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Патент USA US2131098

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1 2,131,098
- Patented Septt27t 1938
coLona'rIoN or MATERIALS
Henry Dreyius, mason, England
' No
Application September 20, 1935,
Serial No. 41,419. In Great Britain Septem
ber 28, 1934
10 Claims.
This invention relates to the coloration of ma
(Cl. 8-48),
alkoxy or alkyl anilines obtainable by diazotizing
terials made 01' or containing synthetic resins. . the aniline derivative and coupling with cou
‘At the present'time synthetic resins ?nd ex- _ pling components of the naphthalene or other '
‘ tensive and increasing employment in numerous suitable series; unsulphonated coloring matters
5\ industries.
Amongst the many industries in
which these bodies are employed there may‘ be
; mentioned the plastic industry and the textile
‘ During recent years textile materials impreg
1_° nated with‘or containing synthetic resins have
come into prominence.
Such textiles are not so
readily colored by the dyestuilfs customarily em-'
or compounds of the stilbene group, for example 5
stilbene disazobisphenol, stiibene disazobis-m
toluidine,’ stilbene‘ disazobis-a-naphthylamine,
or * .
aminostilbene-azo-metatoluidine; unreduced in
dophenols (aryl or substituted aryl benzo- or 10
naphtho-quinone-mono-imidesJ‘ or insoluble or.
relatively insoluble coloring matters of. polyaryl-' ,
ployed icr dyeing the materials in the absence
of the synthetic resin. I have now found that
15 such materials maybe colored with .unsulphonat
methane,v oxazine, azine, thiazine and thiazole
20 erably, however, water insoluble unsulphonated
droxy-anthraquinone, 1-paratolylamino-4-meth- 20
ylamino-anthraquinone, and especially anthra-l
quinone derivatives substituted in three valpha
series, or unreduced basic derivatives of the an
thraquinone series, e. g. rosanilinev base or its al- 15
ed coloring matters or with sulphonated coloring , kylated or arylated derivatives, pararosaniline
matters in which the sulpho group represents a base, malachite green base,l sairanine base.v
relatively small part of the whole dyestu? mole- ‘ amino- and ‘aminohydroxmanthraquinones or
their derivatives such as 1-paratolylamino-4-hyr
cule, e. g. as in many monosulphonic acids. Pref
colors are used which may conveniently be ap
plied in the form or dispersions or colloidal so-'
' lutions.
I have further found that numerous
unsulphonated compounds which can be convert
25 ed into coloring matters on the materials have
amnity for textile materials impregnated with
or containing synthetic resins. Examples of such
compounds are azo dye components and oxi
group and an amino group respectively; or in
soluble or relatively insoluble acidyl derivatives ‘25
of amino anthraquinones or of substituted amino
anthraquinones, containing one or more ali
phatic acidylamino groups, e. g‘. acetyl-,'pro
pionyl-, only], or sucoinylJ-amino "groups with
Not-only, however, cantextile materials im-‘ or without other substituent groups such as 30‘
positions [by a hydroxyl group, an arylamino
pregnated with or containing synthetic resins be
amino. hydroxy, ‘chlor and the like, for example
terials made or or containing synthetic resins and
4-oxy, -4-methoxy, -4-,amino, -4-methyla'mino
colored by the above means, but also other ma- , 1-acetyl-amino—anthraquinone or l-acetylamino
having at least one dimension small in relation ' or -4:5:8-triamino anthraquino'nes and soforth;
hetero-nuclear di-a-hydroxy anthraquinones 35-'
35 to another, ior example ?lms or ?laments.
‘ Various coloring matters may be employed for 'substituted in one ofthe remaining a-positions
coloring textile materials impregnated with or by an arylamino group and in the other a-DOSI
containing. synthetic resins ,or other synthetic tion by an amino or a non-.aromatically substi
resin materials in accordance with the present tuted amino group. e. g. 4-amino-8-phenylami
no-lzb-dihydroxy'anthraquinone or 4-amino-5- 40 .
