CA1079456A - Colouration process - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
A process for the colouration of textile materials by printing with a composition containing (a) A dyestuff capable of forming a covalent bond with the fibres of the textile material or of becoming covalently linked into an amino/formaldehyde condensate, (b) a curable fully alkylated amino/formaldehyde precondensate, (c) a high molecular weight material containing acidic groups, (d) a volatile basic substance present in sufficient quantity to make the pH of the composition at least 8, and heating the printed textile material to volatilise the basic substance and to cure the fully alkylated amino/formaldehyde precondensate. Useful for producing printed textile requiring minimum wash-off before use.

Description

iO79456 The present invention relates to a process for the coloration of textiles in particular to a process of coloration by printing associated with high levels of dye fixation so that the need to wash the printed textile material before sale or use is reduced or eliminated.
According to the present invention there is provided a process for the coloration of textile materials by printing with a composition containing ; (a) a dyestuff capable of forming a covalent bond with the fibres of the textile material or of becoming covalently linked into an ` amino/formaldehyde condensate, (b) a curable fully alkylated amino/formaldehyde precondensate, (c) a high molecular weight material containing acidic groups, (d) a volatile basic substance present in sufficient quantity to make the pH of the composition at least 8, and heating the printed textile material to volatilise the . ., ; 20 basic substance and to cure the fully alkylated amino/formald-ehyde precondensate.
Dyestuffs suitable for use in the process of the present invention may contain any of the known chromophoric groupings such as, for example, those present in dyes of the . . .
nitro, azo, anthraquinone, phthalocyanine or formazan series and may if appropriate contain metal in complex formation.

-~ The dyestuffs may also contain a grouping reactive with - textile fibres such as any of the well known groups which - can form a covalent link with the hydroxyl groups in cellulose, ~ 30 for example, triazine pyrimidine, pyridazone, quinoxaline or -- 1 -- .

~ ~ .

., .
; :
.~ ' .. . ~ .

10~9456 quinazoline bearing one or more halogen especially chlorine atoms on a carbon atom of the heterocyclic ring adjacent to a nitrogen atom, acryloyl, 2,2,3,3-tetrafluorocyclobutane ca:rbonyl or sulphonyl groups or 2,2,3 trifluoro c~clobut-l-ene ca:rbonyl or suphonyl groups, a beta-halogenopropionyl, beta-halogenoethylsulphonyl, beta-halogenoethylsulphamyl, beta-sulphatoethylsulphonyl, beta-hydroxyethylsulphonyl, chloro-acetylamino, beta-(chloromethyl)-beta-sulphatoethylsulphamyl, beta-(alkyl- and aryl- sulphonyloxy)alkyl sulphonyl, beta-acyloxyalkysulphonyl, vinyl- sulphonyl, alkyl phosphite, or sulphon fluoride radical.
The dyestuff may alternatively or in addition contain one or more groups capable of reacting with fully alkylated amino/formaldehyde precondensates or with partially cured condensates therefrom, for example a group of the formula:

- -CONH2, -- NHCOWH2, --NHCONHCH20H, -NHC(NH)NHCN, -NHC(NH)NHCONH2, -S02NH2 ~ NHCONH2 -SO2NHCONH2, -S2 ~ CH3 ~ -NH2, -NH alkyl, :., NHCONH2 ~ - -NH ~ - NHCOCNH2, -N(CH2CH20H)~,-QH, -SO2NHCH2CH2Cl, . , .

-NH ~ SO2NHCONH2, -N(CH3)CH2(CHOH)4CH20H, -NHCH2CH2NHCONH2 .
; It is often preferred that the groups capable of reacting with the fully alkylated amino/formaldehyde condensate are present as, or as part of, substituents on one or more s-triazine groups in the dyestuff. Preferred reactive groups of this type contain ureido, i.e. NHCONH2 groups. It is usually preferred that the triazine groups are linked to the . remainder of the dyestuff molecule by an -NR- group, where R is Cl_4 alkyl or especially H.

1~7945~i Particularly valuable dystuffs are those having one of the following structures:

~;N~ ~ o:t D~ N A

(1) N

(2) or ~ N ~ ~
~ ' . .
where D is a chromophoric group, n = 1 or preferably 2 and Z is a bivalent linking radical of the aromatic or aliphatic series.
In the dyestuffs of formula (1), A or B may be the ' same and selected from Cl, -OH, -NH2, -N(CH2CH20H)2 alkylamino or substituted alkylamino or A and B may be different when A may be selected from Cl, -OH, -NH2, alkylamino or -SO3H
and B may be selected from alkoxy, -NH ~ , -NHC(NH)NHCN, -NH ~ SO2NHCONH2 , -N(cH3)cH2(cHoH)4cH2oH , -N(CH2cH20H)2~ -NHcH2cH2NHcoNH
anilino, sulphoanilino, disulphoanilino or any of the last named three groups having further substituents in the aromatic nucleus e.g. -CO2H, lower alkyl or lower alkoxy but preferred dyestuffs have B as -NH ~ HCONH2 Ol -NHCH2CH2NHCONH2.
In dyestuffs of formula (2) E may be Cl, OH, NH2, alkylamino, substituted alkylamino, N(CH2CH20H)2 or alkoxy and A and B
may have the meanings given above in connection with formula (1).
In dyestuffs of formula (3) A may be Cl, OH, NH2, alkylamino, substituted alkylamino or N(CH2CH20H)2.
As Examples of the divalent linking radical Z there may be mentioned N,N'-divalent radicals of diamines such as , 107~456 piperazine, aliphatic amines, e.g.
ethylene diamine, 1,2- ana 1,3-propylenediamines, 1,6-hexamethylene diamine, 2,2'-diaminodiethylether;
It is preferred to have Z derived from a diprimary aromatic diamine such as mono- and di-cyclic diamines of the benzene series, e.g.
1,3- and 1,4-phenylenediamines 4,4'-diaminodiphenylurea

- 3,3'-diaminodiphenylurea

4,$'-diaminodiphenylmethane, 4,4'-diaminophenyl sulphone, 4,4'- diaminodiphenyl ether, 4,4'-diaminostilbene , 4,4'-diaminodiphenoxyethane ; and it is particularly preferred to have Z derived from sulphonated diprimary aromatic diamines such as :
1,3-diaminobenzene-4-sulphonic and 4,6-disulphonic acid, 1,4-diaminobenzene-2-sulphonic and 2,5-disulphonic acids r or naphthalene diamines e.g.
2,6-diaminonaphthalene-1,5- and 4,8-disulphonic acids, ~ 1,5-diaminonaphthalene-3,7-disulphonic acid or ,;~ 30 comp~unds of the formula:

`'~ ,' ' .' .

