CA1056557A - Process for the dry transfer of organic compounds to webs of material - Google Patents
Process for the dry transfer of organic compounds to webs of materialInfo
- Publication number
- CA1056557A CA1056557A CA207,421A CA207421A CA1056557A CA 1056557 A CA1056557 A CA 1056557A CA 207421 A CA207421 A CA 207421A CA 1056557 A CA1056557 A CA 1056557A
- Authority
- CA
- Canada
- Prior art keywords
- carrier
- web
- process according
- suction
- organic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/025—Duplicating or marking methods; Sheet materials for use therein by transferring ink from the master sheet
- B41M5/035—Duplicating or marking methods; Sheet materials for use therein by transferring ink from the master sheet by sublimation or volatilisation of pre-printed design, e.g. sublistatic
- B41M5/0358—Duplicating or marking methods; Sheet materials for use therein by transferring ink from the master sheet by sublimation or volatilisation of pre-printed design, e.g. sublistatic characterised by the mechanisms or artifacts to obtain the transfer, e.g. the heating means, the pressure means or the transport means
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
- D06B11/00—Treatment of selected parts of textile materials, e.g. partial dyeing
- D06B11/0076—Transfer-treating
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
- D06P5/003—Transfer printing
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Treatment Of Fiber Materials (AREA)
- Paper (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
Abstract of the Disclosure The invention provides a process for the continuous, dry transfer of organic compounds, in particular of finishing and improving agents, to webs of air-permeable organic materials, preferably to textile webs are of polyester, polyamide, poly-acyclonitrile and/or cellulose, The process comprises the following steps:
(1) applying to a carrier such as polytetrafluoroethylene or polyester sheet or glass cloth preparations which contain one or several compounds e.g. textile finishing agents that are converted into the vapour state at atmospheric pressure and at a temperature above 80°C, preferably 100 to 220°C optionally a binder which is stable below 250°C and/or a solvent, and, optionally, drying said preparations.
(2) bringing said carrier into contact with the side of the air-permeable web of organic material to be treated in such a manner that web and carrier advance together synchronously, the one superimposed on the other, (3) subjecting carrier and web alternately, optionally under mechanical pressure, to at least one heat treatment of at least 80°C applied from the carrier side and one suction treat-ment from the web side, optionally combined with a second heat treatment of at least 80°C applied from the carrier side, and continuing or repeating this treatment until the com-pound has been transferred to the web, which is fed in one or up to 10 layers, so that the same section of the web passes through the same heating/suction cycle one or up to 10 times, and (4) separating the treated web from the carrier.
Advantageously, the web or alternately subjected to 2 to 20 heat and suction treatments, whereby the running speed of the web is up to 100 m/min. preferably 20 to 50 m/min.
The invention also provides a suitable apparatus for carrying out the above process.
(1) applying to a carrier such as polytetrafluoroethylene or polyester sheet or glass cloth preparations which contain one or several compounds e.g. textile finishing agents that are converted into the vapour state at atmospheric pressure and at a temperature above 80°C, preferably 100 to 220°C optionally a binder which is stable below 250°C and/or a solvent, and, optionally, drying said preparations.
(2) bringing said carrier into contact with the side of the air-permeable web of organic material to be treated in such a manner that web and carrier advance together synchronously, the one superimposed on the other, (3) subjecting carrier and web alternately, optionally under mechanical pressure, to at least one heat treatment of at least 80°C applied from the carrier side and one suction treat-ment from the web side, optionally combined with a second heat treatment of at least 80°C applied from the carrier side, and continuing or repeating this treatment until the com-pound has been transferred to the web, which is fed in one or up to 10 layers, so that the same section of the web passes through the same heating/suction cycle one or up to 10 times, and (4) separating the treated web from the carrier.
Advantageously, the web or alternately subjected to 2 to 20 heat and suction treatments, whereby the running speed of the web is up to 100 m/min. preferably 20 to 50 m/min.
The invention also provides a suitable apparatus for carrying out the above process.
