Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
:~056556
The lnvention provides a process for the continuous,
dry transfer of organic compounds, ln particular finishing and
improving agents, to a web of organic materlal, which comprises
(1) applying over the entire surface of an inert carrier an
organic compound which is converted into the vapour state at
atomospheric pressure and a temperature above 80,
(2) bringing said carrier into close alignment with the web
of material to be treated in such a manner that each moves
parallel to the other without their comlng into direct contact,
13~ subjecting carrier and web ln a closed heating chamber,
without contact, to a heat treatment of at least 80C, pre-
ferably 100C to 220C and, in particular, 150C to 200C,
until the organic compound has been transferred to the web,
and
(4) transporting the treated web away again from the carrier.
The carrier required for the process according to
the invention is preferably endless.
Endless carriers are used principally in xepeated
application of the compounds to be transferred to the web.
However, the carrier can also be adapted to suit the webs
or organic material to be treated, i.e. they can be cut
into shorter or longer lengths. As a rule the carrier is
inert, i.e. it possesses no affinity for the preparation
that contains the compound to be transferred. The carrier
can be air-permeable or, preferably airtight.;
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~1
~ 0 S 6 ~S 6
Desirably, tlle carrier is a flexible, preferably ~hree-
dimensionally stable ribbon or web or a foil which is stable
to heat. Air-permeable carriers with continuous surface are
e.g. perforated or porous.
The carriers can be made rom a wide variety of
materials, e g. metal, plastic, glass, paper or textile
fibres. Examples of suitable carriers are those of per-
forated or porous metal strips (steel, aluminium, copper),
metallic meshes, perforated or porous plast;c sheets, glass fibre
i~ fleeces or glass cloths, airtight or perforated or porous paper,
nonwoven fabrics, woven or knitted textiles or felts.
Metal strips, e.g. of aiuminium or steel, plastic
sheets o~ e.g. polyester, or coated textiles have proved
particularly advantageous.
Desirably, carrier and material web are s-o trans-
ported that the treated side of the carrier and the side
of the web to be treated are adjacent, When using perforated
or porous carriers, it is therefore also possible for the
treated side of the carrier to be turned away from the side
of the web to be treated.
In addition to the compounds which are transferred
to the material web, the preparations used according to
the invention can optionally contain a small amount of a
binding agent which is stable below 250C, water and/or
an organic solvent.
~ ~ ~ 6 S S 6
Suitable binding agents are synthetic, semi-synt-
hetic or natural resins, both polycondensation and poly-
addition products being possible. In effect, it is possible
to use all binding agents conventionally used in the paint
and printing ink ;ndus~ry. The binding agents are used to
fix the compounds to be transferred at the treated area
of the carrier. But at the transfer temperature they should
not melt, react with each other, i.e. crosslink, and should
be capable of releasing the compound to be transferred.
Preferred binding agents are those that dry rapidly in a
warm current of air and form a fine, desirably non-tacky
film on the carrier. Examples of suitable water-soluble
binding agents are: alginates, tragacanth, carubin (from
locust bean meal), dextrin, ehterified or esterified muci-
lages; carboxymethyl cellulose or polyacrylamide. Examples
of binding agents that are soluble in organic solvents
are: cellulose esters, e.g. nitrocellulose or cellulose
acetate and, in particular, cellulose ethers, e.g, methyl
cellulose, ethyl cellulose, propyl cellulose, isopropyl
cellulose, benzyl cellulose or hydroxyethyl cellulose, and
mixtures thereof.
Suitable organic solvents are those that are mis-
cible or immiscible with water or solvent mixtures with
boiling point at normal pressure below 150C, preferably
below 120~C. It is advantageous to use aliphatic, cyclo-
~ ~ S ~ S S 6
aliphatic or aromatic hydrocarbons e.g. toluene, cyclo-
hexane, petroleum ether; lower alkanols, e.g. methanol,
ethanol, propanol, isopropanol, esters of aliphatic mono-
carboxylic acid, e.g. ethyl acetate or ethyl propylatei
aliphatic ketones, e,g. methyl ethyl ketone and halogena~ed
aliphatic hydrocarbons, e.g. perchloroethylene, trichloro-
ethylene, l,l,l-trichloroethane or 1,1,2-trichloro-2,2,1-
trifl~loroethylene. Particularly preferred solvents are lower
aliphatic esters, ketones or alcohols, e.g, butyl acetate,
acetone, methyl ethyl ketone, ethanol, isopropanol or
butanol and mixtures thereo~, e.g. a mixture of methyl
ethyl ketone and ethanol in the ratio 1:1. The desired vis-
cosity of the printing pastes can then be regulated by
addition of the cited binding agent with a suitable solvent.