40 invention.- Thus there may be employed unsui
phonated or other relatively insoluble derivatives p-tolylamino-‘l:8-dihydroxyanthraquinone; , un
reduced vat dyestuffs or the indigoid or anthra
of the "am" class, e. g. unsulphonated azo, dye
stuiis obtainable from amino naphthols or their quinone series such for example as those sold
nuclear substitution products and containing the under the registered trade-marks “Indanthrene”,
45 azo group linkedto the naphthalene nucleus in ‘-‘Cibanone”, “Algol” and "Helindone”; vesterifledA'iS
unsulphonated azo dyestuil's obtainable from
leuco vat dyestuffs; insoluble or relatively insol
uble nitro derivatives 01‘ diarylamines such for
naphthylene diamines; unsulphonated azo dye
example as 2:4-dinitro-diphenylamine and 2:4- ‘
a position ortho or peri to an auxochromic group;
stu?s containing an anthraquinonenucleuae; g.
50 2-methyl-anthraquinone-l - azo-dimethyl-meta
amino-phenol; insoluble or relatively insoluble py
razolone derivatives, for example unsulphonated
azo derivatives of pyrazolone compounds, such for
' example as those obtained by coupling l-phen
65 yl-S-methyl-B-pyrazolone, or 1.3-dimethyl-5
pyrazolone with diazotized amino compounds, e. g.
. diuo compounds from aniline. ‘para-anisidine,
“f"“para-aminobenzene-azo-dimethylaniline, para
dimethyl-amino-aniline or fpara-amino-phenol;
dinitro-44'-hydroxy-diphenyl-amine or their al-v
kyl, alkoxy, hydroxy,>halogen or amino deriva-_ iii)-v
tives; 4-nitro-diphenylamine, or its alkyl, a1
koxy or-halogen derivatives; 2-nitro-diphenyl
amine and its ‘halogen, alkyl and alkoxy-amino
or acidyl-amino derivatives, e. g. 2-nitro-4-chior
4'-methyl-diphenylamine, 2 - nitro - 4: chlor-4'- 65 1 ‘
ethoxy-diphenylamine; nitro amino diaryl com
pounds, ’ for example 8_-nitro-4-amino-diphenyl,i
3 - nitro-4 -, amino-'4'-acetylamino-dipheny1,1 or
' ‘
other, nitro-amino-diaryl ‘compounds and com
obtainable by diazotizing these bodies and 60 60 unsulphonated. azo derivatives of ‘2:4-dinitroY6-m
- 2,181,098
coupling with suitable coupling components; the
nitrogenous bodies obtainable by introducing ni
Again the dyestuii’ preparation employed in
the coloration oi’ synthetic resin materials may 7
contain any other desired ingredients, e. g. swell
trogen ‘into naphthazarine' or nuclear substitu
tion products thereof with the aid oi.’ ammonia;
ing agents other than and in addition to any 01'
the bodies listed above. As swelling agents there
'may be employed solutions or dispersions oiv sub-.
N-‘(nitro-aryl)-ar-tetrahydro-s—-or p-naphthyl
amines; or there may be employed unsuiphonat
ed compounds obtainable by the introduction of stances having a solvent action on the resin.‘
one or more p-keto-acidyl groups into aminov It will ‘readily be appreciated that the swelling
compounds of the azo, nitro-diarylamine, nitro
agents must be chosen with reference to- the
properties of the synthetic resin in the'material.
