁

X dl)

wherein R _{4 is} hydrogen or a methyl group, R _{5 is} an alkyl group having 2 to 4 carbon atoms. Hydroxyalkylcn- (jruppc or

(- CH ₂ CH ₂ OCH ₂ CH ₂ -HIrIiPPc,

R ₆ , R ₇ and Rn each represent a methyl, ethyl or propyl group and X represents an anion, or an unsaturated monomer such as, for example, a qualernary product of such a nitrogen-containing heterocyclic unsaturated compound such as an N-vinylimidazole compound or vinylpyridine.

This means acrylic polymer containing nitrogen groups or polymer composition:

1. Acrylnilrileopolymcrisal made of acrylonitrile and the basic unsaturated monomers explained above and, if desired, one or more neutral, ethylenically unsaturated monomers, or

2. Polymer mixture from (a) homopolymer of the basic unsaturated monomer explained above or its copolymers with others copoiymerisierbaicr, unsaturated compound (including acrylonitrile and neutral, mono-ethylenically unsaturated monomers) and (b) Acrylonitrile homopolymer or copolymer.

Examples of the aforementioned neutral, monoethylcnisch unsaturated monomers si; id lister (e.g. methyl, ethyl, propyl, butyl, etc. lister) the Acrylic acid and methacrylic acid; Vinyl esters of carboxylic acids, such as elwa vinyl formate, vinyl acetate, etc .: Acrylamide, methacrylamide and their derivatives: vinyl or vinylidene halides such as vinyl chloride, Vinyl bromide, vinylidene chloride, etc .; Styrene, cyanostyrene, etc.

The copolymer preferably contains the polymer mixture or the polymer mixture for forming the basic groups containing acrylic fibers at least 75 percent by weight acrylonitrile, 0.5 to H) percent by weight of the basic, unsaturated monomer and 0 to 15 percent by weight of the neutral, noniono-ethylenically unsaturated monomers.

When an acidic, unsaturated monomer with a Dissocial acid group such as a suffonic acid residue or a carboxyl group in the Acrylnilril Copolymcrisat, which forms the above-mentioned basic group-containing acrylic fiber is copolymerized is contained, the leakage according to the invention is reduced. So should use a such acidic mono ice should be avoided.

However, it is used for the production of the copolymer with persulfate, sulfite or hisulfite in the Polymcrisalions initiator system used, a small amount of such dissociative acidic groups as sulfuric acid is used! or sulfonic acid terminal in d; is containing the aforementioned basic groups, the Acrylic fiber-forming polymer was introduced, but this has no liquid effect on the overall dimensions.

The term pKi used in this invention means the electrolytic dissociation exponential. and its relation to the electrolytic? !! The dissociation consistency (ionization consistency λ 'of the basic unsaturated monomer is as follows:

pKi, log, "A '

The acrylic fiber with dissociative acid groups, which, as desired, mixed with an acrylic fiber and wool containing basic groups, Mischvcrzwinit, Mischgewcbl or Mischgewirki is a fiber that can be dyed with a cationic dye and is made from an acrylonitrile polymer or -copolymeiisal formed, in whose molecular Fndc such strong acid groups capable of dissociating such as a chemical acid group or a sulfonic acid group by using persulfal. Sullit or BisuUit in the Polymcrisalions-Initialorsystcm in a stage for the production of an acrylonile homopolymer or copolymer or a dissociable acid group through the copolymerization with acrylonitrile of an unsaturated monomer with such a sulfonic acid group as slyrolsulfonic acid, Vinylsulfonic acid, allylsulfonic acid or mclhallylsulfonic acid or its salt or such a carboxyl group as that of acrylic acid, methacrylic acid or itaconic acid or its salt was filled. The previously described basic, unsaturated The fiber-forming polymer does not contain monomers.

The copolymer preferably contains for the formation of the acrylic fibers with acid groups capable of dissociation at least 80 percent by weight of acrylonitrile, 0.01 to 5 percent by weight of the unsaturated monomer with Silfonsäurereslen or carboxyl groups and 0 to

35

20 387

15 percent by weight of at least one neutral, mono Example 1 ethylenically unsaturated monomers.