Description
~ 5 ~7 The invention provides a process for the continuousJ
dry transfer of organic compounds, in particular of textile finishing and improving agents, to webs of air-permeable organic materials~ which comprises (1) applying to a carrier preparations which contain at leas~
one compound that is converted into the vapour state at at~os-pheric pressure and at a temperature above 80~, optionally a binder which is stable below 250C and/or a solvent, and, optionally, drying said preparations, ~2) bringing said carrier into contact with the side of the air-permeable web of organic material to be treated in such a manner that web and carrier advance together synchronously, the one superimposed on the other, (3) subjecting carrier and web alternately~ optionally under mechanical pressure, to at least one heat treatment of at least 80C applied from the carrier side and one suction treatment from the web side, optionally combined with a contin-uing or repeating this treatment until the compound has been transferred to the web, which is fed in one or more layers, so that the same section of the web passes through the same heating/suction cycle one or more times, and (4) separating the treated web from the carrier.
The carrier required for the process according to the invention is preferably endless~ but it can also be adapted to suit the webs of organic material to be treated, i.e, they
dry transfer of organic compounds, in particular of textile finishing and improving agents, to webs of air-permeable organic materials~ which comprises (1) applying to a carrier preparations which contain at leas~
one compound that is converted into the vapour state at at~os-pheric pressure and at a temperature above 80~, optionally a binder which is stable below 250C and/or a solvent, and, optionally, drying said preparations, ~2) bringing said carrier into contact with the side of the air-permeable web of organic material to be treated in such a manner that web and carrier advance together synchronously, the one superimposed on the other, (3) subjecting carrier and web alternately~ optionally under mechanical pressure, to at least one heat treatment of at least 80C applied from the carrier side and one suction treatment from the web side, optionally combined with a contin-uing or repeating this treatment until the compound has been transferred to the web, which is fed in one or more layers, so that the same section of the web passes through the same heating/suction cycle one or more times, and (4) separating the treated web from the carrier.
The carrier required for the process according to the invention is preferably endless~ but it can also be adapted to suit the webs of organic material to be treated, i.e, they
- 2 ~
~565S7 can be cut into pieces. As a rule ~he carrier i9 inert, i.e.
i~ possess~ no a~finity for the preparation that contains the compound to be transferred. The carrier can be air-permeable or, preferably, airtight.
Desirably, the carrier is a flexible, preferably thre~-dimensionally stable ribbon or web or a foil which is stable to heat. Air-permeable carriers with continuous surface are e.g. perorated or porous.
The carriers can be made ~rom a wide variety of ma~erials, 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), met fibre fleeces, perforated or porous plastic sheets, glass fibre fleeces of glass cloths, air~ight or perforated or porous paper, nonwoven fabrics, woven or knitted textiles or felts.
Examples of materials which have proved particularly suitable are paper, aluminium, or steel strips which can be perforated or unperforated, glass cloths, plastic sheets which can be perforated or unperforated, in particular those of polyester or polytetrafluoroethylene, and nonwoven fabrics, e.g. webs of polyester or polyamide fibres.
Also suitable are carriers with plastic coatings in the form of perforated or unperforated films, e.g. coa~ings of polyvinyl resins, ethyl celluloseJ polyure~hanes or poly-~056557 tetrafluoroe-thylene.
In addition to the compounds which are transferred to the material web, the preparations used according to the invention can contain at least one binding agent which is stable below 250C, water and/or an organic solvent.
Suitable binding agents are synthetic, semi-synt-hetic or natur~l resins, both polycondensation and poly-addition products being possible. In eff~ct, it is possible to use all binding agents conventionally used in the paint and ~rinting ink industry, The binding agents are used to fix the compounds to be transferred at the treated area of the carrier. But at the ~ransfer temperature they should not melt, react with each other, i~eO crosslink, and shoul~
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. Exampl~s 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, pxopyl cellulose, isopropyl cellulose, benzyl cellulose or hydroxyethyl cellulose, and mixtures thereo~.
Suitable organic solvents are those that are mis-cible or immis~ible with water or solvent mixtures with a boiling poin~ at normal pressure belbw 150C, preferably below 1~0C. It is advantageous to use ~liphatic, cyclo-~liphatic or aromatic hydrocarbons, e.g. toluene, cyclo-hexane, petroleum ether; lower alkanols, e.g. methanol, ethanol, propanol, isoprop~nol, esters o aliphatlc mono-carboxylic acid, e.g. ethyl acetate or ethyl propylate;
aliphatic ketones, e.g. methyl ethyl ketone and halogenated aliphatic hydrocarbons, e,g. perchloroethylene, trichloro-ethylene, l,l,l-trichloroethane or l,1,2-trichloro-2,2,1-B trifluorocthylene. Particularly preferred solvents are ~s~
aliphatic esters, ketones or alcohols, e.g. butyl acetate, c acetone, methyl ethyl ketone, ethanol, isopropanol or butanol and mixtures thereof, 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 solvent or solvent mixture within 0 to 99.9%, based on the total weight of the pre-~ S 65S7 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 m2.