Thus phenol-aldehyde resins in the A stage of
10 diaryl, nitro-diarylmethane or anthraquinone se
ries, and unsulphonated products obtainable by
the esteri?cation of a .phenolic hydroxyl group
of an unsulphonated pyrazolone azo-dyestu?
with an organic carboxylic residue, e. g. the prod-°
condensation are soluble in a ‘large number of
organic solvents by which they are merely swol-‘
len when in the B stage of condensation, whilst in
the 0 stage they are una?ected' by those solvents. 15
Examples of swelling agents which may be em
ployed‘ in the treatment of phenol-aldehyde
uct obtainable by acetylation of para-hydroxy
The coloring matters may be applied in various
ways. " The invention particularly envisages their
resins when in the B stage of condensation are
application, however, in the form oi their aque
alcohols, e. g. ethyl butyl or amyl alcohol, ketones,
20 ous dispersions or in more or less colloidal form _ esters or other organic compounds, for example 20
as obtainable for instance with the aid of one acetone, methyl ethyl ketone or ethyl or butyl
or‘. more suitable dispersing agents. For ex
acetate. For polyvinyl resins hot water may
amples of dispersing agents suitable for use in‘ have a su?icient swelling effect. Phenols and
the production of dispersions of dyestuifs for phenolic compounds may also'be employed as ~ '
25 use in accordance with the present invention swelling agents for some synthetic resins, while,. 25
reference may be made to U. S. Patent Nos. as has been indicated, many of the auxiliary sol
1,618,413, 1,618,414, 1,694,413, 1,690,481, 1,803,008, vents mentioned in connection with the produc-- ‘_
1,840,572, 1,716,721, 1,928,647, 1,959,352, and U. tion 01' dispersions may exercise a swelling action
S. application S. N02 493,224 ?led 3rd November’ on resinous materials.’ .
30 1930.]
Wh‘en dyeings or colorings are ‘to be produced 30
If desired the dispersing‘ agent may be used in by the azoic or development process the insoluble
conjunction with an organic solvent for the color
or relatively insoluble component or components
ing matter, particularly a substantially water-in,- ‘ (whether-base or developer or both) may be ap
soluble organic solvent.‘ Such solvents are here
plied in‘either order or simultaneously to the
35 inafter referred to as_“auxiliary solvents". This materials and diazotization and development ei
' process of using auxiliary solvents is of especial iected, or the diazo compound itself may be 'ap
use in the dispersion of di?lcultly dispersible _ plied to the material before or after application
coloring matters or compounds.
of the coupling components and the color de
Examples of auxiliary solvents which may be
40 employed include the following:-—
veloped on the materials. The relatively insoiu- >
ble components are conveniently 'applied in the 4:0~
(a) Aliphatic hydrocarbons, e. g. hydrocarbons _
the aid
of of
01' the
for agents
with v ' '
from petroleum;
(b) Aromatic and hydroaromatic hydrocarbons,
e. g. benzene, toluene, xylene, eymene, cyclo- . mentioned above. "The invention further in
cludes theproduction- of black and other colora
tions on materials made of or containing
hexane, t'etrahydro-naphthalene and decahy
dronaphthalene; '
(c) Terpenes, e. g. turpentine or constituents _‘ synthetic resins by the oxidation of aromatic
compounds, particularly aromatic amino com
" pounds, e- g. aniline, thereon.
For printing or stenciiling synthetic
aliphatic hydrocarbons such as tetrachloreth- .terials,
ane, trichlorethylene, and carbon tetrachloride, more coloring matters or compounds may. be
and halogenated aromatic hydrocarbons such
thickened by the use of such substances as
starches. ?our, gums and the, nice and applied
55 (e) Alcohols or phenols, e. g. butyl alcohol, 'amyl in the usual manner. Where the dyestu?s are
, alcohol, cyclohexanol, methyl cyclohexanols, soluble in water they mayiurther be applied,
' phenol and cresols;
Mixtures oi.I auxiliary solvents may be used if
from aqueous solutions. Dyeing, printing or
other treatments in accordance with the ‘present
invention may be followed by steaming, ageing
fractions of petroleum etc. It will be apprecie
(I) Esters, e. g.'butyl acetate and my] acetate.