The weight ratio of the individual components to
the preparation used for the preliminary treatment can
vary widely and is e.g. for the compounds to be transferred
to the fibrous material within 0.1 to 100%, for the binding
agent within 0 to 30%, for the sol~ent or solvent mixture
within 0 to 99.9%, based on the total weight of the pre-
paration, The amount in which the compound to be transferred
to the fibrous material can be applied to the carrier is 1 g
to 100 g, preferably 15 g to 40 g per m .
The preparations used according to the inventicn
can be manufactured e,g. by dissolving or finely dispersing
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.. . .. . ... . .. . .. . . ... .. . .. .... . .. . . . .. ... . .. ..
l~S~SS~
in water a compound which is transerred to the fibrous
material a~ atmospherlc pressure and a temperature above
80 C, advantageously in the presence of a binding agent
which is stable below 250C.
It is expedient to apply these preparations to the
inert moving carrier ~on~inously, for example by spraying,
coating or printing it over the entlre surface.
Ordinar~ly, the eompounds ~ be trans~erred to the
1bro~ls material are applied by the!nselves t i~ e. without
addition of binding agen~s ~nd solvents. Binding agents and
~olvents are used a~ mos~ in relatively small amounts to
form paste-like products. The powder~ or pastes can be applied
by sprinkling, spraylng, pouring or coating with a doctor
blade. The application csn be effected once or repeatedly.
. After the prepàrations have been applied to the
carrier they may be dried, e,g, in a warm current of air
or by infrared irradiation~ op~ionally with recovery of the
solvent employed. However, such a drying is normally un
necessary since the products are applied preferably withou~
.
B~
1056556
solvent.
The treated carrier is subsequently brought into
alignment with the material web, carrier and web being so
arranged that they move yarallel to each other and pre-
erably in the same direction without coming into direct
contact. As a rule, the spacing between carrier and web
is from l to 50 mm, preferably from 2 to 10 mm. ~Iowever,
the spacing can also with advantage be reduced to less than
1 mm, e.g, 0,5 to 50 mm, preferably 0,5 to 10 mm and, in
particular, 0.5 to 5 mm, Desirably, carrier and web move at
the same speed, normally 25 m/min., but. this speed can be
reduced to 4 to 16 and, in particular, to 7 to g m/min. But
it is also possible to proceed in such a manner that both
webs run through the heatin~ chamber, where the heat treat-
ment and transfer takes place, at different speeds without
coming into contact.
Depending on the length of the heating chamber,
which is normally up to 15 metres, transfer times are ob-
tained (i.e. the length of time taken for the organic com-
pounds to be transferred to the material web~ which vary
~Jo
between ~ and 120 seconds, in particular 60 to 90 seconds.
When products in powder form are used, the appli-
cation is effected from a powder dispenser and products
in paste form are applied with a doctor blade or an inclined
plane. The application of products in powder or paste form
:105~;55~
has the advantage that a binding agent need not be used,
for binders often lead to the formation of incrustations
in the apparatus. The cleaning of -the carrier, provided it
is endless, can also be dispersed with. A special dissolving
in a solvent ~nd the specific problems in connection therewith
(solvent vapours) also do not arise.
Since in the process according -to the invention the
transEer is effected no~ by direct corltact ~u~ ~hrough the
vapours of the compounds to be transferred, it is important
10 i` that the trans~er be carried out in a closed heating chamber.
An expedient system is one with a heating chamber in which
the poin-ts of entry and exit for the material web are sealed.
Useful devices are also ~hose that are provided with
a means for regulating an overpressure or underpressure in
the interior of the chamber.
Another possibility consists in forming a closed
treating chamber with an airtight carrier, an ou-ter belt
which runs parallel to the carrier, and metal side plates.
However, such a chamber is not completely sealed and is
suitable principally for readily transferable compounds.
The invention therefore also provides the apparatus
for carrying out the dry transfer process. This apparatus
comprises
(a) a web-shaped carrier which can be transported in long-
itudinal direction,
\
~()56S56
(b) a means for applyin~ the compounds to be transferred
to the carrier, then follo~ing upon sai~ means in the direction
of travel
(c) a sealable heating chamber through which web of rnaterial
and carrier can be transported parallel to each other without
coming into direct contact,
(d) means for conveying the web of organic material to the
carrier and means for transporting the treated web away
from the carrier again after transfer of the compounds has
been effected, said apparatus being so constructed that carrier
and textile web do not come into direct contact but move parallel
to each other and are to~ether conveyed to the heating chamber
and, after the compounds have been trans~erred, ~aterial web
and carrier are separated from each other.