The preparations used according to the invention can be manufactured eOg, by dissolving or finely dispersing in water and/or an organic solvent a compound which is trans~erred to the fibrous material a-t atmospheric pressure and at temperature above 80C, 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 continously, for example by spraying, coating or, preferably, by printing it over part of or over the entire surface. Principa71y when using paper carriers and those made of stainless steel, it is possible to use the most diverse printing methods3 e.g, relief printing (e,g, book printing, flexoprinting), intaglio printing (e g. roller printing), silk-screen printing (e.g. rotary screen printing, flat-screen printing) or electrostatic printing.
It is also possible to apply organic compounds by 2~ themselves direct, i.e. without the addition o bînders and solvents, by spinkling, spraying, pouring, slop padding or with a doctor blade.
A particular embodiment of the present process consists in applying the organic compound in pattern form to a web o~
material, e.g. by printing it, or instead of a complete web, 1~)56~57 applying ~ut pieces of the carrier to the fibrous material to be treated. These patterns are obtained by punching or cutting suitable segments into the carriers cited herein-above.
A~ter the preparations have been applied to th~
carrier they may be dried, e.g. in a wanm current of air or by infrared radiation, if appropriate with recovery o~
the solvent employed. But i~ the organic compounds to be trans~erred are applied direct by themselves, ~hen such a drying is unnecessary.
Depending on the sublimation behaviour of the compounds to be trans~erred, the treated s~de of the carrier and, if this latter is air-permeable, the untreated or treated side of the carrier, is then brought into intimate contact with the surface of the web o~ material to be treated and carrier and web are together subjected to a heat treat ment of at least 8QC and preferably 100C to 220C, in particular 150C to 200C. Particularly good results are obtained with temperatures of 180C to 220C.
According to the invention, this heat treatment is combined with a vacuum treatment in that the carrier/web sandwich which moves in the same direction and at the same speed is alternately heated and subjected to suction. While suction is being exerted, it is also possible to heat simul-taneously. The vacuum is so regulated that as lit~le of the ~56S57 substance to be trans~erred as possible is carried away by the current of air. This heating/suction cycle is repeated until the agents have been transferred from the carrier to the web of material.
A suitable apparatus for carrying out the process according to the invention consists of at least one hea-ting cylinder and one suction cylinder, preferably of a series of altogether 2 to 20, in particular ~ to 16, heating and suction cylinders into which the web oE materîal to be treated can be fed in one single layer or in several layer~.
If the web is fed in a single layer, it is therefore sub-jected to 2 to 20, preferably 4 to 16, heating and suction treatments. The se-ries of heating and suction cylinders can advantageously be grouped in units of e.g, 6 cylinders each. NorMally, one heating cylinder alternates in each case with one suction cylinder. But depending on the subli-mation behaviour of the compounds to be transferred, the number of suction cylinders can also be reduced in proportion to the number of heating cylinders by e.g. connecting one or possibly two suction cylinders after every second, third or sixth heating cylinder. An arrangement in which only 1 to 2 suction cylinders are connected after a series of 2 to 18 or 19 heating cylinders has also proved suitable.
Depending on the unit, the web of material ~o be treated can be fed in as a single layer or in several layers, e,g.
singly in a first unit and in several layers in a second unit.
The heating cylinders can be heated electrically or with heated liquids, e g. oil, or with gas, so that the surface temperature of the cylinder is desirably about 170C
to 220C. The vacuum action of the suction cylinder can be suported in addi-tion by e.g. a heat radiator on the opposite side. Such suction cylinders are normally wrapped in felt.
The material input depends on the desired application form o~ the finishing agents. The application to the carrier can be effected on each side individually or on both sides;
but if a carrier which is impermeable to air is used, only ; the single sided application is desirable. The application of the finishing agents can be carried out on the desired side or on both sides by appropriate conveyance of the ; carrier web. If as superficial a deposit as possible of the ; finishing agents is desired, only a single layer is fed in or if several layers are fed in, ~he material is first brought into contact with the carrier. The penetra-tion of the entire material is improved if each freshly introduced layer of material is fed into the machine e.g. as 4th. or 5th. layer, in other words having no direct contact with the carrier. The penetration of the material with the finishing agents is then effected according to the countercurrent principle. This multiple passage of the material through _ g _ ~56557 the suction/heating cycle makes it possible to compensate for high treatlnent temperatures by longer treatment times.
