GB1567059A - Liquid dye preparations - Google Patents

Description

(54) LIQUID DYE PREPARATIONS (71) We, DAIDO-MARUTA FINISHING CO. LTD. a Japanese Body Corporate of No. 31, Ochiai-cho, Kisshoin, Minami-ku, Kyoto, Japan, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- This invention relates to liquid dye preparations, and more specifically to liquid dye preparations cqntaining water-insoluble or sparingly water-soluble dyes which are dispersant-free and have improved dyeability, a process for preparation thereof, printing pastes or dyeing baths containing these preparations, and to a method for printing or dyeing textile articles using printing pastes or dyeing baths containing these preparations.

Water-insoluble and sparingly water-soluble dyes such as disperse dyes or vat dyes are generally dispersed in water with dispersants when used for dyeing or printing textile articles. This practice has the disadvantage that although the dispersants are required to disperse these dyes in water they rather adversely affect the dyeability of these dyes on the textile articles. For example, when synthetic fibres such as polyester fibres are dyed or printed, the color yield is not entirely sufficient, and no satisfactory deep color consistency can be obtained. Moreover, the dyeings obtained tend to assume a dark hue. For this reason, practice has been prevalent heretofore to use the dyes in verv high concentrations or together with deep dyeing assistants.When water-insoluble or sparingly water-soluble dyes are used together with dispersants for textile printing, the generally hygroscopic nature of surface active agents used as the dispersants causes the printed and dried printing paste to absorb water and induce bleed-out. This also causes soiling jt the time of plaiting-down or batching-up.

According to the present invention, there is provided a liquid dye preparation comprising (1) a vehicle consisting of a polymer containing -COONH4 groups which has a water-solubility of at least 100 g per 100 g of water and either a watermiscible organic solvent or a water-miscible organic solvent and water, and (2) a water-insoluble or sparingly water-soluble dye dispersed in said vehicle.

The present invention also provides a process for producing a liquid dye preparation which process comprises mixing a polymer containing -COONH4 groups which has a water-solubility of at least 100 g per 100 g of water, either a water-miscible organic solvent or a water miscible organic solvent and water, and a water-insoluble or sparingly water-soluble dye, and grinding the mixture so as to uniformly disperse the dye in the mixture in the form of fine particles.

The present invention further provides a printing paste or dyeing bath comprising (A) a liquid dye preparation in accordance with the invention, and (B) a stock thickener or water.

The invention additionally provides a method of printing or dyeing textile articles using such a printing paste or dyeing bath.

The primary feature of the invention is that a water-soluble polymer containing COONH4 groups is used instead of an ordinary dispersant in producing a dye preparation by dispersing a water-insoluble or sparingly watersoluble dye in water and/or a water-miscible organic solvent.

It has been found that according to the present invention, the use of the watersoluble polymer markedly improves the dispersion and color yield of a dye in textile articles although no clear reason has yet been able to be assigned to this phenomenon. The water-soluble polymer used in this invention can be selected from a wide range of --COONH,-containing polymers which have a solubility in water of at least 100 g/100 g of water, preferably at least 200 g/100 g of water, and contain -COONH4 groups as a pendant side chain. The number of -COONH4 groups that can be present in the water-soluble polymers used in this invention is not critical so long as the groups can impart water solubility to the polymer.

Typically, such -COONH4-containing water-soluble polymers contain at least 3 mole % of at least one repeating structural unit of the formula

wherein R, represents a hydrogen atom, an alkyl group of up to 7 carbon atoms, or the group -COONH4, Rz represents ahydrogen atom or an alkyl group of up to 7 carbon atoms, and~R3 represents a hydrogen atom, an alkyl group of up tq 7 carbon atoms or the group -C2-COON4. Preferably, the alkyl group contains up to 5 carbon atoms.

In the above formula (I), the alkyl group may be straight or branched chain, and includes, for example, methyl, ethyl, n- or iso-propyi, and n-, iso-, sec- or tertbutyl Methyl is especially preferred. Specific examples of the repeating unit of formula (I) are:

Thus, preferred groups of the repeating unit of formula (I) are those expressed by the following formula

wherein R,t represents a hydrogen atom, a methyl group or a -COON H4 group, and R3, represents a hydrogen atom, a methyl group or a -CH2-COONH4 group, and above all, those expressed by the following formula

wherein R,2 and R32, independently from each other, represent a hydrogen atom or a methyl group.

The polymer having the repeating structural unit of formula (I) may be a homopolymer composed of only one kind of the repeating unit, but generally, it is advantageous to use it in the form of a copolymer containing at least one repeating structural unit of formula (I). The copolymer may be either one containing two or more structural units of formula (I), or one containing at least one repeating unit of formula (I) and at least one other repeating unit. The latter type of copolymer is especially desirable, and in this case, the copolymer may contain at least 3 mole %, usually at most 50 mole %, preferably 5 to 35 mole Ós more preferably 7 to 15 mole %, of the at least one repeating structural unit of formula (1).

The other repeating structurai unit that can be present in the -COONH4- containing copolymers is advantageously a unit derived from an ethylenically unsaturated monomer. Typical examples of ethylenically unsaturated monomers include monomers of the formula

wherein R4 and R5, independently from each other, represent a hydrogen atom or an alkyl group of up to 7 carbon atoms and R8 represents an alkoxy group of up to 7 carbon atoms or an acyloxy or alkoxy carbonyl group of up to 8 carbon atoms.

In formula (II), the alkyl group may be of straight or branched chain, preferably contains up to 5 carbon atoms and includes, for example, methyl, ethyl, n- or iso-propyl, and n-, iso-, sec- or tert-butyl group. Methyl is especially preferred. The alkoxy group preferably is one containing up to 5 carbon atoms and includes, for example, methoxy, ethoxy, n- or iso-propoxy, and n-, iso-, sec- or tertbutoxy. The acyloxy group is a group of the formula -OCOR7 wherein R7 is an alkyl group of up to 7, preferably of up to 5, carbon atoms such as acetyloxy or propionyloxy. The alkoxycarbonyl group is a group of the formula -COOR8 wherein Ras is an alkyl group of up to 7, preferably of up to 5, carbon atoms such as methoxycarbonyl, ethoxycarbonyl, n- or iso- propoxycarbonyl, and n-, iso-, sec- or tert-butoxycarbonyl.