The apparatus or this invention will now be illustrated,
merely by way of example, with reference to the accompanying
drawings in which Figures I and II illustrate schematically
typical apparatus (longitudinal sections) of this invention.
In Figure I, the web to be treated is shown at (1) and the
treated web is shown at (2). A carrier, e.g of paper, to
which the compound is to be transferred is shown at (3) while
(4) is the means for applying the compound; the carrier after
transfer of the compound is shown at (5). The web (1) is fed
to the charged carrier (3) by a roller (6) and the treated
web is led away from the carrier after transfer by a roller
(7). The web is conveyed to the carrier in such a manner that
contact between carrier and web is prevented. (8) represents
a closed heating chamber in which the transfer of the compound
from the carrier (3~ to the web (1) is effected.
. .
~q~S~SS6
In the embodin~ent illustrated in Fi~ure II, the web of
material to be treated is shown at (9) and the treated web
is shown at (lO)~ (11), (12) and (25) represent an endless
circulating arrangement with, e.g. , a metal strip (25)
or a plastic sheet, guided on rollers. (13) represents a
sprinkling chute which may be, for example, elec~ro-
magnetically controlled, for the application of the compound
to be transferred. Lateral limiting sheets of me-tal are
indicated at (16) and these also provide the side plates of
a heating chamber. (17), (18) and (19) are, e.g. infrared
radiators or jets for warm air. The web (9) is fed to the
charged carrier (25) by a roller (20) whilst preventing
direct contact between web and carrier; and (21) is the
device for transporting the treated web away from the carrier
(25) by roller (21).
The process according to the invention possesses
the advantage that products in powder and paste form can
be used direct as such, thereby making drying and solvent
removal unnecessary. The process according to the invention
also ensures a uniform~transfer of the compounds to the
fibrous material in that unequal amounts on the carrier are
fully offset by the transfer via the vapour phase. The less
exact applica*ion which is thereby mad~ possible constitutes
a significant saving in the construction of suitable appara-
tus. Unnecessary deformations of the material webs can also
be eliminated,to a very large extent. In particular, it is
possible to treat organic fibrous materials, e.g. velvet,
plush or carpets, which are sensitive to contact pressure.
Because the accompanying use of binders is not always
necessary, no incrustations occur in the apparatus
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, .
lOS~556
employed and specia] clissolvin~ operations for the products
do not arise.
Suit~ble air-permeable, organic material tllat may
be treated according to the invention is principally organic
but above all textile fibrous material. The fibrous ma~erial
can be in the most diverse forms of processing, e,g~ y~rn,
especially in piece form, or example woven or knittecl
fabrics or non-wovens. The material can be dyed in the con-
ventional way, printed or finished before or after the ~re~t-
i` ment according to the invention.
The fibrous material itself can be of natural,
regenerated man-made or, above all, synthetic man-made fibres.
Examples of natural fibres are in particular those of wool
or cellulose, e.g. cotton, linen~ hemp or ramie, and examples
of regenerated man-made fibres are those of viscose. Pre-
ferably, textile materials containing synthetic man-made
fibres are used.
As examples of synthetic man-made fibrous material
that can he treated according to the invention there may
be mentioned: cellulose ester fibres, e.g. cellulose 2 lt2-
acetate and cellulose triacetate, synthetic polyamide fibres,
e.g. those of poly-~-caprolactam (nylon 6~, polyhexamethylene-
diamine adipate (nylon 66), poly-~-aminoundecanoic acid
(nylon 7), polyurethane or polyolefin fibres, e.g. poly-
propylene fibres, acid modified polymides, e,g. polyconden-
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.
lOS6556
- s~tion prod~lcts of 4~4'-diamino-2,2'-diphenyl-dis~llphonic
acid or 4,4'-diamino-2,2'-diphenylalkane-disulphonic acids
with polyamide-forming starting materials, polycondensation
products of monocarboxylic acids and their amide forming
derivatives or dibasic carboxylic acids and diamines wi~h
aromatic dicarboxy-sulphonic acids, e.g. polyconclensation
products of -caprolactam or hexametllylenediammonium adipate
with potassium-3,5-dicarboxybenzenesulphonate, or acLd modi-
fied polyester fibres, e.g. polycondensation products of
aromatic polycarboxylic acids, e.g. terephthalic acid or
isophthalic acid, polyhydric alcohols, e.g, ethylene glycol
and 1,2- or 1,3-dihydroxy-3-(3-sodium sulphopropoxy)-butane~
2,2-bis-~3-sodium sulphopropoxyphenyl)-propane or 3,5-di-
carboxybenzenesulphonic acid or sulphonated terephthalic
acid, sulphonated 4-methoxybenzenecarboxylic acid or sulpho-
nated diphenyl-4,4'-dicarboxylic acid.