Preferably, the process according to the invention is carried out with 1 to 10, in particular with 1 to 5, layers. If series of heating and suction cylinders are grouped in several units, the number of these layers can be varied in the diEferent unl~s.
The heat treatment which may be combined with the suction treatment can be effected in various ways, e.g.
by means of a heating plate, a current of warm air, a heated backing roll or, in particular, by infrared radiation.
A further advantage of the process according to the invention is that it is possible to operate with very high speeds on account of the large amount of material fed in. For example, it is possible to carry out the process with running speeds of up to 100 m/min. 9 e,g. 20 to 90 m/min.
or, in particular, 20 to 50 m/min At a transfer time of about 30 seconds and with 5 layers of material, for example, the speed is 90 m/min. In contradistinction thereto, running speeds of only 2 to 3 m/min, are attained using known transfer processes.
By appropriate choice of the carrier structure (e.g.
woven fabric, nonwovens, grained paper) and of the material feed, i.e. lighter, or heavier contact pressure or no pressure at all on the carrier/web sandwich, it is possible to pro-i~ S 65 57 ~uce deslred cal~nder ~ffec~s on the material to be treated.
Suitable air-permeable, organic material that may be treated according to the invention is principally organic but above all textile fibrous material. The fibrous material can be in the most diverse forms of processing, e.g, yarn, especially in piece form, or example woven or knitted ~abrics or non-wovens, The material can be dyed in the con-ventional way, printed or finished be~ore or af~er the treat~
ment according to the invention.
The ~ibrous material itself can be of natural, regenerated man-made or, above all, synthetic man-made fibres.
Examples o~ natural fibres are in particular those of wool or celluloseJ e.g. cotton, linen, hemp or ramie, and examples of regenerated man-made fibres are those of viscose. Pre-ferably, textile materials containing syn~hetic 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 1/2-ace~ate and cellulose triacetate, synthetic polyamide ~ibres, e.g~ those of poly-~-caprolactam (nylon 6)~ polyhexamethylene-diamine adipate (nylon 66), poly-~-aminoundecanoic acid (nylon 7), polyurethane or polyolefin ~i~res, eOg. poly-propylene fibres, acid modified polymides, e g. polyconden-l~S~iSS~
sation procl~lcts of ~,4'-diamino-2,2'-dipl~enyl-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 with aromatic dicarboxy-sulphonic acids, e.g. polycondensation products of ~-caprolactam or hexamethylenediammonium adipate with potassium-3,5-dicarboxybenzenesulphonate, or acid modi-~ied 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, 2g2-bis-(~-sodium sulphopropoxyphenyl)-propane or 3,5-di-carboxybenzenesulphonic acid or sulphonated terephthalic lS acid, sulphonated 4-methoxybenzenecarboxyiic 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, primarily, linear polyester fibres, especially of polyethylene glycol terephthalate or poly-(1,4-cyclohexane-dimethylol)-terephtllalate.
If the material is of acrylonitrile copolymers, the acrylonitrile proportion is desirably at least 50% and preferably at least 85% by weight of the copolymer. Other 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 aI~ide or styrenesulphonic acids.
These materials can also be used as blends with one another or with other fibres, e.g, blends of polyacrylo-nitrile/polyes~er, polyamide/polyester, polyester/viscose and polyester/wool, polyester/cellulose, in particular poly-ester/cotton, The preparations used according to the invention are applied to the carrier e.g. by spraying, coating, sprinkling or printing them over entire surface or over part of the surface.
When products in powder form are used, they are applied form a powder dispenser and products in paste form are applied with a doctor blade or an inclined plane. If the product is in dilute form, it can be applied by a slop pad roller or with a spray device.
The application of products in powder or paste form has the advantage that a binder need not be used s~multane-ously, for binders often lead to incrustations in the appara-tus. The cleaning of the carrier~ providing it is endless, can also be dispensed with. A special dissolving in a solvent and the specific pFoblems in connection therewith (solvent ~L05~;5S7 vapours) also do not arise.
The invention also provides the apparatus for carrying out the dry transfer process described hereinbefor~.