Thus, preferred groups of the monomer of formula (II) are monomers expressed by the following formula

wherein R4, and R51, independently from each other, represent a hydrogen atom or methyl group, and Rs, represents an alkoxy group of up to 7 carbon atoms or an acetyloxy or alkoxycarbonyl group of up to 8 carbon atoms.

Typical examples of monomers of formula (II) or (II-a) are methyl acrylate, ethyl acrylate, n-, iso-, sec- or tert-butyl acrylate, n- or iso-propyl acrylate, vinyl acetate, methylvinyl ether, ethyl vinyl ether, isobutyl vinyl ether, methyl crotonate ethyl crotonate, ethyl isocrotonate, ethyl itaconate, methyl methacrylate, ethyl methacrylate, n-, iso-, sec- or tert-butyl methacrylate, and n- or iso-propyl methacrylate. Of these, vinyl acetate and lower alkyl esters of acrylic acid are especially preferred.

The molecular weight of the water-soluble polymer used in this invention is not critical. However, polymers having extremely high molecular weights are generally difficult to obtain in a water-soluble form, and therefore, it is generally preferred that the water-soluble polymers used in this invention have a number average molecular weight of not more than 10,000. On the other hand, the lower limit of the molecular weight is neither critical, and although depending upon the type of the polymer, the polymer preferably has a number average molecular weight of at least 2,000, preferably 2,500 to 5,000, more preferably 2,800 to 3,600.

The water-soluble polymers containing -COONH4 groups can be easily prepared. For example, they can be easily prepared by polymerizing at least one carboxyl-containing monomer of the formula

wherein R', represents a hydrogen atom, an alkyl group of up to 7 carbon atoms or a carboxyl group, R'3 represents a hydrogen atom, an alkyl group of up to 7 carbon atoms or the group -CH2-COOH, and R2 is as defined above, and if desired, at least one monomer of formula (II) or (II-a), and neutralizing the resulting carboxyl-containing polymer with ammonia or an aqueous solution of ammonia.

Typical examples of the carboxyl-containing monomers of formula (III) include crotonic acid, acrylic acid, methacrylic acid, maleic acid, itaconic acid, citraconic acid, and tiglic acid. They may be used either singly or in combination of two or more. Of these, crotonic acid, acrylic acid, methacrylic acid, and itaconic acid are preferred, the crotonic acid being especially suitable.

The polymerization can be carried out by any known methods such as solution polymerization, emulsion polymerization, suspension polymerization, or bulk polymerization. Generally, the solution polymerization method is suitable for obtaining molecular weights of the above-specified range effectively.

Especially suitable monomer combinations for the preparation of polymers for use in this invention are combinations of the carboxyl-containing monomers of formula (III), especially crotonic acid, with at least one monomer selected from vinyl acetate, (C1-C7) alkyl esters of acrylic acid and (C1-C7) alkyl esters of methacrylic acid.

Another characteristic feature of the present invention is that a water-miscible organic solvent or a mixture of water and a water-miscible organic solvent is used as the liquid medium for dispersing water-insoluble or sparingly water-soluble dyes, whereby the water-insoluble or sparingly water-soluble dyes can be dispersed uniformly in a very fine form in the liquid dyestuff preparation.

The water-miscible organic solvent may be any organic solvent which is inert to the dyes and does not substantially dissolve the dyes (even when they dissolve the dyes, the solubility of the dyes is generally less than 3% by weight). Generally, the organic solvent used in this invention is desirably selected from alcohols, ethers and esters.Examples of usable alcohols are monohydric (C1-C7) alcohols such as methanol, ethanol, n- or iso-Propanol, n- or tert-alcohol or allyl alcohol; polyhydric alcohols such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3butylene glycol, 2,3-butylene glycol, a-methyl-2,4-pentanediol, 2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, polyethylene glycol (molecular weights 200, 300, 400, or 600), or glycerin; and ether alcohols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether.Examples of the ethers are diethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, and dioxane.

Examples of the esters are ethyl acetate and amyl acetate. These solvents can be used either singly or in combination of two or more.

Especially preferred organic solvents that can be used in this invention are alcohols having a boiling point of at least 60"C, preferably monohydric or polyhydric alcohols having a molecular weight of not more than 600. Ethylene glycol has been found to be a very useful medium because it maintains the liquid dye preparation stable over long periods of time.

The water-miscible organic solvent may be used as such, or as a dispersing medium in the form of a mixture with water.

The water-insoluble or sparingly water-soluble dyes used to produce the liquid dye preparations in accordance with this invention are dyes which do not substantially dissolve in water, and include, for example, disperse dyes, vat dyes, and the raw powders of metallized dyes and cationic dyes (dyestuff cakes) which have not been complex with a metal or quaternised, respectively, in order to produce soluble dyestuffs. Typical examples of these dyes are listed below.

Disperse dyes C.I. Disperse Yellow 71 C.I. Disperse Orange 73 C.l. Disperse Red 83 C.I. Disperse Violet 56 C.I. Disperse Blue 113 C.I. Disperse Blue 198 Vat dyes C.I. Vat Yellow 12 C.I. Vat Orange 11 C.I. Vat Red 41 C.I. Vat Violet 15 C.I. Vat Blue 67 C.I. Vat Blue 22 Raw powders of the following Cationic dyes C.I. Basic Yellow 24 C.I. Basic Red 51 C.I. Basic Orange 33 C.I. Basic Violet 34 C.I. Basic Blue 7 Thus it is the unquaternised form of these cationic dyes which is used in the liquid dye preparations of the invention. For example, C.I. Basic Blue 7 in quaternised form is a compound of formula:

It is not this compound but its unquaternised form of formula:

which is employed in the present invention.