Preferably, however~ the fibrous material is of
polyacrylonitrile or acrylonitrile copolymers, synthetic
man-made polyamide fibres, preferably polyhexamethylene-
diamine adipate and, primarilyj linear polyester fibres,
especially of polyethylene glycol terephthalate or poly-
(1,4-cyclohexane-dimethylol)-tereph~halate.
I the material is of 2 rylonitrile copolymers,
the acrylonitrile proportion is desirably at least 50% and
preferably at least 85% by weight of the copolymer. Other
~56556
vinyl compounds are normally used as comonomers, e,g, vinyl-
idene chloride, vinylidene cyanide, vinyl chloride, metha-
crylate, methyl vinyl pyridine, N-vinylpyrrolidone, vinyl
acetates,vinyl alcohol, acrylic amide or styrenesulphonic
acids.
These materials can also be used as blends with
one another or with other fibres, e,g. blends o~ polyacrylo-
nitrile/polyester, polyamide/polyester, polyester/viscose
and polyester/wool, polyester/cellulose, in particular poly-
10 i` ester/cotton,
Organic compounds which ~re converted into the
vapour state at atmospheric pressure and above ~0C, especially
at 100C to 220C, are principally sublimable disperse dyes
and, in particular, finishing agents. By finishing agents
are meant e.g. fluorescent brighteners and, above all,
textile improving agents, which include pretreatment, textile
finishing, and textile protective agents.
The sublimable disperse dyes which can be used
according to the invention ~an belong to the most diverse
dyestuff classes. In particular- they are monoazo, quino-
phthalone, methine and anthraquinone dyes, as well as nitro,
styryl, azostyryl, naphthoprinone or naphthoquinone-imine
dyes.
The commercial products of these dyes usually contain
dispersants, i.e, a product with surface-active properties
,
- 13 -
, . . . , , , , , . _, . _. . _ __ _ , .-- _ _ _ _ . _ _ . . ., _ _ ... , .. ... _ _ _. ., .,. .. .. . .. _
.. . .. _ ~ . _ _ _ . _ ,
:~05~556
which makes it possible or malces it easier to disperse these
dyes in water. Dispersants are not necessary i~ anhyd~ous
preparations are used.
Examples of sublimable disperse dyes which can be
used accorcling to the invention a~e:
N02
O ~J~3 ~ N - C~12Cll~-O~;
j~ C~]19
( 2 ) ~ ~ OH
- OH
3) C1~3-CO~H ~ N ~ N ~
C~13
(4) 02N~--N - N~NH
( ~3
(5) 02N~--N - N~ ,C~-12C1~20}1
CH2C~ OH
(fi) N - ~ - CH=C 2 5
- ~4~ `C~
- 14 -
~0565S6
.
(7) 113C~N = ~ ~ C - C ~ C~3
~C~ ,N
1~0 11 N
(8) ~]
O Nl~ ~)
. ` .
O 1~1
- O ~IICH
(10~ ~3
O N~IC~l3
O N~2
(11) e~ (n -- 3 or 4
g ~12
~10 0 ~l C~l
(12) ~3
H2 }32
~5~6556
(13) ~ ~{-~
- . 0~1
2~ ' 1'
h~ (J3 r ) (Il :- 1 or 2 )
}1 0 N112
i~
O I }~
(15)
2~ N~2
(l~ ~q
B3C ]14C2 CO ~H
. ~1
2~C21~40~1
' 0~1
H~2
H 01-1
'
- 16 -
~OS6S56
o ~11
( 1~ ) ~3J~ CO - Na2
~H- C113
(20)Cl--~ Nll ~ OC}13
~2
` (21)~3~C113
O
( 2 2)Cl 3 ,COOC2H5
(23)O~N ~N - ~ - C - C - C~3
Cl 112N H
~IN O
(24) f¢~
, 11
~05~S56
C1-13- CH2 - C~12 - C0 ~ N 3~3
(26) ~ ~2
(27) ) 5C2~ ~ \N ;~
The disperse dyes of the formulae (2), (10) and
(13) are preferred.
The sublimable fluorescent brighteners can belong
to any desired class of brightener. In particular they are
cumarins, benzocumarins, pyrazones, pyrazolines, oxazines,
o~azolyl, thiazolyl, dibenzoxazolyl or dibenzirnidazoIyl
compounds, and also naphthalic imides. Examples of subli-
mable fluorescent brighteners which can be used according
to the invention are:
- 18 -
l(~S65S~
( 2 ~ N~ CH3
(2~ ~ C - CH - CH - C~
C112Cll? 0~1
(30)~ C C C~C - Cl-32 - C C113
i` ` S' ~ C~13 ~133
~C - CH COOCH3
" ~,N~
(31) ~=~ C~S,c - C~ o,~J
113C~ C-- C~ = Cl-l--~ COOC1~3
CII
HC - CH HC - Cll N~ ' 3
H3COO ~ \C ~CIl-CH~ ~N)~)--COOCH3
' ' .