This apparatus comprises (a) a web-shaped carrier which advances in the longitudinal direction, (b) a means for applying organic compounds to the carrier, and following said means in the direction of ~ravel, (c) a sequence of at least one heating unit and one suction unit and optionally additional heating units which are combined with the suction unit, and (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, said apparatus being so constructed that carrier and web advance together synchronously, the one super~
imposed on the other, and are together transported to the heating and suction units, and, after the organic compound has been transferred from the carrier to the web at a temperature above 80D C, web and carrier are separated from each other, it being possible to feed the web into said apparatus in one or more layers simultaneously.
The apparatus of the present invention will now be iilustrated, 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 (1) and the treated web is shown at (2). The carrier to which the organic compound is to be applied is at (3), the means for applying organic compounds is shown at (4) while the carrier after the organic compounds '.~
- 14 ~
~S6557 'have been transferred to it is shown at (5). The web ~1) is fed via a roller (6) 'to the charged carL-l~r and the discharged carrier is led away via a roller (7); (~) is a heating unit in the form of a heatable cylinder, and (9) is a suction unit in the form of a suction cylinder. The source o~ the suction of the suction unit is show at (lo);
(11) is an additional heating unit; e.g. infrared heater, which may be combined with the suction device.
A preferred embodiment of the process according to the invention can be carried out in the apparatus illustrated in Figure II. The textile material to be treated is on roller (12) and is wound onto roller (13) after the compounds have been transferred to it. An endless carrier belt (14), which is advanced or driven by rollers (15) and (16) is an air-permeable carrier, e.g. a metal fibre fleece, a polyamide fibre web or a glass cloth. The compounds are applied at (18) by means of a sprinkler shute or roller. A doctor blade (17) ensures uniform application. Rollers (19), (21) and (23) are oil-heated with a surface temperature of 190 C to 210 C. Each of rollers (20) and (22) consists of a suction cylinder wrapped in felt, provided with suction means (24) and (25). Infrared heaters are show at (26) and t27). The application means (17) and (18) can also be located on the other side of the carrier, but this requires corresponding direction-changing devices for the carrier (14) in order that the application can still be effected from above,(28) is the means ta roller) for conveying the web of material (12) to the charged carrier (14) and (29) is the means ta roller) for transporting the treated web (13) away ~,. .~
3L~56557 `from the carrier (14).
Organic compounds which are converted into the vapour state at atmospheric pressure and above 80 C, especially at 100~ C to 220 C, are principally sublimable disperse dyes and, in particular, finishing agents.
By finishing agents are meant e.~. 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 can belong to the most diverse dyestuff classes. In particular they are monoazo, quinophthalone, methine and anthraquinone dyes, as well as nitro, styryl, a~ostyryl, naphthoprinone or naphthoquinone-imine dyes.
The commercial products of these dyes usually contain dispersants, i.e. a product with surface-active properties which maXes it possible or makes it easier to disperse these dyes in water. Dispersants are not necessary if anhydrous preparations are used.
Examples of sublimable disperse dyes which can be used acc-ordlng to the invention are :
~S~iS57 02N~ N c~l2cl~2~oH
C~19 (2~ ,CO~
~3) C1~3~CO-N~ N ~ N
~::}~3 (~) 02 ,Cll~Cl~20 5) ~21~ N - N ~ ~CH2cll20 Cl- c~i2 -~T2c~ Cl'l=C
C4]19~ `CN
(7) . ~13C~N - N - C - C C~13 - N02 HO ~ - ~
~56S5~
~8) O Nll.
~12 II I OCH
(9j ~ 3 IC~3 (lOj ~
O ~C~13 ~ .
(11) ~ O O-Cn~2~
~ (n ~ 3 or 4) - O ~H2 ~10 O ~ C~13 (12) [~
1C~56S5~
}~2~ p~-~
(14) ~ (n -- 1 or 2) ~I ~2 O Nll~
~15) N ~ S
(16) ~¢~
- H3C 3~4C2 CO ~H
0 ~11 (17) ~2~ C2H401 t)H
~6557 (1~) 1~12 H 0~1 1~
(1~) ~CO~ 2 C1~3 (20) Cl~ ~E ~OC}13 ~0~
~21) ~ ,0C1~3 O N1~2 - ' (22~ C27150 g~ ~ ~ `CN
Cl 3 ~23) 02N ~ ~ 3 - Ci ~12 H
~L056557 ~lN
(24) ~L~ ~ Br }~
C~3-~n2-C~12-C ~ CH3 ~ N ~ C ~ ~
- . 1, - . .