, ~0794S6 ~ Ql ~ i4) (H3S)m ~ 03H)m where one m is 1 or 2 and the other is 0, 1 or 2, and Ql is one of the radicals O, NH, S, S-S, CH2, CH=CH, NHCONH and OCH2CH2O, e-g-4,4'-diaminodiphenylurea -2,2'- and 3,3'-disulphonic acids, - 3,3'-diaminodiphenylurea-4,4'- and 6,6'-disulphonic acids, 4,4'-diaminodiphenylurea-2,2', 5,5'-tetrasulphonic acid, ` 4,4'-diaminodiphenyldisulphide-2,2'-disulphonic acid ; and 4,4'-diaminodiphenoxyethane-2,2'-disulphonic acid.

; It should be noted that many groups including some described above, can react with textile fibres and are ; ~ also capable of becoming convalently linked into amino/
formaldehyde condensates. Thus the fact that a particular group has been described as reactive to textile fibres should not be taken to mean that it cannot also become covalently linked into an amino/formaldehyde condensate or vice versa.
The dyestuff is preferably soluble in the liquid . .
`"t`' medium, usually water which contains the components of the printing paste.

Dyestuffs of the above types are now very well ` known and examples of them may be found in many patent specifications e.g. UK specifications Nos. 875712, 898958, .

8~6505, 922403, 9061~0,1033778 and the further specifications referred to therein.
By the term curable, fully alkylated amino/
formaldehyde precondensate we mean the reaction product of formaldehyde Withcompounds containing NH or NH2 groups and sufficient alcohol such that the products contain no free methylol groups but contain a plurality of etherified methylol groups and are capable upon heating, usually in the presence of acidic catalyst, of condensing to yield --insoluble r cross linked resins. Such products are well known for a variety of uses including textile finishing.
It is preferred to employ fully alkylated amino/formaldehyde condensates which contain lower alkyl methylol ether groups e.g. ethyl, propyl, butyl and especially methyl ethers.
Such groups are derived from the use of the corresponding lower alkanol in the preparation of the alkylated amino/
, formaldehyde precondensate.
As examples of compounds containing NH or ~H2 groups which can be reacted with formaldehyde and an alcohol to produce curable, fully alkylated amino/formaldehyde . precondensates there may be mentioned monomeric or polymeric -compoundscontaining a plurality of amino or mono substituted amino groups, said compounds being known from the art, or used in practice for the formation of resins by condensation with formaldehyde. Suitable compounds include, for example, monomeric nitrogen compounds such as urea, thiourea, substitued ureas and thioureas, dicyandiamide, dicyandiamidine, biguanides, amides, carbamates, allophanates and heterocyclic compounds such as aminotriazine, urons, ureins, ureides, imidazolidones, triazones and hydantoins, or mixtures of such compounds, and polymeric nitrogen compounds such as the polymeric amides maAe by the reaction o~ dibasic acids with diamines.
Particularly useful curable, fully alkylated amino/formaldehyde precondensates include fully methylated hexamethylol melamine and fully methylated trimethylol melamine.
Amino/formaldehyde precondensates, including fully alkylated materials will not only react with themselves during curing to cross-linked resins but can also interact with other substances resulting in resins which incorporate these other substances by covalent chemical bonds. It : will be appreciated that the term "capable of becoming covalently linked into an amino/formaldehyde condensate"
used to defined dyestuffs for use in the process of the present invention means that the dyestuffs so defined (and exemplified above) are capable, of co-reacting with the fully alkylated amino/formaldehyde pre-condensate at ' any stage during the curing process which converts it to a cross linked cured resing thereby themselves becoming a covalently linked part of the resulting cured resin!.
The high molecular weight material containing .`, acidic groups may be any polymeric material of suitable ~, properties but is usually found that preferred materials are synthetic polymers having molecular weights of at least 50,000 in particular 500,000 or higher. Also it is generally preferred that these polymers should be cross-linked rather than linear in structure and that, apart from the acidic groups, these polymers should contain no active hydrogen atoms which can interact with reactive dyestuff . ., . .

10794S~i urder normal conditions of storage of printing compositions e.g. from 10 to 40C. Such synthetic polymers include the addition polymers of unsaturated monomers having acidic groups such as acrylic acid or methacrylic acid and their copolymers with other unsaturated monomers free from acidic groups such as ethylene propylene and vinyl ethers such as vinyl isobutyl ether. Cross-linking may be provided by copolymerising with monomers containing two or more unsaturated groups per molecule e.g. ethylene glycol dimethacrylate or divinyl benzene. Alternatively synthetic polymers containing acidic groups may be obtained by polymerising or copolymerising monomers containing groups which are capable of being converted to acidic groups and subjecting the resulting ~co~polymer to appropriate treatments.
For example polymers of or containing acrylonitrile may be hydrolysed to produce polymers having acrylic acid units.
Also polymers from maleic anhydride may be treated with water to give polymers incorporating maleic acid residues - or they may be treated with ammoniaor amines to give polymers with pendant amido groups and acid groups in the form of (substituted) ammonium salts. Particularly valuable polymers of this type are derived from ethylene/maleic anhydride copolymers, especially when cross-linked.
Other high molecular weight materials containing acidic groups which may be useful in the present invention are condensation polymers bearing acid groups such as polyesters or polyamides obtained by condensing stoichiometric deficiency of polyol or polyamine with polybasic acid.