60 desired, for example commercial liquids such as
or '1 any other after-treatment that may be de
ated, of course; that the auxiliary solvent should - '
be chosen with due attention to the solubility
characteristics of the particular synthetic resin
65 to be treated, one being chosen that will not
deleteriously affect the resin. At the same time,
a suitable choice of auxiliary solvent may‘ fur
ther lead to better penetration of the dyestuif
into the material treated. Thus the penetration
of dyestuil's, azo components and the like into
synthetic resin materialsmay be facilitated by
means 01 swelling agents for thesynthetic resin,
- and some of the above auxiliary solvents may act
as swelling agents for the resin and so aid pene
75 tration of the dyestuif into the material. ’
While the invention is broadly applicable to '
the coloration of any materials made oi! or con
taining synthetic-resins, such ior example as ?lms ' or ?laments. e. g. ?laments or a polymerized vinyl
compound such as a polymerized vinylv acetate.
it is, as has been indicated, of especial importance
‘in connection with the coloration of textile ma- ' ~
teriais coated or impregnated ‘with synthetic.
resins, e. g. textile ‘materials to which an anticrease ?nish has been imparted by‘ impregna- > ., '
tion with a synthetic resin. The textilebase
may be colored in the same shade as is the resin
impregnant or in a different shade. Cross dyed
effects may be obtained on knitted, woven, or
"3000 parts of 7 water‘
other fabrics‘ containing yarn impregnated with
-in Example 1.
a synthetic resin, .or synthetic resin yarn, and
in't'he manner
The fabric is dyed inthis dye- ' _
bathv for about 1511/2 hours at-80-90° C.‘ It is=-. '
then rinsed and dried and ?nished as desired. .‘j
a cellulose yarn, e. g. cotton yarn, which is not
impregnated with a synthetic resin, by dyeing the
impregnated yarn or synthetic resin yarn with
dispersed insoluble colors a cording to the pres
100 parts of cotton fabric impregnated with
ent invention, and the cotto or-other yarn with phenol-formaldehyde resin as described in Ex-I
dyestuffs having af?nity therefor but not for em ' ample 1 'isidyed for 1 hour in. adyebath consist
' ing of 2 parts of 1-amino-4-hydroxy-anthaqui-_-".1 10
Examples. of synthetic resins which may be . none dissolved " in. 8000 parts of carbon tetra- ' ,
colored in accordance with the present invention
are the-phenol-aldehyde resins, diphenylol-pro
chloride, the dyeing temperature being about 60
vfurfural resins, and diphenylol cyclo parai’?n-al
dehyde resins,“ the condensati‘on‘products of urea
centrifuged and dried,
70° C. When dyeing is complete the material is
pane-formaldehyde resins, diphenylol-propane-v
What I claim and desire
or thiourea with aldehydes with or without phei
to secure by Letters V‘
' 1. Process for, the ‘coloration, of_ textile‘ ma- '
nols, aromatic sulphonamide-aldehyde resins, the
polyhydric alcohol-polybasic acid resins such for.
terial or ?lm comprising ‘a synthetic resin, which
of a water-insoluble
applying thereto
dye compound
an aqueous
at 20'
' example as the glycerol-phthalic anhydride res
ins, synthetic resins obtainable from Phenols, the most onesulphonicgroup. ‘
cresols,‘ xylenols and other phenolic bodies by‘ _. 2. Process for the coloration of textile material.
condensation with chlor-acetone, furfural, allyl . or ?lm comprising a syntheticresin, which com- A
alcohol and other allyl compounds, sulphur > prises incorporating therein awater-insoluble- dye.
chlorides, acetaldehyde, croton‘eldehyde, beto component containing at the most one sulphon'ic
butanolv and chloral, the resinous products ob
group by treatment with an aqueous dispersion‘
tainable from phenolic bodies includingphenol ‘ of the’ dye component, and thereafter converting
itself, the cresols, the xylenols, resorcinol'and said dye "component, into dyestu? on the material.