Raw powders of the following Metallized dyes C.I. Acid Yellow 129 C.I. Acid Orange 86 C.I. Acid Red 211 C.I. Acid Violet 73 C.I. Acid Blue 171 C.I. Acid Blue 188 Similarly, these metallised dyes as such are not employed in the present invention. Rather, it is their corresponding raw powder form that is employed. The raw powder form is substantially insoluble in water and is not complexed with a metal.

The proportions of the ingredients in the liquid dye preparation of this invention can be varied over wide ranges according, for example, to the purpose of use of the preparation. Generally, the proportion of the water-soluble polymer is at least 50 parts by weight per 100 parts by weight of the dye although it varies according to the type of the polymer. Although there is no particular upper limit, the use of too much polymer does not bring about corresponding merits. Hence, the suitable amount of the water-soluble polymer is up to 250 parts by weight, preferably 80 to 200 parts by weight, more preferably 100 to 150 parts by weight, per 100 parts by weight of the dye.

The amount of the water-miscible organic solvent is not critical, and can be varied according, for example, to the type of the solvent, or the type of the polymer and the dye. Generally, the amount of the solvent is at least 50 parts by weight per 100 parts by weight of the dye. The upper limit is preferably 1500 parts by weight.

The suitable amount of the organic solvent is usually 80 to 1,000 parts by weight per 100 parts by weight of the dye. When it is used in combination with water, its amount is advantageously 80 to 200 parts by weight, especially 100 to 150parts by weight. In the absence of water, the amount of the organic solvent is advantageously 100 to 1,000 parts by weight, particularly 200 to 800 parts by weight.

When water is used, the amount of water is at most 250 parts by weight, preferably at most 200 parts by weight, per 100 parts by weight of the dye.

The liquid dye preparation of this invention can be directly used in applications such as are described below. If desired, adjuvants usually employed for preparation of printing pastes or dyeing baths from water-insoluble or sparingly water-soluble dyes, for example, conditioners, such as polyethylene wax, may be incorporated in the liquid dye preparation in small amounts (for example, not more than 5% by weight based on the total weight of the dye preparation).

The liquid type dye preparation provided by the present invention can be prepared by mixing the -COONH4-containing polymer, either the water-miscible organic solvent or both the organic solvent and water, and the water-insoluble or sparingly water-soluble dye, and grinding the mixture. Grinding can usually be carried out in various known apparatus such as a roll mill, ball mill, sand grinder or attriter. The above ingredients in the specified proportions are charged into such an apparatus in any order, and sufficiently pulverized to a fine size.

Thus, the present invention can afford a dye preparation in which the waterinsoluble or sparingly water-soluble dye is uniformly dispersed in a very fine form, generally in the form of ultrafine particles with a size of less than I micron, in a vehicle consisting of the -COONH4-containing polymer and the water-miscible organic solvent with or without water.

The liquid dye preparation of this invention can be applied in its as-obtained form to textile articles in order to dye them. Advantageously, it is mixed with a stock thickener or water, and used in the form of a printing paste or dyeing bath.

The printing paste can be prepared by mixing the liquid dye preparation of this invention with a stock thickener. Any stock thickener generally used for the preparation of printing pastes can be used. Examples of such stock thickeners are starch, sodium alginate, gum arabic, tragacanth rubber, etherified starch, carboxymethyl cellulose, polyvinyl alcohol, and the synthetic resin pastes described in British Patent Specification No. 1,335,586 and Japanese Patent Publication No. 18914/72.Furthermore, in the present invention, synthetic resin pastes obtained by completely neutralizing with ammonia or ammonia water copolymers of maleic acid with at least one copolymerizable monomer such as vinyl acetate, (C1-C7) alkyl vinyl ethers, (C1-C7) alkyl acrylates, or (C1-C7) alkyl methacrylates, preferably a synthetic resin paste obtained by completely neutralizing a copolymer of 1 mole of maleic acid and 10 moles of vinyl acetate (having an average molecular weight of 2,500 to 4,000) with ammonia, are advantageously used.

If desired, it is possible to incorporate additives in the stock thickener.

Examples of such addltives are hydrotropes such as urea, glycerin, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether or diethyiene glycol monobutyl ether; dye dissolving agents such as thiodiethylene glycol; deep dyeing assistants such as polyoxyethylene pentaerithritolorolyoxyethlene oleyl ether; and defoamers such as octyl alcohol or decyl alcohol. Such additives are used in conventional amounts.

Furthermore, if required, the water-soluble polymer described hereinabove can be incorporated in the stock thickener in an amount of up to 10% by weight base on the weight of the stock thickener so as to improve the hand of textile articles dyed.

The stock thickener can be prepared as an emulsion, and in such a case, a white spirit (boiling point 170 to 1800C) and an emulsifier can be added to the paste described above.

The mixing ratio between the liquid dye preparation and the stock thickener can be varied over a wide range according, for example, to the method of printing, the structure of the textile article, and the color consistency required.

Advantageously, the dye preparation of this invention can be uniformly mixed in any desired proportion with the stock thickener. Generally, however, the dye preparation is mixed in an amount of up to 50 parts by weight per 100 parts by weight of the stock thickener.

Textile articles can be printed with the printing paste so prepared by any desired method. Printing can be performed by using any of a flat screen printing machine, a rotary screen printing machine and a roll printing machine, and the printed textile articles can be treated by any fixing methods such as steam fixing, dry heat fixing or superheated steam fixing, and post-treated by a conventional method, for example, alkali soaping.

On the other hand, the dyeing bath can be prepared by mixing the liquid dye preparation of this invention with water. The mixing proportion can be varied over a wide range according, for example, to the structure of the textile article and the color consistency required. For example, the dye preparation can be used in an amount of up to 10 parts by weight per 100 parts by weight of water. If desired, assistants, for example, levelling agents such as ammonium sulfate, anhydrous sodium sulfate or acetic acid, or surface-active agents can be added in appropriate amounts.

Textile articles can be dyed with the dyeing bath by any desired methods such as carrier dyeing, high temperature dyeing, or liquid flow dyeing. the dyeings are post-treated in a conventional manner.

Textile articles which can be printed or dyed with the liquid type dye preparation of this invention include, for example, natural fibres such as cellulosic fibers or wool; semi-synthetic fibers such as acetate, diacetate or triacetate; synthetic fibres such as polyamide, polyester, polyacrylonitrile or polypropylene fibres; and mixtures of these fibres, which are in the form of yarns, woven fabrics, knitted fabrics, or non-woven fabrics, etc.

The liquid dye preparation provided by this invention contains the water insoluble or sparingly water-soluble dye in the form of very finely and uniformly dispersed particles, and has superior thermal stability and storage stability. It has a good color yield and superior dyeability irrespective of the type of the dyeing or printing method employed, and can afford dyeings having brilliant colors with high color fastness.

Moreover, since the liquid type dye preparation of this invention does not contain a dispersant, it has the advantage of causing no such troubles as in the conventional printing techniques, such as bleed-out, soil by rubbing, or specks.

Still another advantage of this invention is that since the liquid type dye preparation of this invention has superior dyeability, the waste effluent from soaping after printing and fixing contains little unused dyes and can be treated easily.

The following Examples further illustrate the present invention. It should be noted that these Examples are merely illustrative, and various changes and modifications are possible without departing from the scope of the invention.

In the following Examples, the relative surface color density, color fastness to crocking and color fastness to perspiration of the dyeings were determined by the following methods.

(1) Relative surface color density The spectral reflection ratio of the surface of a sample dyeing was measured using a spectrophotometer (Model 307, a product of Hitachi Limited) with a band width of 5 nm. The relative surface density K/S was calculated in accordance with the Kubelka-Munk equation [see P. Kubelka, F. Munk, Z. Tech. Phus. 12, 593, 1931].

(l-R)2 K/S = 2R wherein R is the spectral reflection ratio measured, that is, the reflection ratio of a single-color light.

(2) Test on color fastness to crocking A sample dyeing was rubbed with a white test cloth 100 times under the following conditions under a load of 200 g using a crock meter, II type (a product of Nippon Senshoku Kigaki K.K.), and then the degree of staining of the test white cloth was evaluated on a gray scale as grades 1 to 5.

Dry crocking: Test performed while the white test cloth (cotton, plain-weave) was in the dry state Wet crocking: Test performed while the white test cloth (cotton, plain weave) was in the wet state (3) Color fastness to perspiration Two sample dyeings were immersed in an artificial acidic or alkaline perspiration solution for 30 minutes, and then interposed between plain-weave cotton-polyester white cloths. The assembly was compressed at 10 pounds/cm2 and 370C + 5"C for 24 hours using a perspiration tester, and then, the stained condition of the white cloth was examined. The evaluation of the staining was performed on a gray scale as grades I to 5.

Artificial acidic perspiration solution L-histidine hydrochloride 0.5 g Sodium chloride 5 g Monosodium phosphate 2.2 g To a mixture of the above compounds was added 15 ml of a 1/10 N aqueous solution of sodium hydroxide to adjust the pH of the mixture of 5.5, and then distilled water was added to make the entire volume 1 liter.

Artificial alkaline perspiration solution L-histidine hydrochloride O.~s g Sodium chloride 5 g Disodium phosphate 5 g To a mixture of the above compounds was added 25 ml of a 1/10 n aqueous solution of sodium hydroxide to adjust the pH of the mixture to 8.0. and then distilled water was added to make the entire volume 1 liter.

The VOONH4 containing water-soluble polymers used in the following Examples were prepared as follows: A reactor equipped with a stirrer, a reflux condenser and a nitrogen gas inlet was charged with the monomers shown in Table I in the amounts indicated, and 150 parts by weight of dioxane as a solvent and 0.02 part bq weight of azobisisobutyronitrile as a polymerization initiator are added. The reaction mixture was polymerized under reflux (95 to 1000 C) until there was substantially no increase in the viscosity of the mixture (usually 6 to 8 hours). After the polymerization, dioxane was distilled off at reduced pressure. A sufficient amount of 28% ammonia water was added to the residual polymer to neutralize it completely. The properties of the resulting water-soluble polymers are also shown in Table 1.

TABLE 1

Polymers (parts by weight) Monomers A B C D E F G H Acrylic acid 10 5 10 Itaconic acid 30 Crotonic acid 10 10 10 8 Methacrylic acid 10 Ethyl acrylate 40 5 n-Butyl acrylate 50 5 5 10 1U 10 Vinyl acetate 85 63 80 80 80 80 92 Number average molecular weight 3400 2900 3000 '900 3000 3500 3300 3950 Proportion of a -COONH4 -containing monomer unit (mole Sc) 6.47 9.76 43.24 9.7 9.5 8.1 9.5 7.6 Example 1.

The dyes, water-soluble polymers, water-miscible organic solvents and water shown in Table 2 in the amounts shown in Table 2 were charged into an attriter (Model MA-I 58, a product of Mitsui Miike Seisakusho K.K.; rotating speed 120 rpm, stainless steel balls with a diameter of 3/16 inch), and mixed and dispersed for 2 hours.

Examination by a grind gage of the liquid type dye preparations obtained showed that the dye particles had a particle size of less than 1 micron, and were very uniform. Even when they were stored at room temperature for more than 3 months, their dispersibility scarcely changed.

TABLE 2

Dye preparation (parts by weight) Ingredients A B C D E F G H C.I. Disperse Yellow 79 15 C.I. Disperse Orange 73 IS C.I. Disperse Blue 113 15 C.I. Disperse Blue 198 15 C.I. Disperse Yellow 42 15 C.I. Vat Red 41 10 Raw powder of C.I. Acid Violet 103 10 Raw powder of C.I. Basic Orange 33 10 Polymer A 20 Polymer B 20 Polymer C 20 Polymer D 20 Polymer E 15 Polymer F 15 Polymer G 15 Polymer H 20 Ethyl alcohol 15 15 10 10 45 45 40 15 Isopropyl alcohol 10 10 15 15 20 20 15 10 Ethylene glycol 5 5 5 5 5 5 5 5 Ethylene glycol monobutyl ether 5 5 5 5 5 5 5 5 Water 30 30 30 30 ~ 10 30 Example 2.

A printing paste was prepared in the following manner using dye preparation A formed in Example l.

12 Parts by weight of etherified starch ("sorbitose C--5", a product of Scholten Company), 0.5 part by weight of sodium meta-nitrosulfonate and 87.5 parts by weight of water were mixed uniformly by a high-speed homogenizer (a product of Nihon Tokushu Kikako K.K.) to form a stock thickener. 60 Parts by weight of the resulting stock thickener, 6 parts by weight of dye preparation A, 5 parts by weight of urea and 29 parts by weight of water were placed in a high-speed homogenizer, and stirred for 15 minutes at a speed of 5,000 rpm to form a printing paste A having a viscosity, as measured by a B-type viscometer at 25"C., of 8,500 centipoises.

For comparison, printing pastes I and II were prepared by the same method as described above except that dye preparations I and II of the following formulations were used instead of dye preparation A.

Dye preparation (parts by weight) I 11 C.I. Disperse Yellow 79 15 15 CresoVSchaffe?s acid/formaldehyde condensate (dispersant; "NEKAL" SS, a product of BASF, "NEKAL" is a Registered Trade Mark) 20 6 Sodium dibutylnaphthalenesulfonate 2 2 Anhydrous sodium sulfate 5 4 Water 58 73 The dye preparations I and II were prepared by mixing and dispersing the above ingredients for 2 hours in an attriter. (The same procedure was employed in the production of dye preparations III to X to be described hereinbelow).

A polyester jersey was printed using each of the printing pastes A, I and II by a flat screen printer (a product of Buser Company) with a 130-mesh screen. After drying, the printed article was treated with high temperature steam at 180"C. for 7 minutes, and then washed with a reducing bath containing 2 g/liter of sodium hydrosulfite, 2 g/liter of sodium hydroxide and 3 g/liter of a nonionic surface active agent, washed with water, and dried.

Dyed articles printed yellow were obtained. The color shades, relative surface densities and color fastness characteristics of the resulting particles were determined, and the results are shown in Table 3.

TABLE 3

Relative 7 Fastness to Fastness to surface crocking perspiration Printing color paste density used (K/S) Dry Wet Acid Alkali Color shade A 0.253 5 5 5 5 Very brilliant yellow I 0.229 5 4 ' 4 4 Slightly dull yellow II 0.239 4 4 4 4 Slightly dull yellow Example 3.

A printing paste was prepared by using the dye preparation B formed in Example 1.

Etherified starch (Sorbitose C--5) 9 parts by weight Sodium meta-nitrobenzencsulfonate 0.5 Polyoxyethylene nonyl phenol ether (EO 12 mole-added product) 0.5 White spirit (b.p. l70-1800C.) 15 Water 75 The above ingredients were uniformly mixed in a high-speed homogenizer (a product of Nihon Tokushu Kikako K.K.) to form a stock thickener.

70 Parts by weight of the resulting stock thickener, 4 parts by weight of dye preparation B, 5 parts by weight of urea and 21 parts by weight of water were charged into a high-speed homogenizer, and stirred for 15 minutes at a speed of 5,000 rpm to form a printing paste B having a viscosity of 6,500 centipoises (determined by a B-typer viscometer at 250C.).

For comparison, printing pastes III and IV were prepared in the same manner as above except that dye preparations III and IV prepared in a conventional manner were used instead of the dye preparation B.

Dye preparation parts by weight) III IV C.I. Disperse Orange 73 15 15 Cresol /Schaffer' s acid/formaldehyde condensate (NEKAL SS) 10 4 Sodium naphtha1enesu1fbiiate'forma1dehyde condensate ("TAMOL" SS, a product of BASF, TAMOL is a Registered Trade Mark) 10 2 Sodium dibutylnaphthalenlsulfonate 2 2 Anhydrous sodium sulfate 5 4 Water 58 73 Polyester textured woven fabrics were printed using the resulting printing pastes B, III, and IV by a rotary screen printer (RP--III, Stork Brabent B.V.) with an 80-mesh screen.

After drying, the printed fabrics were treated with high pressure steam at 2 kg/cm2 for 30 minutes to fix the dye, washed with a reducing bath containing 2 g/liter of sodium hydrosulfite, 2 g/liter of sodium hydroxide and 3 liter of a nonionic surface active agent, washed further with water, and dried.

Thus, articles printed orange were obtained. The color shades, relative surface color densities and color fastness characteristics of the articles were determined, and the results are shown in Table 4.

TABLE 4

Relative Fastness to Fastness to surface crocking perspiration Printing color paste density used (K/S) Dry Wet Acid Alkali Color shade B 0.319 4-5 4-5 5 5 Very brilliant orange III 0.292 3-4 3-4 4 4 Dull orange IV 0.290 3-4 3-4 4 4 Dull orange Example 4.

A printing paste was prepared using the dye preparation C formed in Example 1.

Etherified starch (Sorbitose C--5) 12 parts by weight Sodium meta-nitrobenzene-sulfonate 0.5 Water 87.5 These ingredients were uniformly mixed by a high-speed homogenizer (a product of Nihon Tokushu Kikako K.K.), and stirred for 15 minutes at a speed of 5,000 rpm to afford a printing paste C having a viscosity of 9,000 centipoises (as determined by a B-type viscometer at 250 ). C.).

For comparison, printing pastes V and VI were prepared in the same way as above except that dye preparations V and VI of the following formulations prepared in a conventional manner were used instead of dye preparation C.

Dye preparation (parts by weight) V VI C.I. Disperse Blue 113 15 15 Cresol 'Schaffer's acid/formaldehyde 10 4 condensate (NEKAL SS) Sodium naphthal ene sulfonate /formaldehyde condensate (TAMOL SS) 10 2 Sodium dibutylnaphthalenesulfonate 2 2 Anhydrous sodium sulfate 5 4 Water 58 73 Polyester interlock fibers were printed with the printing pastes C, V and VI by a flat screen printing machine (a product of Busen Company) with a 130-mesh screen.

After drying, the printed fabrics were treated with high temperature steam at 180"C. for 7 minutes, washed with a reducing bath containing 2 g/liter of sodium hydrosulfite, 2 g/liter of sodium hydroxide and 3 liter of nonionic surface active agent, washed with water, and dried.

Articles printed blue were obtained. The color shades, relative surface color densities and color fastness characteristics of the articles were determined, and the results are shown in Table 5.

TABLE 5

Relative Fastness to Fastness to surface crocking perspiration Printing color paste density used (K/S) Dry Wet Acid Alkali Color shade C 0.339 5 4 5 5 5 Very brilliant blue V 0.272 4 3-4 4 4 Dull blue VI 0.286 4 3-4 4 4 Dull blue Example 5.

Dye baths of the following formulation were prepared using the dye preparations B, C and D formed in Example 1, and polyester tricots were dyed at high temperatures under the conditions shown below.

Dye bath formulation Ammonium sulfate 1 liter Acetic acid (50% aqueous solution) l cc/liter Levelling agent [polyoxyethylene lauryl sulfate adduct (ethylene oxide 7 moles)] 2% o.w.f.

Dye preparation B, C or D 2.5% o.w.f.

Goods-to-liquor ratio 1:30 Dyeing temperature and time The bath temperature was raised to 130"C. at a rate of 2.5 C./min., and the dyeing was performed at 130"C. for 60 minutes.

After the dyeing, the articles were washed with a reducing bath containing 2 g/liter of sodium hydrosulfite, 2 g/liter of sodium hydroxide, and 2 g/liter of a nonionic surface active agent, washed with water, and dried.

For comparison, polyester tricots were dyed in the same way as above except that the same dye preparations III and V as used in Examples 3 and 4, and a dye preparation V11 of the following formulation were used instead of the dye preparations B, C and D.

Dye preparation VII (parts by weight) C.I. Disperse Blue 198 15 CresoUSchaffer's acid/formaldehyde condensate ("NEKAL" SS) 10 Sodium naphthalene-sulfonate/formaldehyde condensate ("TAMOL" SS) 10 Sodium dibutylnaphthalene-sulfonate 2 Anhydrous sodium sulfate 5 Water 58 The relative surface color densities and color shades of the resulting dyeings were determined, and the results are shown in Table 6.

TABLE 6

Dye Relative surface preparation color density used (K/S) Color shade B 0.200 Very brilliant deep orange It 0. 151 Somewhat pale orange C 0.277 Very brilliant deep blue V 0.260 Somewhat pale blue D 0.384 Very brilliant turquoise blue Viz 0. 367 Dull turquoise blue Example 6.

Using the dye preparation E formed in Example l, a design pattern was printed on a polyester taffeta by a roller printing machine (a product of Wakayama Iron Works Ltd., Japan) equipped with a gravure roll with a depth of 50 microns (100 lines/inch).

After drying, the printed taffeta was treated with high temperature steam at 180"C. for 8 minutes to fix the dye, washed with a reducing bath containing 2 g/liter of sodium hydrosulfate, 2 g/liter of sodium hydroxide and a 3 g/liter of a nonionic surface active agent, washed with water, and dried.

For comparison, printing was performed in the same way as above except that a dye preparation VIII of the following formulation was used instead of the dye preparation E.

Dye preparation VIII (parts by weight) C.I. Vat Red 41 10 Cresol/Schäffer's acid/formaldehyde condensate ("NEKAL" SS) 10 Sodium dibutylnaphthalene-sulfonate 5 Anhydrous sodium sulfate 4 Carboxymethyl cellulose 3 Water 68 The relative surface color densities, color fastness characteristics, and color shades of the articles obtained were determined, and the results are shown in Table 7.

TABLE 7

Relative Fastness to Fastness to surface crocking perspiration Dye color preparation density used (K/S) Dry Acid Alkali Color shade E 0.343 4-5 4-5 5 5 Very brilliant red VIII 0.310 4 3-4 4 4 Dull red; marked bleed-out Example 7.

Using the dye preparation F formed in Example 1, a design pattern was printed on a nylon taffeta by a roller printing machine (a product of Wakayama Iron Works Ltd., Japan) equipped with a gravure roll with a depth of 45 microns (100 lines/inch).

After drying, the taffeta was treated with steam at 0.3 kg/cm2 for 20 minutes to fix the dyes, subjected to alkali soaping (soda ash 2 liter and a nonionic surfactant 2 g/liter), washed with water, and dried.

For comparison, printing was performed in the same way as above except that a dye preparation IX of the following formulation was used instead of the dye preparation F.

Dye preparation IX (parts by weight) Raw powder of C.I. Acid Violet 103 10 CresoVSchäffer's acid/formaldehyde condensate ("NEKAL" SS) 10 Sodium dibutylnaphthalene-sulfonate 5 Anhydrous sodium sulfate 4 Carboxymethyl cellulose 3 Water 68 The relative surface color densities, color fastness characteristics and color shades of the resulting dyeings were determined, and the results are shown in Table 8.

TABLE 8

Relative Fastness to Fastness to surface crocking perspiration color Dye density preparation (K/S) Dry Wet Acid Alkali Color shade F 0.322 4 5 5 5 Very brilliant violet IX 0.298 3 4 4 4 Dull violet; marked bleed-out Example 8.

A printing paste was prepared using the dye preparation G formed in Example 1.

12 Parts by weight of etherified starch (Sorbitose C-l), 0.5 part by weight of sodium meta-nitrosulfonate and 87.5 parts of water were mixed uniformly in a highspeed homogenizer (a product of Nihon Tokushu Kikako K.K.) to form a stock thickener.

