CA1056556A - Process for the dry transfer of organic compounds to webs of organic material - Google Patents

Abstract

Abstract of the Disclosure The invention provides a process for the continuous, dry transfer of organic compounds, preferably of finishing and improving agents to a web of organic material, in particular to textile webs which contain synthetic fibres and are sensi-tive to contact pressure.
The process comprises the following steps:
(1) applying over the entire surface of an inert carrier such as a paper carrier or a strip of stainless sheet steel an organic compound e.g. a textile finishing agent, which is converted into the vapour state at atmospheric pressure above 80°C, preferably at 100°C to 220°C, (2) bringing said carrier into close alignment with the web to be treated in such a manner that each moves parallel to the other without coming into direct contact, (3) subjecting carrier and the web spacing between carrier and web being e.g. 0.5 to 5 mm to a heat treatment of at least 80°C in a closed heating chamber until the organic compound has been transferred to the web, and (4) transporting the treated web of material away again from the carrier.
The invention also provides a suitable apparaturs for carrying out the above process.

Description

:~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.;

~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 .. . .. . ... . .. . .. . . ... .. . .. .... . .. . . . .. ... . .. ..

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~

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 - lQ -, .

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-.

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 , , . . . , , , , , . _, . _. . _ __ _ , .-- _ _ _ _ . _ _ . . ., _ _ ... , .. ... _ _ _. ., .,. .. .. . .. _ .. . .. _ ~ . _ _ _ . _ , :~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:

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~

~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 ' ~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:

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 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) (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 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 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

- (50) CH2=c-co(cH2cH2o~7cH3 (Sl) [H23cll-co-Nl~-c}l2-cH2-cu2-N-cH3 ~ CH3COO
`

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

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 .

~05~i5~6 & 17 2 ~

O

(59) C8F17CH2CH20~-C~I-C~I-C O C112C ~ ~ l7 N - C / ~ C N / 2CC17H35 H3CO~I2C / N \ ~ N C1l20CH3 i` I ~CH2COOC17H35 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 ~[)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 .- ~6 -1~56556 (67) 110~ " C21 5 (6~) ~10-~3 CllP/ 3 COoC~13 HO

, (G9) ~ 5 (70) Cz115~If\OC2H5 (71) C13;~ 2~ 5 (72~ Cl~ 2 Il\OC H

... . . .. .. , , . , . ., . , .. , .. , . , ~ . ,, ~ . .

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 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 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, 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, 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.

~ ~ 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 .

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 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 - ~0 - `

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.

Claims (14)

CLAIMS :

1. A process for the continuous, dry transfer of organic compounds to a web or organic material which comprises (1) applying over the entire surface of an inert carrier an orga-nic compound which is converted into the vapour state at atmos-pheric pressure above 80° C, (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 coming into direct contact, (3) subjecting carrier and web of material, without contact, to a heat treatment of at least 80° C in a closed heating chamber until the organic compound has been transferred to the web of material, and (4) transporting the treated web of material away again from the carrier.

2. A process according to claim 1, which comprises the use of finishing and improving agents as transferable organic compounds.

3. A process according to claim 1, which comprises the use of compounds with transfer at temperatures of 100° C to 200° C as organic compounds.

4. A process according to claim 1, which comprises the use of an endless carrier consisting of a metal strip or plastic sheet or a coated textile material.

5. A process according to claim 1, which comprises the use of a paper carrier.

6. A process according to claim 1, which comprises the use of a web of textile material that contains synthetic fibres which is sensitive to contact pressure.

7. A process according to claim 1, wherein the spacing between carrier and web during the transfer is 0.5 to 5 mm.

8. A process according to claim 1, wherein the transfer takes from 40 to 120 seconds.

9. A process according to claim 1, wherein carrier and web are transported synchronously in the same direction.

10. A process according to claim 1, wherein carrier and web are transported at a speed of 4 to 16 m/minute.

11. An apparatus for carrying out the process according to claim 1 which comprises (a) a web-shaped carrier which can be transported in long-itudinal direction, (b) a means for applying the compounds to be transferred to the carrier, then, following in the direction of travel, (c) a sealable heating chamber through which material web and carrier can be transported parallel to each other without their coming into direct contact, (d) a means for conveying the web of organic material to the carrier and a means for transporting the treated web away from the carrier again after the transfer of the compounds from the carrier to the web has been effected.

12. An apparatus according to claim 11, wherein the heating chamber is sealed at the points of entry and exit of the textile web.

13. An apparatus according to claim 12, wherein the heating chamber is provided with a means for regulating an overpressure or underpressure in the interior of the chamber.

14. An apparatus according to claim 11, wherein the heating chamber is constructed of an airtight carrier, an outer belt that rotates parallel to the carrier and metal plate side walls.