The anionic to be used according to the invention A 36-thread spun double yarn with S-twist

active agent is an anionic, aromatic poly- direction (36's / 2) was made from an acrylic fiber (in the fol-

condensate with dissociable acid groups 5 gende ■> referred to as »fiber Α«) made of an acrylic

such as the sulfonic acid group, e.g. B. a naphthalene nitrile copolymer with 90% acrylonitrile, 7% vinyl

sulfonic acid-formaldehyde condensate of the following acetate and 3% N, N-dimethyl-aminoethyl methacrylate

chemical formula: with a p / ftr value of 6.8 containing basic groups Acrylic fiber made. Two kinds of

_{ΓΗ ίο} Spun yarns (36's / 2) were each made from an acrylic

,. ^a \. , ■., Fiber made of acrylonitrile copolymer with 90% acrylic

_Mn "j_ : ' ! 1 j J " _nN] nitrile, 9.7% methyl acrylate and 0.3% sodium allyl

Nau ₃ i>,. II ^ jj SU ₃ INa, sulfonate (hereinafter referred to as "fiber B"), the

consisted of acrylic fiber and wool which can be dyed with a basic dye. The obtained three kinds of spun yarns were knitted in the form of strips of mixed water-soluble product from the reaction of a to obtain smooth knitting work. Formaldehyde condensate with a polyvalent Phe- The knitted fabric obtained in this way was nolcarboxylic acid with a sulfite in the first bath (published yes- at a rate of 1 ° C / min of 60 ⁰ C on panic patent application 7044/1968); Sulfomethylate ao heated to about 100 ° C and then 30 min at about a condensation product of di- (4-hydroxy 100 ⁰ C and a formulation of 2%, based on the phenyl) sulfone and a lower aliphatic Aide weight of the fiber ACI . Direct Blue 78, a pH hyd (Published Japanese Patent Application 24205 / of 7.0 (adjusted with sodium acetate) and a 1968); water-soluble polycondensate, obtained by liquor ratio of 1:50, in order to dye the heating of bisphenolsulfone or its derivative 25 fiber-A content. Then the goods were treated with an aromatic sulfonic acid under acidic conditions of 100 ° C for 45 minutes with a formulation of 2%, conditions in the presence of formaldehyde (based on the weight of fiber A, an anionic published Japanese patent application 10424/1966 ); active agent, a pH of 3.0 (adjusted with sulfuric acid aqueous solution of an alkali or ammonium salt) and a liquor ratio of 1:50 in a condensation product from a lower ali- 30 treated in the same bath.

phatic aldehyde and a sulfonic acid of dioxy- The above anionically active agent was

diphenyl sulfone (published Japanese patent- made as follows: 265 parts bisphenolsulfone and

registration 23231/1965); Reaction product of 2.2'- 220 parts of ß-naphthalenesulfonic acid were together-

Bis (hydroxyphenyl) sulfone and oxymethane sulfone mixed. 2 parts of concentrated

acid (French patent 1274,939); Bis- (4,4'-di- 35 trated sulfuric acid and further slowly 105 parts

hydroxyphenyl) sulfone, sulfonated and added with form- a 30% aqueous formaldehyde solution-

aldehyde condensed (British Patent 975 307) or set. The mixture was at 110 ^° C. for 2 hours

Triethylol monomethanesulfonic acid compound of stirred to start the reaction. Then became

4,4'-diphenyldimethylmethane (U.S. Patent 2,522,569). the mixture is neutralized and saturated with aqueous

In the case of treating a textile product with 40 sodium sulfate solution to salt out the polycondensation

Wool and a dyed synthetic acrylic fiber sats, which was recovered and dried. The

an acrylonitrile copolymer with the pre-dry powder was used as the anionically active agent

containing basic groups mentioned, unused.