(35) Cl--~C1~2-C112 ~- COOC}~3
- 19 -
1~5~i5S6
(36) ~-C~I. C~
S02- ~}'~ C~ 7
N (C2~15 ) ?
(37) ~ C~ ~C - 1~11 ~D
(33) C1~3--Cl~ = C~ - C
(39) ~I~N/ ~`
.
~1~
O - G G - O
(40)
CH3
(41~ ~13C Cl `~ m~O
11C = ~
--
- l~)St;SS6
.
(42) ~ i~ ~IC - CU ~ ~ ~
(431 C113 T ~IC C~l ~ ~ (C~3)
C~3 - C ~ C - C C - C~ ~
.
C~i3 ~ C = Cll~ C C- ~
According to the invention however, preferably
finishing agents are -transferred. As finishing agents which
are transferred to the organic material at atmospheric
pressure and at a temperature above 80C, preferably at
100C to 220C, there may be cited principally textile
finishing agents, textile protective agents, in particular
biologically active protective substance that impart to
the textile material e.g. bacteriostatic and/or fungistatic
and/or fungicidal properties and actual textile finishing
agents that impart to the textile material the desired effect,
e.g. antistatic, water repellenf, handle-improving or flame
resistant effects. The cited textile pro~ective and/or
finishing agents can, if desired, be applied to the material
- 21 -
J ~56556
to be finished ~ogether with dyes and/or ~luorescent bright-
eners that are converted into the vapour state at atmos-
pheric pressure and at temperatures between e.g, 150C and
220C.
The finishing agents which can Le used according
to the invention are known or they can be manufactured
by processes ~hich are known per se. 'rhey belong to the most
diverse classes of chemlcals.
As an example of a bacterlostatic pro-tective sub-
stance tllere may be mentioned the compownd of the formula
(45) Cl ~ 0 ~ - Cl
CL ~lO
and as example of a fungistatic protective substance the
compound of the formula
CH Gl-l OH
(~6) C12H25-1_C~12c~2 Cl
~ , C~12-~ I .' . '
and of the formula
- 22 -
1~56556
Cl Cl
(47) CllH23C - ~ ~ Cl
Cl Cl
An example o a compound that imparts hanclle-
improving properties to the.textile fabric is that of the
formula
/ C~}2CH2~
j (48) C17H35-CN
CH~CH20H
and examples of compounds that impart antistatic properties
to the textile fabric are the compounds of the formulae
(49) HO-~C~12C~120)7_15H
11
- (50) CH2=c-co(cH2cH2o~7cH3
CH3
(Sl) [H23cll-co-Nl~-c}l2-cH2-cu2-N-cH3 ~ CH3COO
`
- 23 -
105~ii5S6
~1 71~3scONll (cl l2 ) 3N ~ c2ll5 ~ so~ Cl13 (3
5 3 ) C9M19~9--o- ( Cl-12- C~12 Q) 8
(54) ~C17~35-C CH2
\ ~ / C 2 CH3COO
C112CH20H
r ~ I ,CH2cH2 0Hl ~
(55) LC 11 - N I CH3COO
.
and examples of compounds that impart oil and/or water
repellent properties are those of the formulae
(56) C17H35 C
-
g~l7C~12C~1-~C~C~I CH2
CH3
- 24 -
.
~05~i5~6
& 17 2 ~
- CH3
O
(59) C8F17CH2CH20~-C~I-C~I-C O C112C ~ ~ l7
N - C / ~ C N / 2CC17H35
H3CO~I2C / N \ ~ N C1l20CH3
i` I ~CH2COOC17H35
CH20CH3
and perfluoroisopropyl alcohol or methylhydrogen poly-
siloxanes or dimethyl methylhydrogen polysiloxanes. The
prefeLred compounds are the compound. of the formula (56)
and the dimethyl methylhydrogen polysiloxanes.
- The following compounds are examples of suitable
flameproofing agents:
A) methylenedioxybenzene compounds of Lhe formulae
o ~CH2 - C~l = C,H2
(61) CH2 ~ ~ ~ OC,~5
o OC~H5
- 25 -
~[)5655~
(62) ~~X Pr OC l{
~ C2115
Cll - P
2 O~ OC2115
o ~ Cl~2 - ~C~ C~l~ P.r
(63) C112~ ~ O
Cl-12 p 2 5
i` . o~ OC2~15
Cll - CJl - CH Br
(64) CH2 ~ 2. 1 2
B) phosphorus compounds of the formulae
(65) ~ /C2}~5
'- O OC2ll5
.