. . ~
As examples of volatile basic substances suitable for use in the present invention there may be mentioned ' .

`

iO79456 low boiling point amines such as methylamine, dimethylamine, ethylamine, diethylamine or propylamine but it is particularly preferred to use ammonia.
The composition used to print the textile material comprises the components listed as (a) to (d~ above dissolved or dispersed in a liquid medium. For reasons of cost and toxicity it is preferred that this liquid medium is entirely or largely water but materials may be included to increase the solubility of the components of the printing composition, for example, caprolactam, ethylene carbonate, sulpholane, ethylene glycol, diethylene glycol or a poly (alkylene oxide)diol such as a polyethylene or polypropylene glycol.
For satisfactory printing it is fre~uently desirable that the printing composition has a high viscosity or a pasty consistency particularly when intricate patterns are being printed. The high moleculàr weight material ~; containing acidic groups present in the textile printing composition used in the present invention frequently ;~ 20 show thickening properties which are of value in producing the desired consistency in the printing composition.
Additional thickening may be achieved by incorporating conventional thickening agents in the printing composition, for example, solutions of aliginates but it is usually found that this is not necessary.
The printing compostion used in the present invention may optionally include any of the other conventional : .
additives employed with printing compositions of this type.

For example, one or more wetting and dispersing agent may be present such as salts of alkyl naphthalene sulphonic acid, . _ g _ ~ .

:

the reaction products of ethylene oxide with fatty alcohols or amines or alkylphenols, or metals or ammonium salts of fatty acids.
Also, materials may be included to impart water-repellent characteristics, e.g. N-methylol stearamide, silicone derivatives and fluorocarbons.
Also, materials may be included to modify-the handling properties of the printed textile fabric, e.g.
long chain fatty esters or stearamide, or to impart antistatic or soil-repellent characteristics, e.g. those mentioned in U.K. Patent Specification No. 1,088,984, or compounds containing fluorocarbyl groups.
Further, it may be desirable to incorporate in the print paste materials which increase the tinctorial strength of the colour obtained, e.g. liquid paraffin.
Preferred print pastes for use in the process of the present invention especially when deep shades are required showing good resistance to washing treatments, will incorporate diethylene glycol, stearamide and liquid paraffin.
The printing compositions used in the present invention will normally be associated with adequate cure of the fully alkylated amino/formaldehyde precondensate after being subjected to the heating stage. It is believed that the acidic groups present in the high molecular weight material containing acidic groups provide sufficient catalysis to promote this cure, however, in some instances it may be desirable to include a catalyst for the cure of fully alkylated amino/formaldehyde precondensates. Any . 30 conventional acid or acid forming catalyst known for this purpose may be added but it is generally preferred to use the relatively mild catalysts such as ammonium sulphate or diammonium phosphate rather than known power~ul catalysts such as ammonium nitrate or chloride.
The printing composition Eor use in the present invention are prepared by dissolving or dispersing the specified components in a liquid medium usually water.
Preferred proportions of the various components will be determined by the properties e.g. depth of coloration desired and these proportions wLll usually lie in the following ranges.
(a) Dyestuff: 1% to 4.0% by weight of the printing composition ; (b) Fully alkylated amino/formaldehyde precondensate solution ~concentration 60 parts of precondensate per 100 parts of solution): 5~ to 12% by weight of the printing composition.
(c) High molecular weight material containing acidic groups: 0.4:to 2.0~ by ~eight of the printing composition.
(d) Volatile basic substance: 0.2 to 5% by weight of the printing composition.
- When surface active materials are included for their wetting, dispersing or levelling properties they are usually employed at from 0.5~ to 2.0% by weight of the printing composition.
The amount of volatile basic substance used is , controlled by the requirement to produce a printing composition having a pH of at least 8. The preferred pH
is from 8 to 11.
; 30 It is preferred, especially when the printed ..

textile material is to be sold without a prelimin~ry washing treatment that the amount of fully alkylated amino/
formaldeh~de precondensate shall be at least 3 preferably at least 4 times the weight of dyestuff in the printing composition.
The components may be incorporated into the printing composition in any order using any conventional technique of mixing or blending. It is often found in practice, however, that certain mixing procedures may be preferred, for example, it may facilitate the preparation of uniform printing compositions if components such as the dyestuff or the high molecular weight material containing acidic groups are mixed thoroughly with a small amount of liquid medium optionally together with a wetting or dispersing agent, before being added to the remainder of the liquid medium. Also it may be found advantageous to mix the volatile basic substance with the high molecular ., j .
weight material containing acidic groups in the presence of a small amount of liquid medium especially water and wetting agent before these components are mixed with the remainder of the printing composition.
The printing composition may be applied to the textile materials by any conventional means such as rollers, rotary screen printing, flat bed screen printing, surface printing or wet transfer printing techniques.
After application of the printing composition the printed textile material is subjected to a heating stage to volatilise the volatile basic-substance and cure the fully alkylated amino/formaldehyde precondensate. This ` 30 heating stage also removes the liquid medium in which the - , "' .