saturated monomers with a treatment solution. The knitted fabric treated in this way with the anionically active at least one such anionically active agent, 45 agents, was then appropriately dyed in another bath as described above. For example, the bath was made with a formulation of 1%, amounts for the application of the treatment agent based on the weight of the fiber B, CI basic and the treatment conditions (such as the pH value yellow 11, 3%, based on the weight of the wool, and the temperature) as a function of the type of CI Acid Red 118, 1 g / l of a nonionic Disper treatment agent. Generally 50 sion agent, 3%, based on the weight of the Fajedoch the treatment solution contains 0.5 to 10 Geer B, a cationic retarder, a pH before weight percent, preferably 1 to 5 weight percent, 3.0 (adjusted with sulfuric acid) and an end Flott anionic active agent, based on the overall ratio of 1: 50, at a speed voi weight of dry fiber, and becomes acidic, preferential heated 2 ° C / min from 6O ⁰ C to 8O ⁰ C, 15 minutes proof to a pH of 2 to 7, adjusted. Furthermore kept 55 80 ⁰ C, then for 15 minutes on un it is necessary to promote the treatment effect heated to 100 ⁰ C and at this temperature 45 Mi dig, the treatment kept at a temperature above utes to the fiber B content as well as the 6O ⁰ C to be carried out. To dye the wool content.

In order to adjust the pH of the treatment bath, the dyed knitted fabric obtained in this way was used

put, organic or inorganic acids 60 cannot cause the slightest mutual discoloration of the thin

such as acetic acid, oxalic acid, formic acid, hydrochloric acid, types of fiber, the red-yellow-blue stripes to

Sulfuric acid or nitric acid can be used. was very nice.

For a better understanding of the invention, B e i s o i e 1 2 typical examples are given below. In

The percentages relate to the examples and 65 Using mixed spun yarn (30's /

Unless otherwise stated, parts by weight are composed of 15 parts of wool and 85 parts of fiber A a

given, and percent means percent by weight, be warp threads and mixed spun yarn (30's / 2) a

pulled on the dry fiber. 15 parts of wool and 85 parts of fiber B as a shoe

Threads a commodity was made. It was first in the fiber A portion under the same conditions as in example 1 with a formulation of the first bath of 2%, based on fiber A, CI direct brown 84, a pH of 7.0 (with Na ₂ SO ₃ set) and a liquor ratio of 1:50 and then treated for 45 minutes at a pH of 3.0 (adjusted with sulfuric acid) at about 100 ° C in the same bath, the 3%, based on fiber A, anionic active agent (a high molecular weight condensate of aromatic sulfonic acid) was added.

Then the goods in the second bath with 1%, based on the weight of the fiber B, C.I. base shot 18 and 1.5%, based on the weight of the wool, Cl. Acid blue 82 in the wool and fiber B content by the same method as in example 1 dyed.

The dyed fabric thus obtained was a speckled dyed yarn with no mutual discoloration of the three types of fiber used could be determined from one another, and the aesthetic appearance was attractively priced.

Example 3
5

Was the multicolor dyeing process in Example 1 using an acrylic fiber made of an acrylonitrile copolymer with 91 ° / _e acrylonitrile, 6% methyl acrylate and 3 ° / ₀ NN diethylaminoethyl methacrylate

ίο with a p ^ value of 6.6 or an acrylic fiber a polymer mixture of 10 parts of an acrylonitrile copolymer from 82% acrylonitrile and 18% 2 - hydroxy - 3 - methacryloxy - propyltrimethylammonium chloride with a ρΛΊ, value less than 1 and 115 parts of an acrylonitrile copolymer of 90% acrylonitrile and 10% methyl acrylate instead of the Fiber A repeated in Example Ϊ, a multi-colored dyed product was obtained, which is very cheap Had a multicolor contrast effect and no mutual discoloration of the fibers could be seen.

Claims (2)

Patent claims: 1. Process / ur production of a multi-colored, woolly aeryl TcKtilprodiiktes, gek e η η / eich η et by dyeing an acrylic fiber, consisting of a mixed polymer of acrylonitrile and a basic unsaturated monomer with a /> \ V value at 25 C. from below N, 0 or from a polymer mixture of homo- or copolymers !! the aforementioned basic monomers and homo- or copolymers lies acrylonitrile (a) and wool (b) containing Textilprodiikts in a dye bath at a pH value \ on 5 to 9 with ^e: NEM Direktfarhstoff / to dyeing of the acrylic fiber content, treating then the Textilprodiikts init an anionically active agent from the group of anionic aromatic polycondensates with sulfonic acid residues and then dyeing the wool portion in another dye in a dye bath under acidic conditions using an acid dye 2. The method according to claim I, characterized in showering the use of a laser made of a copolymer with at least 75 percent by weight of acrylonitrile, 0.5 to K) percent by weight at least a compound of the formula: