Note: Descriptions are shown in the official language in which they were submitted.
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.
-- 2
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
-- 3 --
,
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
H2N 2
~ 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,
.
1079456
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
-- 6 --
1079456
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
- 8 -
' .
`
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 _
~ .
:
1079456
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
-- 1 0 --
1079456
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
- 11 -
..
1079456
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
- 12 -
- ,
"' .
,
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
- 13 -
~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
.
-14 -
: -
.
,. : . . :
.
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~
EXAMPLE 1
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.
- 15 -
* 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.
EXAMPLE 2
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.
, , .
. .
,
- 16 -
.
,: . . . .
1~7g456
.~ 3 ~ ; `,
i-
~ ~_~z ~o~ ~0~
~,Z~/Z ~ / 7 ~/
~ ~ ? ~ z~
I o ~ I ~~
u~ ~
~= ~ n
-- 17 --
~079456
~, ~ o~
1l ~ r
. U .
~ . X . ~
o~ I ;
~1 3 /u~ ~ ~
3 Y ~ ~
Z--~ ~
~ . ,~
:''" , ~
` ' _ -
. .
1079456
1~
~¦ L ~ ~ --
~ ~ =
.
-- 19 --
:
1079456
~ 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
.
'
1079456
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,
- 21
~0~9456
TABLE II
No.; Structure Shade-
_ ~,
. ~ ~ N = ~ ~ CH
8 503H \ N - R Orange
S03H
. , . ...
. 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
NHCONH2
- 22 -
.:, ,
10'~9456
- TABLE III
Dyes o the general formula:
SO3H pH R
N = N ~ N\ ~ X
SO3H
~ 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 -
~',
' .
:, :
1079456
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 _ . .
. . ...
.
- 24 -
~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 .-
, ,. :: .
,, .
- 25 -
~ . . .
. ~ .
'
. . .
, ,
1079456
TABLE V
.
No. Structure _ S~ld~__
¦31 ¦ ~ 3 ~ ¦ Red
S03H S3H
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
. .
- 26 -
1079456
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 .. .-
- 27 -
'
:
,
.
~d.27561
TA~~I,`r~ V 10794S6
_ . . ..
Numh~r~ Str~lcturc Shade
___ ~ .
31 ~ ~ Red.
-~ N = N - ~ NH2
S03H 3
. ~ 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
3 S03H
' ':
'.
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~
. . . ' . ~ -
.
.~ ' , . '. . . :'
~ ~ .
: , ' . ` ' ' ` .
' ' , .
- 32 - -
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
1079456
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
.
TABLE XII 1-
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
N02
~', ' ' ' . ' ,.
.
.Number Shade
:i ~-~NHCONH :-
¦ B1 ¦ -NB ~ 2 I Blaok
82 -~C~2CB2NHCNH2 .
3 l -NBCN2 W2N~2
- . ':'
, , , - :
1~ - 3~ ~ ` .
~ ~....... ' ' ' ' ' .
. ' .
'i ' ' ' ' ' ' ,', ' , .
: :. : : : : . . .1 . -: - :-
:,::, - :, - - : . : . ~
:: :: . - . ~ :. .- .
, ::;~ ~ - : . .,:
1079456
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 .
. ~ .
. ~ . . .
- 39 -
., . ,' ' . .
.: . . . ;, . . . .. . . .
-" 1079456 Dd . 27561
._ ___.__ , , , ' .' .
~ hO ~ ~ . .'
0
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 . , .
- 41 -
~?
' ' - . . . : :
~,. . ` . . ` . . : - : - .
`' . . ,. : . ' :, ` .
~ '`~ . ' ;
1079456 Dd . ~7561
. ~ ~ ~,
,q a ~ ~ .
~ .
_ u
fi
U~ ~ " .
~ o o~O ~ j
. . ., . ~
;, . _ , . .
.,, . . . , -.
'1 . ~ o . o . o
. ~
.- 42 - :
` ',~
~, . .
. ~.~,.. . . .
.:
.
.. . .
.'... :
, - : : -
"~ ,' .
1079456 Dd.275~1
. ___ .~
0 0
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
EXAMPLE 4
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
- 44
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
EXAMPLE 7
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.
- 45 -
~ ~ I
'
'`,':'' ' - , ,
1079456
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.
EXAMPLE 9
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.
EXAMPLE 10
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.
- 46 -
, . .: , . : .~. .: -
,., .. .; .. ~ , ~. . :: : ,
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.
EXAMPLE 11
-
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.
EXAMPLE 12
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`.
EXAMPLE 13
To compare the stability of print pastes of the
present invention with similar compositions at lower pH
the following are mixed:
- 47 -
,, .
''
:
.: .
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 - ~
,