, 107~56 printing composition is prepared if it is volatile as in the case of preferred medium water.
The heating of the printed textile material may be achieved by any conventional means such as heated rollers, infra red lamps, hot air or high temperature steam and may take place immediately after printing or after a period of storage.
It is frequently found convenient and advantageous to conduct the heating stage in two steps. The first step is a drying, preferably carried out at 75 to 125C but the temperature of drying is not critical. The second step is a baking usually carried out at higher temperature than the drying step.
The heat treatment step may be carried out at a wide range of temperatures, provided the temperature is sufficiently high to cure the fully alkylated amino/
formaldehyde precondensate. The time of heat treatment will depend upon the temperature used, a short period of heating, for example, about 10 seconds being sufficient at temperatures of the order of 200C whilst a period of about 1 to 8 usually 5 minutes is required at a temperature of about 155C. The heat treatment is preferably at between 130C and 210C especially 150-210C adiusting the time to minimize thermal degradation of the cellulose.
convenient method of heat treatment is to expose the printed, dried fabric to high temperature steam at, for example, 160-180C for 4 to 6 minutes.
A wide range of textile materials may be coloured by printing using the process of the present invention, for example, it may be used with woven or non-woven fabrics ~79~56 such as p~lyetlly1e~e terephthalate, polyamides such as polycaprolactam or polyhexamethylene adipamide and is particularly useful ~or fabrics from natural or regenerated cellulose fibres such as cotton or viscose rayon. The process of the present invention is a~so applicable to fabrics from blends of fibres in particular to cellulose/
polyester unions. When printing cellulose/polyester unions particularly with deep shades, it may be found desirable to additionally include a disperse dyestuff in the printing composition.
The process of the present invention provides a means of colouring textile materials by printing, associated with various advantageous features. The proportion of applied dyestuff fixed is very high and the printed fabric frequently needs no washing or other treatment before sale and use. At the pHs specified for the present process the printing composition is much thicker than the same composition at more acidic pHs thus economies on the use of thickening component are possible. The printing composition used in the present process is compar-atively stable and may be stored without deterioration for long periods before application to the textile substrates but this stability is not associated with a need for significantly increased heating to produce adequate cure and dye fixation.
The textile materials coloured by the present process have a good resistance to loss of colour during a variety of washing, dry cleaning and similar treatments.
Also the textiles coloured by the present process are associated with a low tendency for any uncoloured portions .

: -.
,. : . . :
.

107~45G
to be stained during washing treatments. The printed textiles also have good handle properties.
The invention is illustrated by the following Examples in which all parts and percentages are by weight~

A printing paste of the following composition a) 20 parts of Dyestuff No. 1 in Table I
b) 80 parts of "Acrafix*M" (a commercially a~ailable 60%
solution of etherified melamine/formaldehyde resin).
c) 10 parts of "Viscofas*X 100,000" (a commercially available methyl vinylether/maleic anhydride copolymer).
d) 10 parts of an 8% aqueous alginate solution.
e) sufficient ammonia solution to give a pH of 9.0 to the total composition f) water to give a total of 1000 parts;
is prepared by adding the "Viscofas X 100,000" to the water whilst vigorously agitating and the pH is then adjusted to 9.0 additions of 28~ aqueous ammonia solution :j~
followed by the gradual addition of the alginate solution, the '!Acrafix M" and the dyestuff in that order whilst again ~,...
agitating vigorously.
This composition is printed onto a plain weave cotton fabric using an engrave roller. The printed fabric is dried at 80C and baked at 150C for 5 minutes. Ammonia is evolved particularly in the early stages of the dry/
baking step. The resulting printed fabric is coloured with a greenish-yellow pattern and needs no washing before use.
The p~inted fabric has a good, soft handle and the uncoloured ` parts of the pattern show no staining during subsequent ; 30 launderings which also do not result in any loss o colour from the coloured parts of the pattern.

* Trademarks ,, 1~)'79456 By replacing the dyestuff No. 1 in the above composition wi~h any of the dyestuffs 2 to 7 in Table 1 it is possible to obtain similar prints having the shades indicated in that Table.

Using the procedure given in Example 1 a printing paste of the following composition was prepared.
a) 20 parts of Dyestuff No. 1 in Table 1.
b) 80 parts of "Acrafix M".
c) 12 parts of "Viscofas X 100,000"
d) 10 parts of an 8% aqueous alginate solution.
e) sufficient aque~us ammonia solution to give pH
of 9.0 to the total composition.
f) Water to give a total of 1000 parts.
This composition is applied to plain weave - cotton fabric through patterned screen using a standard screen printing technique.
The printed fabric is dried and baked as : described in Example 1 resulting in a similar greenish yellow print with similar properties.
By replacing the dyestuff No. 1 in the above composition with any of the dyestuffs 2 to 7 in Table 1 it is possible to obtain similar prints having the shades indicated in ~hat Table.

, , .
. .

, .

,: . . . .

1~7g456 .~ 3 ~ ; `, i-~ ~_~z ~o~ ~0~

~,Z~/Z ~ / 7 ~/

~ ~ ? ~ z~
I o ~ I ~~

u~ ~

~= ~ n ~079456 ~, ~ o~
1l ~ r . U .
~ . X . ~

o~ I ;

~1 3 /u~ ~ ~

3 Y ~ ~
Z--~ ~

~ . ,~
:''" , ~
` ' _ -. .

1~

~¦ L ~ ~ --~ ~ =

.

:

~ XAMPLE 3 A printing paste of the following composition:-(a) 15 parts of dye No. 1 in Table I
(b) 90 parts of 'Acrafix M' (Bayer) (c) 5 parts o~ am~onium sulphate (d) 5 parts of diammonium hydrogen phosphate (e) 40 parts of diethylene glycol (f) 30 parts of the thickener concentrate prepared as given below (g) 50 parts of liquid paraffin (h) 150 parts of the 10% stearamide emulsion prepared as given below (i) sufficient aqueous ammonia solution to give a pH
of 10 to the total composition (j) water to give a total of 1000 parts is prepared by mixing the ingredient with vigorous agitation Thiscomposition is printed on to a plain weave cotton fabric using an engrave roller. The printed fabric is dried at 80C and baked at 160C for 6 minutes. Ammonia is evolved particularly in the early stages of the dry/
baking step. The resulting printed fabric is coloured with a greenish-yel}ow pattern and needs no washing before use. - - -The printed fabric has a good, soft handle and the uncoloured I parts of the pattern show no staining during subsequent `- launderings which also do not result in any loss of colour from the coloured parts of the pattern.
The print paste remains usable for up to 2 weeks.
, The thickener concentrate is prepared as follows:-a mixture of:-liquid paraffin oil 6 parts white spirit 12 parts water 25 parts .

' Cirrasol EN-MP* 3 parts Lubrol 17-Al-* 1 part Matexil D~-VL* 3 parts * trademarks for commercially available surfactants is agitated vigorously together. Then the following are added in the order given, with cooling, and stirred well into the emulsion EMA 91 10 5 parts (EMA 91 is a trademark commercially available ethylene/maleic anhydride copolymer of high mol.wt.) ammonia solution sp.gr 0.890 14.5 parts EMA 91 10.5 parts ammonia solution sp gr 0.890 14.5 parts Stirring is continued until a smooth creamy paste is obtained.
The 10% stearamide emulsion (h) is made by stirring at high speed a mixture of stearamide (10 parts), water (88 parts), and thickener concentrate (f) (2 parts) until a smooth emulsion is obtained.
The dyestuffs in the above print paste can be re-placed by any of dyes 2-109 in Tables I-XVI giving prints o the colour listed and needing little or no washing before use, ~0~9456 TABLE II

No.; Structure Shade-_ ~, . ~ ~ N = ~ ~ CH
8 503H \ N - R Orange . , . ...

. 9 R NH ~ N ~ 503H Yellow N = N

. S03H C~2H
~ ."'' ;: .

- lo I ~ - N = N ~ I ~ Yellow I ~ 03H C33 ,., ~.' ~11 ¦ ~ N = N ~ Orange , S03H NH R
., ~ ~ , _ .... . . .. . . ':

., ,., NHCONH2 in dyes No. 8 to 11 R = -02S ~ CH3 .:, , 10'~9456 - TABLE III

Dyes o the general formula:

SO3H pH R
N = N ~ N\ ~ X

~ Y
. _ . .
No. R X Shade . _~NHcoNH2 12 H -Cl -NH ~ Orange : 1 3A C113 14 H NH2 .. n 1 4A CH3 n n n H - Cl -NH2 n 1 5A CH3 .. .- n 16A CH3 -N~CH3)CH2~CROH)4CH20H
17 H - NH2 ~ n . 17A CH3 .. .. ..
18 H -Cl -NHC(-NH~NHCN ..
. l~A CH3 .. .. n .~ 19 H -NH2 -NH2 ..
1 9A C 33 . ~, - -. - 23 -~', ' .
:, :

continuation of TABLE III

No. R X Y~_ _ Shade 20 H -Cl -NHC(=NH~NHCONH2 Orange 2OA CH3 ll . , 21 H -NH2 .. n 2lA CH3 ll ll ~
22 H -Cl -NH ~ S02NHCONH2 ..
22A CH3 n . "
23 H -NH2 . ,.
23A CH3 ll ,. . ..
24 H -NHCH3 -NHCH3 n 24A CH3 .. " .
25 H -Cl -NHcH2cH2NHcoNH2 25A C33 _ . .
. . ...

.

~079456 TABLE IV
Dyes of the general formula OEI
CH30 ~ _ N_N ~ N N ~ -S03H ~ ~ ~

-wherein.
. _._ _ Number R X Y Shade .
26 -CH3 -NH2 _N~2j Scarlet 2~ -CH3 -Cl -NH2 ..
28 -H -Cl -NH2 - .
29 -H -NH2 -NH2. .. .
-CN3 -3HCH3 N~CU3 .-, ,. :: .

,, .

~ . . .

. ~ .
' . . .
, , TABLE V
.

No. Structure _ S~ld~__ ¦31 ¦ ~ 3 ~ ¦ Red NH C ~HN . Yellow .
32 ~H ~ ~N ~ S03H

. NH2 ONH S03H OH .

: 33 CuPc(3-S03H)2(3-SO NHCH CH NHCONH ) .
2 2 2 2 Z . urquols~ !

34 CuPc(3-S03H)2 7~3-so2HNcH2cH2NH2 ~ ~ ~ ........... .-NHCH2C~2NHCNH ~ 1.3 CuPc(3-S03H)1 7(3-SO NH ~ CH-C ~ -NH~

: ~03H S03H NHC~NH )2 ' CuPc represents the copper phthalocyanine ~ 3 . nucleus .
~'. .

36 C ~ N OH NH2 N~ _N Bluue " . N ~ NH ~ N=N - ~ N-N ~ N

. S03H S0.3H S03H 503H
. .

TABLE VI
Dyes of the general formula:

N/ ~ Nl~ = N~ I ~N~
S03~S03H X

Number X Shade .
_ . . .
37 H -N (CH2cH20H~ 2 Scarlet - ~ 37A ~ C 3 -NH~

3 8A CH3 .. .-' :

, .

~d.27561 TA~~I,`r~ V 10794S6 _ . . ..
Numh~r~ Str~lcturc Shade ___ ~ .
31 ~ ~ Red.
-~ N = N - ~ NH2 . ~ C~O~N .
32 ~ NH N ~ N_N ~ I ~ Yellow . . NH~CONH 03H OH .
., ' .
~' . . . . 33 CuPc(3-S03H)2(3-S02NHCH2CH2NHCONH2)2 Turquoise .; . ~ Cl 34 CuPc(3-S03H)2 7(3-S02N~CH2CH2N ~ ~ ~ ..
~, . NHCH2CH2NHCONH2) 1 ' i .l . . . Cl ~ . i ¦ 35 CyPc(3-503 J1 7(3-S2N ~ ~ H=CH ~ N3 ~ =< ¦ \ ¦
i 3 NHCONH .
, . . I .3 . :

CuPc represents the copper phthalocyanine nucleu~ l "1~ . . . .

., . . n 1 Cl 36 ~ /> NH ~ N=N ~ N N ~ NH ~/ ~ DbUllul - _ H2 S03H S03H 3 S03H 2 _ ., .
1' ' ' ' . :
~ 28 ~
., . . .
.

~: . . . . .. .. .
: . . - : . . .

- . , . ~ . . .

Dd.27561 TABI~ VI ~
.

Dyes of the ~eneral formula:

N`~= ~ ~ N ~ /NN ~ Cl ' ':
'.

Number R X Shade . 37 H -N(CE~2cH2H)2 Scarlet 37A CH3 ~ ,S0 H ~
38 H . ~ 3 ~-L~i L: ~
., ' ,'' ' ' .': , , , . I

~ 29 -.
.1 .