.
(66) HO--~p~ OC2H5
,~ o~ ~2115
COOCH3
.- ~6 -
1~56556
(67) 110~ " C21 5
(6~) ~10-~3 CllP/ 3
OC113
COoC~13
HO
, (G9) ~ 5
(70) Cz115~If\OC2H5
(71) C13;~ 2~ 5
OC2H
(72~ Cl~ 2 Il\OC H
27
... . . .. .. , , . , . ., . , .. , .. , . , ~ . ,, ~ . .
l~S6556
C) phospl~ol-us compounds of ~he Eormulae
~l~r 13r 0
(73) ~C1~2~CH-CH2-0-)2 P-~H CII~C12
. /Rr Br O . . O CH3
(74) ~C1~2-CH-Cll2-0-)2P-o-c~l2.cll2 2
. Br Br O
~ 1 11
(75) ~C112 C}I-CH2~0-~2 P-OII
i~ .
~r Br O
I I
(76) Cll2-CI~-CH2 )3
The preferred compounds are those of ~he formulae (7~) and
(76).
D) ha~logen compounds of the formulae
~ 3r Br
,
( 7 7 ) C i i 2 C 11 C ~ ~ 2 C ~ 1 2 (~ X 2 C L ~ C 2
.
~r ~r ~ C~12~1
(78~ C~l2- CII- CO-i~; ~ -
Cl Br Br
( 7 9 ~ Cr~2 C~ Z2 COO - Cl~2 ~ Ci1 ~ Ci~
~ 28 ~
~56S56
~3r 17r
2 C~I Ci~2-o-CO-i~,~2
~1) Cli2 C~l-Cil2-0-CO-CI-I=C~i-C
Br ~r
(82) Ci-2 Cil CO ~l 2
C~ r P~r
(83) Cll -COO-C~ U-C~2
Br P,r
(~4) .Cl~2~Cl~-cO ~l2
The preferred compounds are those of the fo~mul.ae (77), (82)
and (83).
E) halogen compounds of the formulae
(85~ ~ \
Cl C1
- 29 -
iOS~SS6
~r
( 86) 13r -~ o-Cll2-CII-CI-12-Br
Br P~r
l3~
(87) }3r--~--OC~!2 ICII 7ll2
13r Br
j~ Br Br Br Br
(S8) ~3 ~
Br Br
Br /CO\O
(89) Br~ CO/
~r Br
( 9 0~ Br ~ OH
- Br
Br CH3
( 91) Br~ OH
. Br Br
- 30 -
1~5~556
The preferred compound is that of the formula (91).
When choosing the- organic compound or compounds and
especially o the textile finishing agent or agents, allo-
wance is made on the one hand for the desired effects and on
the other for the temperature at which these compounds are
transferred to the organic material without decompositi.on.
Preferred compounds are those having transfer temperatures
between 100C and 220C,in particular between 150C and 200C,
To attain several finishing effects in one procedure, it is
preferable to use textile finishing agents with as similar
transfer ~roperties as possible, i,e. those with similar
transfer temperatures that do not differ by more than 20C,
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1056556
The compound of the formula (91j is applied in powder
form by means of a spinkler device to an endless carrier
consisting of an aluminium strip so as to give a uniform
application of 15 g/m2. The treated side o~ the carrier
is then transported a~ a speed of 8 m/min. at a spaclng
of 2 to 4 mn parallel to a web o polyes~er materiRl
(150 g/m ~ t~ravelling at the same speed
While maintaining this dis~ance, carrier and web are intro-
duced into a heating chamber which is sealed at the entrance
and exit by pairs of rollers and sealing tape, so that there
is slight over-pressure in the interior of the chamber,
The plastic sealing lips are so arranged that they are
pressed against the rotating rollers by the internal pressure.
The transfer of the flameproofing agent from the carrier to
the fabric then takes place at a temperature of 200C over
the course of 30 seconds. Carrier and textile web are conti-
nually separated from each other. The textile web is success
- fully subjected to the flameproofing test DOC FF 3-71
(Children's Sleepwear Test). This test is carried out in
the following manner:
5 pieces of fabric, each measuring 8 9 cm x 25.4 cm, are
clamped into a testing frame and dried with circulating
air for 30 minutes at 105C in a drying cabinet. The pieces
~5 of fabric are then conditioned in a sealed container over
1C~56~56
silica gel ~or 30 minutes and subsequently subjected to the
actual flameproofing test in a combustion chamber~ The pieces
of fabric are each ignited with a methane gas flame for
3 seconds in ~he vertical position,
The test is considered as having beell passed if the average
charred zone is not more than 17~5 cm in length and no
single sample exhibi~s a charred zone of over 25,4 crn in
length and tlle individual smowldering times are no~ longer
than 10 seconds.