- . . ~ O ' ,:
(27~ 5C2 ~ N ~ '~ \N~I
~15C2~
, The preferred dirperse dyes are those of the formulae (2), (10) and (13).
~ The sublimable fluorescent brighteners can belong - ~to any desired class of brightener. In particular they are cumarins, benzocumarins, pyrazones, pyrazolines, oxazines, oxazolyl, thiazolyl, dibenzoxazolyl or dibenzimidazolyl ~OS6557 compoundss, and also naphthalic imides. ~xamples of subli-mable fluorescent brighteners which can be used according to the invention are:
113C ~ C - Cl~ = C~l - C ~ C113 (29) ~ ~C - C~-~ ~ Cll - C~
C}l~C~120M
. .
. HC - C~l C~13 CII3 (30) ~ r- C C - C~ ~ ~ C - Cl~2 ~ C - C113 \=~/ ~S' ~ o~ CH3 C~l3 71C - CH N~y~ ,COOCH3 (31) ~ C~s~C -.
H3 ~ C - CH = CH ~ cooc~i3 C~
HC - CH HC - C~l ~N ~,'~ C - C~I
(33) ~ C~O~C- C~s~C - C~O ~ C~13 , ' .
h3CoOC ~ ~ N & ~ C~l=C~ C ~ ~ _CCOC~3 - : . .
~156557 ~35) Cl ~3c N N~ COOC~l3 N 1~1 (36) ~3~H- CH
S02~NH~C~H1 7 N (C2H5 ~ ~
(37) ~ ~ND ~æ
(38) C1~3CH CH - C ~3 (39) ~N
~N~
O -- C C -- ~
(40) - - C~3 .
~0 56 5S7 111 - C~l f ~
(42) ~ N~C C '' ~N
(~3~ C~l C~3 - C ~ C - C C - C ~ ~ (CH3)3 ' ~ ~ S~ ~O
(~4) CH3 N
Cl~3 ~ C 0~ C = C~ ~ 0 ~ \C(CH ) According to the invention howevPr, preferably ; finishing agents are transferred. As finlshing agents which are transferred to the organic material at atmospheric pressure and at a temperature above 80C, preferably at 100C to 220~C, 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 imp~rt to the textile material the desired effect, ' 105~;S57 e.g~ antis~atic, water repellent, handle-improving or flame-resistant effects. The cited textile protective and/or finishing agents can, if desired, be applied to the material to be finis'.ing together with disperse dyes and/or fluorescent brighteners that are converted into the vapour state at atmos-pheric pressure and at temperatures between e.g, 150C and 220~
The finishing agents which can be used according to the invention are known or they can be manufactured by processes which are known per se. They belong to the most diverse classes of chemi~-als.
As an example of a bacteriostatic pro~ective sub-stance there may be mentioned the compound of the formula (45) Cl - ~ - O ~
- Cl HO
lS and as example of a fungistatic protective substance the compound of the formula CH2CH20H (~
(40) LC12}l25- -C~2CH,OH
~L056~57 and of the ormula Cl Cl (~7) C11~123C ~ Cl Cl Cl An example of a compound that imparts handle-improving properti.es to ~he textile fa~ric is that of the formula ~ 12C~120H
(48) C17H35 CO \
CH2CH~OH
and examples of compounds ~hat impart antistatic properties to the textile fabric are those of the formulae (49) HO-(cH2cH20)7-ls o' (50) C~12-C-CO(CH2CH20)7C~3 (Sl) [H C -CO-I~H-C~2-CH2-cH2-N-cH3 ~ cl-l3c (52) ~I23Cll-CO-~cH2cH2 )7 .
~565S7 _ ` (~)/C2H5 (53) C17tl35CONl~(cl~2)3N \ C2 5 S~C~13 Q
. CH3 (S4) C I-l ~30 (C~12 C112 )8 - ; .
C17H35~ C ~ CH2 (55) \ ~3 / 2 CH3COO
HN
CH2C 1~20H .
r ~ _ G9 1, CH2C~2 r OH .
(56) ~12H25 N ~ CH3COO ~3 . CH2CH2-OH
The preferred compounds are those of the formulae (54) and ~56~. :
Examples of compounds that impart water repellent properties ~o the tex~ile material are those of the formulae . .