70 Parts by weight of the resulting stock thickener, 6 parts by weight of the dye preparation G, 5 parts by weight of urea and 19 parts by weight of water were placed in a high-speed homogenizer, and stirred for 15 minutes at a speed of 5,000 rpm to form a printing paste G having a viscosity of 11,000 centipoises (determined by a B-type viscometer at 25cC.).

For comparison, a printing paste X was prepared in the same way as above except that dye preparation X of the following formulation prepared in a conventional manner was used instead of the dye preparation G.

Dye preparation X (parts by weight) Raw powder of C.I. Basic Orange 33 15 CresoVSchaffer's acid/formaldehyde condensate ("NEKAL" SS) 10 Sodium naphthalene-sulfonate/formaldehyde condensate ("TAMOL" SS) 5 Sodium dibutylnaphthalene-sulfonate 4 Anhydrous sodium sulfate 4 Water 62 An acrylic jersey was printed using the resulting printing pastes G and X by a flat screen printing machine (a product of Buser Company) with a 130-mesh screen.

After drying, the printed fabric was treated at 0.3 kg/cm2 for 10 minutes by a steam fixing method, subjected to alkali soaping (soda ash 2 g/liter, and a non ionic surfactant 3 g/liter), washed with water, and dried.

Articles printed orange were obtained. The color shades, the relative surface color densities and color fastness characteristics of the articles were determined, and the results are shown in Table 9.

TABLE 9

Relative Fastness to Fastness to surface crocking perspiration Printing color paste density used (K /S) Dry Wet Acid Alkali Color shade G 0.343 < 5 5 5 Very brilliant orange X 0.318 4-5 4 -1 4 1 5 < Dull orange Example 9.

Maleic acid/vinyl acetate (1/10 molar ratio) copolymer, ammonium salt* 3 parts by weight Polymer H 5 White spirit(b.p. 17Q--180"C.) 30 Polyoxyethylene oleyl ether (12 moles of ethylene oxide added) Water 61 The above ingredients were charged into a high-speed mixer, and thoroughly mixed to form an emulsion-type stock thickener having a viscosity of 60,000 centipoises (determined by a B-type viscometer at 250C.).

Two parts by weight of the dye preparation H formed in Example 1, 60 parts by weight of the stock thickener, 5 parts by weight of urea, 0.5 part by weight of sodium meta-nitrobenzenesulfonate and 32.5 parts by weight of water were stirred for 15 minutes in a high-speed mixer to form a printing paste H.

Using the printing paste H, a nylon tricot was printed by a flat screen printing machine with a 130-mesh screen.

After drying, the printed fabric was treated at 0.3 kg/cm2 for 20 minutes by a steam fixing method, subjected to alkali soaping (soda ash 2 g/liter, a nonionic surfactant 3 g/liter), washed with water, and dried.

A brilliant yellow printed fabric free from staining was obtained. The printed fabric had a very good hand.

The ammonium salt of the maleic acid/vinyl acetate copolymer was prepared as follows: A reactor equipped with a stirrer, a reflux condenser and a nitrogen gas inlet was charged with 12 parts by weight of maleic acid and 88 parts by weight of vinyl acetate, and 150 parts by weight of methanol as a solvent and 0.02 part by weight of azobisbutyronitrile as a polymerization initiator were added. The reaction mixture was polymerized under reflux (70 to 750C) until there was no increase in the viscosity of the mixture (usually in 6 hours). After the polymerization, methanol was evaporated at reduced pressure, and a sufficient amount of 28% ammonia water was added to the remaining polymer to neutralize it. The number average molecular weight of the resulting product was 4,000.

Example 10.

Dye preparation H 5 parts by weight C.l. Vat Yellow 2 5 Stock thickener prepared in Example 9 50 Urea 5 Sodium metanitrobenzene-sulfonate 0.5 Water 34.5 The above ingredients were charged into a high speed mixer, and stirred for 15 minutes to form a printing paste.

A polyester/cotton (50/50) jersey was printed with the resulting printing paste by a rotary screen printing machine with an 80-mesh screen.

After drying, the printed jersey was baked at 2000 C. for 45 seconds, padded with a solution containing 60 liter of sodium hydrosulfite, 100 g/liter of 450 Bé sodium hydroxide and a 2% starch paste by a blotch roll, and passed through a flash ager at l02C. for 30 seconds, followed by oxidation and soaping in a customary manner.

The dyed, printed jersey was a brilliant yellow and possessed good color fastness.

WHAT WE CLAIM IS:- l. A liquid dye preparation comprising (l) a vehicle consisting of a polymer containing COONH4 groups which has a water-solubility of at least 100 g per 100 g of water and either a water-miscible organic solvent or a water-miscible organic solvent and water, and (2) a water-insoluble or sparingly water-soluble dye dispersed in said vehicle.

2. A preparation according to claim l wherein the water-soluble polymer contains at least 3 mole % of at least one repeating structural unit of the formula:

wherein R1 is a hydrogen atom, an alkyl group of up to 7 carbon atoms, or the group COONH4, R2 is a hydrogen atom or an alkyl group of up to 7 carbon atoms, and R3 is a hydrogen atom, an alkyl group of up to 7 carbon atoms or the group CH2COONH4.

3. A preparation according to claim 2 wherein the water-soluble polymer is a copolymer containing from 3 to 50 mole % of at least one repeating structural unit of the formula (I) and from 97 to 50 mole % of at least one repeating structural unit derived from an ethylenically unsaturated monomer.

4. A preparation according to claim 3 wherein the ethylenically unsaturated monomer has the formula:

wherein R4 and R5, independently from each other, represent a hydrogen atom or an alkyl group of up to 7 carbon atoms and R represents an alkoxy group of up to 7 carbon atoms or an acyloxy or alkoxycarbonyl group ot up to 8 carbon atoms.

5. A preparation according to any one of claims 2 to 4 wherein the watersoluble polymer contains from 5 to 35 mole % of repeating structural units of formula (I).

**WARNING** end of DESC field may overlap start of CLMS **.

Claims (27)

1. **WARNING** start of CLMS field may overlap end of DESC **.