10 i Similar results are obtained with the compounds of the
formulae (85) to (90).
~xample 2
40 g of the blue disperse dye of the formula (10) and 100 g
of ethyl cellulose in 860 g of a methyl ethyl ketone/
ethanol mixture` (weight ratio 1:1~ are ground together for
5 hours at 20C in a sand mill and dispersed to give a
homogen~ous printing ink,
This ink is printed on a paper carrier so that after the
solvent has been evaporated at room temperature there is
a uniform dyestuff application of 0.5 g/m2. The carrier
and a polyester fabric (150 g/m2) are then transported at
a speed of 8 m/min. parallel to each other, the spacing
between the printed side of the carrier and the polyester
fabric being 1 mm,
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10~;65S~
The transfer of the dye from ~he car~-ier to the polyes~er
fabric then takes place in the heating chamber described
in Example 1 a-t a temperat-lre of 200C over the course
of 60 seconds. A solid shade polyester fabric dyed a deep,
level blue is obtained after the fabric has beeln sep~ra~ed
from the carrier. Similar results arc obtainecl by substi~
tuting the yellow disperse dye of the Eormula (2) or the
red disperse dye of the Eor~ula (13) ~or the blue disperse
dye o the formula (lO~.
i`
Example 3
Polyamide fabric (140 g/m ) is treated with one of the dis
perse dyes of the formulae (2), (10) or (13) as described
in Example 2. A solid shade polyamide fabric which is dyed
also a deep, level yellow, blue or red is obtained.
Example 4
Polyester or polyamide fabrics are treated as described
in Examples 2 and 3 with one of the disperse dyes of the
; formulae (2), (10) or (13), but using an endless carrier
of stainless sheet steel and keeping a distance of 2, 3
or 5 mm between the printed steel carrier and the respective
polyester or polyamide fabric. At a spacing of 2 mm9 tlle
speed at which the carrier and the fabric travel is re~
duced to 6 m/min, and at a spacing of 3 and 5 mm the speed
.
` ~ ~ S 6 55 ~
is reduced to ~ m/min. The transfer of th~ dyes from -~he
carrier to the fabric takes place in the heating chamber
at a tempera~ure of 200C over the course of 90 seconds
at a spacing of 2 mm and over the course of 120 seconds
at a spacing of 3 and 5 mnl,
A solid shade polyester or polyamide abric with level and
bright dyeings is obtained. The greater the spa~ing be-tween
carrier and fabric the brighter the r~spec~ive yellow, blue
j~ or red dyeings.
Example 5
The compound of the formula (56) is applied with a doctor
blade to a heat resistant polyester sheet so as to give
a uniform application of 12 g/m2. The treated side of the
carrier is then transported at a speed of 16 m/min. parallel
to the pile side of a web of velveteen material travelling
at the same speed and while keeping a spacing of 0.5 to 1 mm,
carrier and web are fed into the heating chamber described
in Example 1, in which the transfer of the water repellent
frsm the carried to the fabric is effected at 195C over
30 seconds. Fabric and carrier are subsequen~ly separated
from each other.
Following this treatment the velveteen retains its sheen.
On the other hand, by carrying out a treatment wherein
velveteen and carrier are kept for 30 seconds between two
~ ~ 5 ~ S 5 6
metal plates heated to 195C, the pile side of the fabric
loses its sheen.
The velveteen which is treated by the process according to
the invention, wherein direct contact be~ween carrier and
fabric is prevented, is tested for its water repeLlent
properties in comparison with untreated velve~een. A drop
of water placed on the treated velveteen remains on the
material for over 3 hours~ wllereas a drop of water on un-
treated material is absorbed by this immediately.
The velveteen is also tested in the following spray test:
` Weighed samples of fabric meas-lring 25 cm in length are
wetted with 500 ml of water. Any drops adhering to the
fabric are removed and the moist samples are weighed. The
weight increase as degree of ~he water repellent effect
is reported in % of the dry weight. For untreated velveteen,
the weight increase is 160%, whereas for untreated velveteen
it is only 25%.
Similar results are obtained with the compounds of the
formulae (57) to (59) and (60).
Example 6
The compound of the formula (77) is slop padded in the form
of an oily viscose liquid on a glass cloth (260 g/m2) so as
to give a uniform application of 40 g/m2. The impregnated
side of the carrier is then transported at a speed of 16 m/min.