. ~' ' ' .' ' '~'. , . ' ' " , ', ' ~ '.,, ~' ' ' ' , `:~ . .. ; ' ! ' ' ' ' " ' '~ . ' ' ` ' . ': . ' -, " ~ ' ', ~07945~; -- . Dd.27561 TABI~ VII :

, Dye6 of the general formula:

X ~N
~r-N OH NH~ N ;
>=N\>--NS~I~ - N~Sbo3=<~

1, , ' , ' ' . i Number X . y Shade l . .
39 -Cl OH Bluish-red .
-ON ¦ 3 ¦ ¦

. 41 . -NH2 . n l ¦~
~ ' . ' . . , . .
42 _Cl -NH ~ 1~
~
. . NHCONH2 I
43 -N~2 ~ ~ ~ _ :
, ~ : 44 -OH -OH . .
: 45 -Cl -NHC~=NH)NHCN . ;
46 -Cl -NHCH2CH2NRCONH2 .
. ,. _~NN2 .

: . 47 -NN2 . ~ . .
: 48 . -Cl -NHCH2CH2NH2 . ;

~1 . 49 -NH2 ~
,~tj ~ _ 30 ~`7~1 !
J ' ' ' : ' ' ~ ' ' ' ' ' .' ' .

~ ;' :
''~ ~ ' ~ ' ';' ' 1079456 Dd,27561 TABLE VIII

Dyes of the general formula:

I

Number _ __ Shade .
. 50 -Cl ~ . Bluish-red .
. ONH2 .

51 -~2 . - "-. 1~ . .

1~ ~ 52 -Cl -NHC(=XN)NHCN

. . 53 ~ 2 " . .

`~ 54 -~2 -NH2 . 11 .

-Cl NE~CH2CN2N~COXN2 . ~;

. 56 -NH2 - . -- - _ G

., . . . . , .~
~1 31 - -.'~ . . -' ' -79456 Dd.27561 ~ABIJE IX
~ .

Dye~ of the ~eneral formula:

' X

~N = N ~ 8 h ~ ~
O K SO H =< .

., , ' . :
.

Number R R y ¦ Shade _ _~,SO H .
57 -N -H NH2 -NH ~ 3 Orange .

¦ 58 ¦ 3 59 -503H -S03H -N82 . l -H -503H I -Cl ^NHCH2CH2NHCONH2 ~ " ¦' `
61 . -H _S03H ¦ NH2 - n 62 -S03H -S03H -Cl . n 63 -S03H -H -Gl . . .
~o~K -S038 -NH2 . 1~

. . . ' . ~ -.
.~ ' , . '. . . :' ~ ~ .
: , ' . ` ' ' ` .
' ' , .

I ~;7 , . , .
,,-',~ ,, .,,' ,' .

. .
. ~: . ' . . . :' . - -:.
., . . . - ~.

~: . : ., .. : ..
~r' r, .

1~794~6 Dd.27561 TA~LE X
.

Dyes of the g~nernl formula:

~N ~ N~

3 SO~

I
. Number R X Y Shade .... _ ~__ __ ~
i 65 -S3H . -Cl -NH ~ Yello~
' . . ~HCONB2 ~ :'.', . . . . . '~, . 66 -S03H NH2 ,l n . . . "::
67 -H . " " " .
68 -H -Cl -NHCH2CH2NHCONH2 .
69 -H -NH2 . n -SO3H ll . ~ .
71 -S03N n -NH2 .
72 -S03H -Cl -NH ~ 02NHCOt ~2 73 -S03H NH2 . ~ .
74 . -S03H -Cl -N(CH3)CH2(CHOH)4CH20 ~:
. . . i~
. . ~ . t `~. . . . . . . _..... . . 1l .
~ ~ 33 ~ ~`
j ` !

~ , . ... , . . I
.. , . . . .... . .. .. . ;

;.... .. . ~ . .... ` .. . ~. . .
..... . . . ~ . ... .... - ~ ... ... ~ .... ... . `
.,... ~. ` ` ...... . .; ~ .... . ;i ..... .. `. ; .. . . ~ .
.... . , . .. . . .. . . ~ . . . . . . . .

... ~ . . . . . . .. , . . ; . .. . . . . .

.~:, . ' ' .`. " ' .' ' . '. . :

Dd. 2756 1 TABLE XI
. .

Dye6 of the general formula: ¦

N ~ N ~ ,O ~ ~ N~
N S03H NHCH2cH2~HcON~
NH2CONHCH2CH2NH S03~1 S03H Cl :

Number X Shade .
-Cl Blue . . .

-NHz . . .
' . ,. ~.

,~' . .
"
: . .
- . . .
- ', ' ' ' .
. :
.' , .
, . . . : .
; . . .
. ~ ' 1 ~J - 34 -,;'1 . .

.i,., . .. . . . ~.... .
.: ~: ..... . ` .. : . . .: ~.
, .. :: . .. . . ~ . . . . : .

.. : . : . :: : : : . : : .: :: ::.: :: :":
`;: : :: :: : :: ~ : .
::. ~ .: . : ` ~ .. : :, : : :

:. :: : , :- .- -::: : - :: . :: : .
, : : ~ - . ::
;:

1079 456 Dd.27561 .

Dye~ of the eeneral formula: l y 03H ~ ~ ~ NH
50 ~ hZ ~ ~ Z

:.:
. ' . :

No- - R X ~ Shade 77 -S03i~ -H 2 `-NH2 ~ 03H Bluish-red 78 -H -S03H -Cl. -Cl ~ MHCONH2 l 79 H -~03H -NH2 NH2 - ~ 503H '- I

1~ ~ I~L ~
, .
. , ' , , . . .

' . ' ` ' .
,: - 35 ~
~1 ' ' ' ` .

~.J ` .
. .
.

.:: :: : . . , . ` :
:. .
r,.;`: : . ' :. ; . ' , '.