“pyrocatechin' and acetone or other aliphatic ke . 3. Process for the coloration ofetextile material v » tones or cyclopara?gn ketones,‘hydroxybenao
or ?lm comprising a synthetic resin, which com- 30
phenone-aldehyderesins', e._g.v2:4- or (4:4'-dihy-p prises applying thereto an aqueous dispersion of "
droxy benzophenone-formaldehyde resins and the
a water-insoluble unsulphonated dyestuif.
methyl dihydroxy benzophenone-aldehyde resins,
4. Process for the coloration of textile material
and the resins or other productsv obtainable by
or ?lm comprising a synthetic resin, which com-~ ~
the Polymerization of vinyl compounds, acrylic
compounds, and other unsaturated compounds or
the condensation products of. vinyl compounds
prises ‘incorporating therein a water-insoluble
unsulphonated dye component by treatment with‘
an aqueous dispersion of. the dye component, and
with aldehydes and the like. The invention ?nds ‘ thereafter converting said dye component into
its chief use where the synthetic resins are not in ~
on the material.
a state of complete insolubilit'y and infusibility. dyestuff
5. Process for the'colo ation of textile material 40
The invention is illustratedfbut not limited ' impregnated with a syn hetic resin, which oom
._ y the following examples, the proportions being ‘ prises
applying thereto an aqueous dispersion of
“ expressed as parts by-weight:-
_' an ~unsulph‘onated water-insoluble dyestuif.
6. Process for‘the coloration of textile material.
' " ’ Example 1
To dye a cotton'fabric which has been impreg-‘ impregnated with a synthetic resin, which com
prises applying theretosn ‘aqueous liquid‘ hav
nated with about 20% of its weight of synthetic ‘ ing
dispersed therein a substantially water-in
- resin by mercerizing with caustic soda solution, '
washing. impregnating while still wet with a solu 4 soluble dye and a liquid'having a softening ac
tion on the synthetic resin.
tion made by boiling 50 parts of 40% formalde
‘fl. Process‘for the coloration of textile material
hyde with 50' parts of phenol and a littlepotas»
impregnated with a synthetic ‘resin, which com
slum carbonate for 5 minutes, squeezing to re
move. excess solution, and drying for 1-3 minutes - prises incorporating therein a water insoluble un-.
at 170° C.
sulphonated dye component by treatment with an
‘aqueous dispersion thereof and thereafter con- , q
- ' ‘u
. none is pasted with 10 parts of xylene and heated vertingthe dye component into ‘a dye. .
1 part of i:4-di-(methylamino)-anthraqui
8. Process for the coloration of textile mate
to about ‘70° .C. The mixture is then'pouredinto '
rial impregnated with a synthetic resin, which
15 parts of Turkey red .oil, heated with’ em‘.
and the whole poured into 8000 parts ‘of soft
comprises incorporating therein a water-insoluble - .‘
diasotizable amine by treatment with'an aqueous
dispersion of the diasotizable amine,‘ and there
" water'at about 50° C. '75 parts of the-resindm
pregnated cotton fabric is‘ dyed in this bath-at
90-100’ 0. for about 1-155 hours. _‘ The material
after diazotising the amine and couplins with an
aao dye coupling component.
0. Process for the coloration of textile
impregnated with a phenol-formaldehyde resin,
' which comprises applying thereto an unsulphon
mixture of 10 parts of 40% formaldehyde, 5
an aqueous dispersion thereof.
‘ 10. Process for the coloration of a textile mate
?nishhasbeen‘impartedbyimpregnating witha ated water-insoluble dyestuff byetreatment with
water, followed by
to remove liquor ; rial fimpreenatedwith a urea formaldehyde resin,
much in excessof the weight of the fabric_.‘and whieh: ‘comprises ‘ applying thereto ‘an unsui- ,n
iihonltcd water-insoluble dyestuif-lry treatment.
drying at about 130° for 20-30 minutes.‘ '
-- ‘ 11M Mes-ammonium .1
wnirrormeor xylene
dyebath with-15 parts of
. with an aqueous dispersion thereof. 1
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