36 -
~ ~ 5 ~ 5 ~ ~
parallel to a polyester fabric (150 g/m ) travelling at
the sallle speed, the spacing between carrier and web being
3 and 6 mm. While keeping this spacing, carrier and fabric
are fed into the heating chamber described in Example 1 in
which the transfer of the ~lameprooing agent Erom carrier
to the fabric takes place at 200C over 30 secorlds. Carrier
and ~abric are subsequent].y separated froDI each other,
The flameproof properties of the treated abric are tested
in comparison with untreated fabric in the vertical test
DIN 53 906 at an ignition time o 3 seconds. The results are
summarised in Table I:
Table I
fabric burn time tear length
in secs. in cm
.
treated at a spacing 14 6
treated at a spacing 15 7
_
untreated burns awa~ compl.etely
Similar results are obtained with the compounds of the
formulae (78) to (81).
1()56~S6
Example 7
The compound o~ the formula (74) or the compound of the
formula (76) is slop padded as oily viscose liquid on a
strip of stainless sheet s~eel so as to give an application
of 55 g/m . The treated side of the steel strip i5 thell
transported at a speed of 12 m/m-ln. parallel to a voluminous
polyester fabric (250 g/m2) travelling at the same speed,
the spacing between carrier and web o~ fahric being about
1 mm, While keeping this spacing, carrler and fabric are ed
into the heating cham~er described in Example 1 in which tlle
transfer of the flameproofirlg agent from the carrier to the
fabric takes place at 190C over 45 seconds. Carrier and
fabric are subsequently separated from each other.
The flame resistance of the treated fabric is tes-ted as des-
cribed in Example 6. The results are summarised in Table II.
'
Table II
.
fabric burn time tear length
in secs. in cm
treated with the
compound of the 13 4
formula (74)
treated with the
compound of the 12 5
formula (76)
_.
untreated burns away completely
.
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1~5655~
Following this treatment ~he polyes~er ~abric has re~ained
its voluminous, plush~like appearance, whereas ~ polyes~er
sample used for comparison purpose has lost this appearance
after it has been kept for 45 seconds between two me~al
plates heated to 190C.
Similar results are obtained with the compounds of the
formulae (61) to (73) and (75),
_a ~
i The compound of the formula (82) or the compound of the
formula (83) is slop padded as oily viscose liquid on a strip
of stainless sheet s~eel so as to give an application of
45 g/m2. The treated strip is transported parallel to a
voluminous polyamide fabric (240 g/m2) as de6cribed in
Example 7. The flame resistance is tested as in Example 6
and the results are summarised in Table III
Table III
: fabric burn time tear length
. in secs. in cm
. .
treated with the
compound of the 13 5
formula (82~ _ .
treated with the
: compound of the 14 6
formula (83)
untreated burns away completely
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10~6S56
Following ~he ~rea~ment, the polyar,lide ~abric has retain~d
its voluminous plush-like appearance, whereas a comparison
sample treated as described in ~ample 7 has lost it.
Similar results are obtained with the compound-of the orrllula
(84).
~ ple 9
Velveteen fabric (260 g/m2) is sprayed on the pile side
with an aqueous 10% zirconium oxychloride solution (catalyst)
so as to give a 2% concentration on the pile based on the
i weight of the fabric. After it has been sprayed, the velveteen
is dried at 70C to remove water.
A dimethyl methylhydrogen siloxane with a molecular weight
of 900 and a hydrogen silane content of 280 ml/g (measured
by splitting off of hydrogen directly bound to silicon ) is
sIop padded on a carrier of stainless shee~ steel so as to
give an application of 10 g/m2. The treated side of the
steel carrier is then transported at a speed of 8 m/min.
parallel to the pile side of the velveteen fabric treated
with the catalyst, the spacing between carrier and fabric
being 1 to 3 mm. Carrier and fabric are fed into a heating
- chamber corresponding to that of figure II. The transfer of
the water repellent from the carrier to the fabric takes
place at 200C over 60 seconds and carrier and fabric are
then separated.
The treated velveteen is tested for its water repellency by
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1[)56556
t~e spray test as described in Examy]e 50 The weight increa.,e
as index of the water repellency ~or untreated velveteen is
160%, whereas for treated velveteen it is only 15%.
In addition, a drop of water placed on the treated velveteen
remains there for over 3 hours~ whereas a drop of water
placed on untreated velveteen is completely absorbed immedia-
tely.
The velveteen treated according to the invention without
direct contact retains its sheen, but a comparison sample
which is kept for 60 seconds between two metal plates
heated to 200C does not do so.
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