(57~ C17H35 Il , (58) C8F17C~12,C~-O-c-cl~-cH2 1, ~S~5~q (59) C8Fl7cH2-c~-oH
O O
) C8Fl7cl~2cEl2oc-c~'~=cll-c-o-c~l2cl-l2c8Fl7 H3COH~C \ f N ~ / CH~Coocl7~l3s (Gi) / N ~~ N \
H3COH2C C C1'120C1'13 ~C~12COOCl7'~-l35 C~12C1~3 or methylhydrogen polysiloxan~s or dimethyl methylhydrogen polysiloxanes.
The preferred compounds are the dimethyl methyl-hydrogen polysiloxanes.
The following compounds are examples of suitable flameproofing agen~s:
A) Methylenedioxybenzene compounds of the formulae ~ ~~r~ r~CH2 ~ CH = CH2 (62) CH ll l 2 O ~ ~ C2H5 CH~ - P
O\ OC2H5 ~16S57 Br ~OC21~5 --~C~I Cll Cl-12 p ~ OC 21~5 C~l -P
2 O~ o~.2~15 0 ~ 2 ~ 2 (~) C~2--O~W, ~ OC2 CH P
O~ OC2~5 CH2 -CH-CHzBr (65~ CH2 ~ C~12-Cl B) Phosphorus co-rnpounds of the formula~
(66)~3p/~)C2~5 -' , O OC2Hs (67)HO--~ ~ OC2H5 ~ O OC2~5 1.
~565S7 (6~) HO -~ 2 ~l ~ OC 11 (69~ ~10~3 2ll \ OCI~
COOC~13 ~IO
" .,., ~ ,. 0 02HS
(71) o OC2115 (72) CH30 ~_ CH -- p / 2 5 (73) Cl~
1~56557 C) Phosphorus compounds of the formtlla~
Br Br O
(74) C~2~Cll CH~--)2 P ~ C~12C~I~H
~r Br O . O C~13 (75) ~CU2-Cll~c~l2-O-)2P-o-c~2cll2 O C 2 ~Br Br O
, , . . 1 (76j ~ 1? C~ C~2-0-)2 P-OH
/
l~r Br O
, , (77) ~H2-CLI-cH2 )3 The preferred compounds are those of the formulae (75) and (77).
D) Halogen compounds of the formulae 13r Er - ~3r ~3r -(78) C'r~2- C;.l - C h O -- C,~1 - O CX - CIi- CII
, CH2~1 (79) CI~2-Cl'-CO ~ ~ .
Cl ~ Br Br , ~80~ C~l 2~ C ~2 ~ C~O--C'l~--Cf 1~ CLI~?
~L056557 }~r ~3r ~81) C~2 C~l C''2 2 ~ Br (~2) Cl-2-C}l-C~12~0 CO-C~-C~I-COOI~
, Br Br `.
~83) Cll2-c;-l-co~ c~l2oH
Cl l~r Br (84) ~ C~l2-coo-c~2-cH-cH2 ~r Br (85) C112-C~-CO~
The preferred compounds are those of the formulae (83) and (84).
E) Halogen compounds o~ the formulae Cl . ~ 1 (86) Cl ~~~ ~ SH
.`'-- ' ~\
Cl Cl Br (~7 ) Br ~ O- CIT2 - Cl-l- CH~, - Br Br Br Br (8~) Br~-- OCf!2~ Cll~ C~12 ~r ~ Br Br Br Br Br \_~ ~/
~89) Br Br Br CO
\ / ~O' (90) Br~--CO
.- ~' >~
Br Br Br (91) Br--~ OH
~ ' ~r Br CEl ~/
(92~ Br--~ \~ OH
~ .
Bx Br 1~56~i~7 l~hen choosing the organic compound or compounds and especially of 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 S are transferred to the organic material without decomposi-tion. Preferred compounds are those having transfer tempera-tures be-tween 100C and 220C, in particular between 150C
and 200C. To attain several finishing effec~s in one procedure, it is preferable to use textile finishing agents with as similar transfer properties as possible, i,e. those with similar transfPr temperatures that do not differ by more than 20C.
~n the following E~amples which illustrate the invention, the percentages are by weight.
1~56SS7 _a~
Dim~thyl methylhydrogen polysiloxane (viscosity 20-~0 cst at 25C) is applied with a slop pad roller to an endless carrier of glass cloth t7 g/m ~.