~079456 Dd.27561 TAB~ Xl:II
-.

Dyes of the general formula: J~l OH OH NH ~/ ~
- 2:1 mixed Cr/Co complex of ~ ~ ~N X

~', ' ' ' . ' ,.
.
.Number Shade :i ~-~NHCONH :-¦ B1 ¦ -NB ~ 2 I Blaok 82 -~C~2CB2NHCNH2 .

3 l -NBCN2 W2N~2 - . ':' , , , - :

1~ - 3~ ~ ` .

~ ~....... ' ' ' ' ' .
. ' .
'i ' ' ' ' ' ' ,', ' , .

: :. : : : : . . .1 . -: - :-:,::, - :, - - : . : . ~
:: :: . - . ~ :. .- .

, ::;~ ~ - : . .,:

TABLE XIV

No . Structure . Shade - ~. __ 41 [~ ~CI 3~(C1!2C1120~1)2 ¦ Orange S03H N:~

- S03H N (CH2CH20H) 2 ,: ~ n , . =
I,, ~ ~

"J
. ' .

.. . . .

Dd. 27561 - 107~456 TA~ f -- .

Dyet3 of the general formula: -_~'H2 .
~;3~OH NH j~ N
. ~ ~S03H A Bluish-red . 2 . . .

_ . . _ .
Number A .
86 ~ -NH 4~NH- .

87 -NH~NHCONH~-NH- . .
~S 3 .
88 -NH ~ NH- .
. . ' . .

89 3 `

~ Ilc'll20~-~ ' ~
,~ ~ ' ' . - .
`3 - 38 _ .~ , ' . ' ' . .

;......... , , . , ~. .

~: ....... . . .: . .
.

io79456 Dd.27561 .__. ____ _ _ o~

l l L ~ ~ ~L
il ~ ;

~' , æ l .
. ~ .
. ~ . . .

., . ,' ' . .

.: . . . ;, . . . .. . . .

-" 1079456 Dd . 27561 ._ ___.__ , , , ' .' .

~ hO ~ ~ . .' u~ h ` ~
__ .

~1 ~e ~ AJ~

~ A
~ . ~ z J ~ ~D .
~.' ., . :
'; . - 40-' ` ` - . :
. .,. ".: . ` .
,`- . ` ` . . :
,: .. ` :
`
. ~" " ' ;

~079 456 Dd . 2 7~;61 __ . ___ i ~

~) ~rl ~1 0 Q~

`r w~

~N . ~
_ ~C X ,~~

:z æ ~8 . .
.
. ~
:1 . , .

~?
' ' - . . . : :

~,. . ` . . ` . . : - : - .
`' . . ,. : . ' :, ` .
~ '`~ . ' ;

1079456 Dd . ~7561 . ~ ~ ~, ,q a ~ ~ .
~ .
_ u fi U~ ~ " .
~ o o~O ~ j . . ., . ~
;, . _ , . .
.,, . . . , -.
'1 . ~ o . o . o . ~
.- 42 - :
` ',~
~, . .

. ~.~,.. . . .
.:
.

.. . .
.'... :

, - : : -"~ ,' .

1079456 Dd.275~1 . ___ .~

a a ~ ,~ 0 ~ ~ Or` ~ Z;
~n ~
C~ ~
- . ~3 ., I ¦ o ,, ~ o ¦

~ ~ i ? ~C`
. ~-. . ~ 2; U~
.~ ~ O ~ ~g ~iR~
R ~ o~ O

~ o ~ R ~ ~
~ .. . ... .
~C X X ~
............... ... __ __ -:
. . . . .
.: . . .
~ U~ .
o o o o o o o 2i . . . . . . .
' _ .. . ~ . .
, -. ..
. . 1.
- 4~- I
~;"t . . . .
J
.~ . ' . - , ' ' , . " ' . .. . , , ' . ' . ' ' , , .. . . . .
: ' ` . ' ,' -. , :
: . . :
~.': ' ' ' :

:1079456 A print paste is made as in Example 3, but omitting items (c) and td) and applied to cotton fabric, The printed dried fabric is baked at 210 for 1 minute to give a similar print to those obtained in Example 3.
EXAMPLE S
The procedure of Example 3 was followed except that the thickener concentrate is prepared as follows:
a mixture of:
liquid paraffin14 parts Cirrasol EN-MP 4 parts aluminium stearate 1 part Carbopol 940* 9 parts Carbopol 941* 9 parts 25% Nafka crystal gum 13.5 parts water 27 parts ammonia solution 22,5 parts - sp.gr. 0.890 * trademark for commerciallyauailable polyacrylic acids (Goodrich) ~, is stirred together until a smooth paste is obtained. Similar '~ `prints to those in Example 3 are obtained.
~Z

1, ` , ,, :

' ', ~0794S6 ~X~PLE 6 The procedure of Example 3 is followed except that in the thickener concentr~te each 14.5 parts of ammonia solution is replaced by 22 parts of 40%
methylamine solution and the pH adjustment of the print .
paste item (i) is made with methylamine solution rather than ammonia. Methylamine is evolved during the drying/
curing of the prints which otherwise are similar to those obtained in Example 3.
j The procedure of Example 3 is followed using a print paste of the following composition:-(a) 15 parts of dyestuff (b) 90 parts of 'Acrafix M' (c) 5 parts of ammonium sulphate :~
(d) 5 parts of diammonium hydrogen phosphate (e) 40 parts of diethylene glycol (f) 30 parts of Acraconc 'O' (a commercially available thickener concentrate) (g) 50 parts of liquid paraffin (h) 150 parts of 10% stearamide emulsion .
(i) sufficient aqueous ammonia solution to give a pH of lO.S to the composition (j) water to give a total of 1000 parts 3 the components being mixed together with vigorous agitation.
. The resulting prints are of the same character-istics as those obtained in Example 3.