   Example 10.

   Dye preparation H 5 parts by weight C.l. Vat Yellow 2 5 Stock thickener prepared in Example 9 50 Urea 5 Sodium metanitrobenzene-sulfonate 0.5 Water 34.5 The above ingredients were charged into a high speed mixer, and stirred for 15 minutes to form a printing paste.

   A polyester/cotton (50/50) jersey was printed with the resulting printing paste by a rotary screen printing machine with an 80-mesh screen.

   After drying, the printed jersey was baked at 2000 C. for 45 seconds, padded with a solution containing 60 liter of sodium hydrosulfite, 100 g/liter of 450 Bé sodium hydroxide and a 2% starch paste by a blotch roll, and passed through a flash ager at l02C. for 30 seconds, followed by oxidation and soaping in a customary manner.

   The dyed, printed jersey was a brilliant yellow and possessed good color fastness.

   WHAT WE CLAIM IS:- l. A liquid dye preparation comprising (l) a vehicle consisting of a polymer containing COONH4 groups which has a water-solubility of at least 100 g per 100 g of water and either a water-miscible organic solvent or a water-miscible organic solvent and water, and (2) a water-insoluble or sparingly water-soluble dye dispersed in said vehicle.
2. 2. A preparation according to claim l wherein the water-soluble polymer contains at least 3 mole % of at least one repeating structural unit of the formula:

   wherein R1 is a hydrogen atom, an alkyl group of up to 7 carbon atoms, or the group COONH4, R2 is a hydrogen atom or an alkyl group of up to 7 carbon atoms, and R3 is a hydrogen atom, an alkyl group of up to 7 carbon atoms or the group CH2COONH4.
3. 3. A preparation according to claim 2 wherein the water-soluble polymer is a copolymer containing from 3 to 50 mole % of at least one repeating structural unit of the formula (I) and from 97 to 50 mole % of at least one repeating structural unit derived from an ethylenically unsaturated monomer.
4. 4. A preparation according to claim 3 wherein the ethylenically unsaturated monomer has the formula:

   wherein R4 and R5, independently from each other, represent a hydrogen atom or an alkyl group of up to 7 carbon atoms and R represents an alkoxy group of up to 7 carbon atoms or an acyloxy or alkoxycarbonyl group ot up to 8 carbon atoms.
5. 5. A preparation according to any one of claims 2 to 4 wherein the watersoluble polymer contains from 5 to 35 mole % of repeating structural units of formula (I).
6. 6. A preparation according to any one of the preceding claims wherein the

   water-soluble polymer has a number average molecular weight of from 2,000 to 10,000.
7. 7. A preparation according to claim 6 wherein the water-soluble polymer has a number average molecular weight of from 2,500 to 5,000.
8. 8. A preparation according to any one of the preceding claims wherein the water-miscible organic solvent is an alcohol, ether or ester.
9. 9. A preparation according to claim 8 wherein the water-miscible organic solvent is a monohydric or polyhydric alcohol having a molecular weight of not more than 600.
10. 10. A preparation according to any one of the preceding claims wherein the dye has a solubility in the water-miscible organic solvent of less than 3% by weight.
11. I 1. A preparation according to any one of the preceding claims wherein the dye is a disperse dye, vat dye or the raw powder of a metallized dye or cationic dye which has not been complexed with a metal or quaternised, respectively.
12. 12. A preparation according to any one of the preceding claims containing the water-soluble polymer in an amount of at least 50 parts by weight per 100 parts by weight of dye.
13. 13. A preparation according to claim 12 wherein the water-soluble polymer is present in an amount of from 80 to 200 parts by weight per 100 parts by weight of dye.
14. 14. A preparation according to any one of the preceding claims containing the water-miscible organic solvent in an amount of at least 50 parts by weight per 100 parts by weight of dye.
15. 15. A preparation according to claim 14 wherein the water-miscible organic solvent is present in an amount of from 80 to 1,000 parts by weight per 100 parts by weight of dye.
16. 16. A preparation according to any one of the preceding claims containing water in an amount of at most 250 parts by weight per 100 parts by weight of dye.
17. 17. A preparation according to claim 1, substantially as hereinbefore described in any one of the Examples 1(A) to 1(H).
18. 18. A process for producing a liquid dye preparation which process comprises mixing a polymer containing -COONH4 groups which' has water-solubility of at least 100 g per 100 g water, either a water-miscible organic solvent or a watermiscible organic solvent and water, and a water-insoluble or sparingly watersoluble dye, and grinding the mixture so as to uniformly disperse the dye in the mixture in the form of fine particles.
19. 19. A process according to claim 18, substantially as hereinbefore described in Example 1.
20. 20. A liquid dye preparation whenever prepared by a process as claimed in claim 18 or 19.
21. 21. A printing paste or dyeing bath comprising (A) a liquid dye preparation as claimed in any one of claims 1 to 17 or 20, and (B) a stock thickener or water.
22. 22. A printing paste or dyeing bath according to claim 21 substantially as hereinbefore described in any one of Examples 2 to 5 or 8 to 10.
23. 23. A printing paste in the form of an emulsion, comprising: (A) a liquid dye preparation as claimed in claim 1, wherein the polymer containing -COONH4 groups also contains units derived from vinyl acetate and (B) a stock thickener containing a white spirit of boiling point 170 to 1800C and an emulsifier.
24. 24. A method for printing or dyeing textile articles, which comprises printing or dyeing a textile particle using a printing paste or dyeing bath as claimed in any one of claims 21, 22 or 23.
25. 25. A method according to claim 24, substantially as hereinbefore described in any one of Examples 2 to 5 or 8 to 10.
26. 26. A method for printing textile articles made up of synthetic fibres which comprises printing such an article using a liquid dye preparation as claimed in claim 1 wherein the polymer containing -COONH4 groups also contains units derived from vinyl acetate.
27. 27. Textile articles whenever printed or dyed by a method as claimed in any one of claims 24, 25 or 26.