~ ~ I
' '`,':'' ' - , , EX~MPLE 8 The procedure of Example 3 is repeated except that the thickener concentrate consists of the following ingredients:-liquid paraffin 18 parts water 25 parts Cirrasol EN-MP 7 parts EMA 91 10.5 parts ammonia solution14.5 parts sp.gr. 0.890 --EMA 91 10.5 parts ammonia solution14.5 parts sp.gr. 0.890 mixed in the above order with vigorous agitation.
The resulting prints are similar to those obtained in Example 3.

The procedure of Example 3 is repeated except , that in the print paste, items ~c) and (d) are omitted, ~
; ~ 20 and Acrafix M (90 parts) is replaced by Fixer M (120 parts~ -(Fixer M being a commercially available etherified melamine/
~- formaldehyde resin 45% solution). The resultant prints are similar to those obtained in Example 3.

The procedure of Example 3 is repeated except that the 15 parts of dyestuff is replaced in turn by 35 parts of each of the following dyestuffs from the Tables:-1, 33, 42, 43, 46, 5~, 51, 55, 56, 58, 59 to 70, 75,76, 81, 82, 91 to 96, 99, 100, 103, 107 and~108.

, . .: , . : .~. .: -,., .. .; .. ~ , ~. . :: : , 10~94S6 The prints so obtained have a much deeper shade than the corresponding print obtained in Example 3, nevertheless they may still be used withou-t prior washing.
These prints also have good, soft handle and the uncoloured part of the pattern shows no staining during subsequent launderings. The coloured fabric has a good res~stance to loss of colour during washing treatments.

-The procedure of Example 7 is repeated except that the print paste is modified to contain 35 parts of any one of the dyes detailed in Example 10,.
The resultant prints have deep shades o~ colour, can be used without prior washing and show no staining of uncoloured fabric or loss of colour during subsequent launderings.

The procedure of Example 9 is repeated except that the print paste is modified to contain 30 parts of any one of the dyes detailed in Example 10.
The resulting prints have deep shade of colouration and may be used without prior washing. The prints resist staining of uncoloured fabric and loss of colour during subsequent launderings`.

To compare the stability of print pastes of the present invention with similar compositions at lower pH
the following are mixed:

,, .

'' :
.: .

10~9456 A mixture of the dyestuffs 2-(4' -methoxy-2'-sulphophenylazo)-6-(N-methyl-N-~2"-chloro-4"-~x"'-sulphophenylamin~ -s-triazin-6-yl~amino)-3-sulpho-1-naphthol, where x is 3 or 4 3 parts Fixer M (see Example 9) 6 parts Thickener concentrate as used in Example 3 3 parts Water 88 parts and divided into three parts. One is adjusted to pH 9 by addition of aqueous ammonia and the other two are adjusted to pH 7 and S respectively by addition of acetic acid.
Initially all these print pastes are bright, cleàr and homogeneous and when applied to textile fabrics give an even bright red shade. However the viscosity of the comp-osition at pH 7 and particularly the composition at pH 5 are lower than that at pH9. The viscosity of the acid compositions is too low for fully satisfactory printing under some conditions.
After two days at room temperature the composition at pH 5 is increased and precipitated material can be seen.
;; 20 After 6 days this composition is unusually thick with gross separation of insoluble material.
After six days the composition at pH 7 shows some lumpyness and when printed gives a dull "gritty"
colouration much inferior to the colouration it gave when freshly mixed.
After six days the compositlon at pH 9 is unchanged i.e. it is a smooth clear paste which gives bright, level colouration when applied printed on textile fabrics.
' - 48 - ~

,

Claims (15)

The embodiments of the invention in which an exclusive privilege or property is claimed are defined as follows:

1. A process for the coloration of textile materials by printing with a composition containing (a) a dyestuff capable of forming a covalent bond with the fibres of the textile material or of becoming co-valently linked into an amino/formaldehyde condensate, (b) a curable fully alkylated amino/formaldehyde precondensate, (c) a high molecular weight material containing acidic groups, (d) a volatile basic substance present in sufficient quantity to make the pH of the composition at least 8, and heating the printed textile material to volatilise the basic substance and to cure the fully alkylated amino/formaldehyde precondensate

2. A process as claimed in Claim 1 wherein the dye-stuff contains one or more s-triazine groups having a substitu-ent or substituents capable of reacting with the fully alkylated amino/formaldehyde condensate.

3. A process as claimed in Claim 2 wherein the dye-stuff is of the formula:

where D is a chromophoric group, A is Cl, OH, NH2, alkylamino or SO3H, and B is or -NHCH2CH2NHCONH2.

4. A process as claimed in Claim 1 wherein the curable fully alkylated amino/formaldehyde condensate contains lower alkyl methylol ether groups.

5. A process as claimed in Claim 4 wherein the curable fully alkylated amino/formaldehyde condensate contains methyl methylol ether groups.

6. A process as claimed in Claim 5 wherein the curable fully alkylated amino/formaldehyde condensate is fully methylated hexa- or tri-methylol melamine.

7. A process as claimed in Claim 1 wherein the high molecular weight material containing acidic groups is a synthetic polymer of molecular weight at least 50,000 having no active hydrogen atoms which can interact with the dyestuffs at from 10-40°C apart from those of the acidic groups.

8. A process as claimed in Claim 7 wherein the molecular weight is at least 500,000.

9. A process as claimed in Claim 7 wherein the high molecular weight polymer containing acidic groups is cross linked.

10. A process as claimed in Claim 7, 8 or 9 wherein the high molecular weight polymer containing acidic groups is derived from an ethylene/maleic anhydride copolymer or an methyl vinyl ether/maleic anhydride copolymer.

11. A process as claimed in Claim 1, 2 or 3 wherein the volatile basic substance is ammonia.

12. A process as claimed in Claim 1, 2 or 3 wherein the pH of the printing composition is from 8 to 11.

13. A process as claimed in Claim 1, 2 or 3 wherein the printed textile material is heated to 150-210°C.

14. A process as claimed in Claim 1, 2 or 3 wherein the printing composition contains diethylene glycol, stearamide and liquid paraffin.

15. Textile materials when coloured by a printing process as claimed in Claim 1.