The side to be treated of the carrier advanclng at a speed of 20 m/min. is brought lnto contact with the web o~ poly-ester/cotton (50:50) popL1n (140 g/m2), which has pr~viously been sprayed with 0~2% o~ ZrOCl~ (catalyst) and whlch ad-vances at the same speed as the carrier, in such a manner -that carrier and web of material are together transported synchronously with the one superimposed the other.
Carrier and web of material are then fed into an apparatus as described in figure II. The lst,, 2nd. and 5~h. cylinder~s (cf. (19), (21) and (23) in figure II) are heating cylinders lS of 90 cm diameter and with a temperature of 190C. The 2nd.
and 4th, cylinder (cf. (20) and (22) in figure II) are suct-ion ~ylinders of the same diameter.
After the first passage, the web of material is fed a second time into the apparatus, so that there are always 2 layers of web in the apparatus (an inner one dir~ctly on the carrier, the outer one in connexion with the inner one but separated from the carrier).
After the entire web of material has run twice through the apparatus on each o~casion, web and carrier are separated from each other. A rleaning of the carrier is unnecessary 105~5~i7 since only pure substance is applied.
The finished polyester/cotton poplin has values of 80 to - 100 in the AATCC Spray Test 12-1966, whereas a comparison sample which was not finished has valwes from O to 20, This ~est for evaluating the water repellent properties of textiles specifies values in the range from O (minimum) to 100 (maximum).
Similar results are obtained with the compounds of the formulae (57), (58), (60) and (61), but without spraying the a~ric with a catalyst, e,g. zirconium oxychloride, before treating it.
Example 2 40 g of one of the yellow, blue or red dyes of the formulae (2) 3 (10) or (13) and 100 g of ethyl cellulose in 860 g of a methyl ethyl ketone/ethanol mixture (weight ratio 1:1) are ground for 5 hours at 20C in a sand mill and dispersed to form a homogeneous printing ink, Paper carriers are then printed with one of these inks so as to give a dye application of 0.5 to 4 g/m2 aft~r the sol-vent has been evaporated at 20C. One of these printed paper carriers together with a polyester fabric (120 g/m2) is fed in a single layer into an apparatus similar to that illust-rated in figure II, The paper carrier is adapted to the length of the web of material to be dyed, The apparatus 1~565S7 comprises 2 units the irst of which, in the direction of ~ravel of the carrier, consists of 6 rollers and the second unit of 4 rollers, The 1st, 3rd. and 5th, roller of the firs~ unit and the 1st and 3rd. roller of the S second unit are heating cylinders of 50 cm diameter which axe heated to 215C, The 2nd,, 4th. and 6th~ rollers of the first unit and the 2nd, and 4th. roller o the second unit are suction cylinders wrapped in felt of S0 cm diameter on which the paper carrier is heated from the reverse side to 220C with an infrared heater during the suc-tion cycle, Carrier and web of material pars once at ~he same speed through the apparatus at a speed of 60 m/min. and are subsequently separated.
A polyester fabric which is dyed a deep, level yellow (or blue or red) is obtained in this way, - Example 3 The compounds of the formula (56) are slop padded as 50%
solution in ethanol to give an application of 5 g/m2 on an endless carrier consisting of a polytetrafluoroethylene web.
This carrier is a component of an apparatus similar to that of figure II, except that it consists of only 4 rollers of which the 1st, and 3rd., in the direction of travel of the carrier, are heating cylinders with a diameter of 50 cm and are heated to 140C, whereas the Znd, and 4th.
~ 5 ~ 5 5~
roller are suction cylinders of 50 cm diameter which cannot be heated.
A polyacrylonitrile fabric (130 g/m2) is then fed into the apparatus. After the fabric has passed once through the 4 rollers it is fed 4 more times into the apparatus and on each occasion the freshly introduced web is removed ~rom the carrier, i.e. i~ passes into the appara~us as 2nd. and 3rd., ~th and 5th. layer. The fabric is subsequently separa-ted from the carrier so that 5 layers of fabric having a total length of about 12 metres are always in the apparatus. ~he 5 layers of abric move synchronously with the carrier at - a speed of 90 m/min. Carrier and fabric are subsequently separated.
The electrostatic proper-ties are tested by measuring the surface resistance in ~ /lOOcm2 and the half life period indicates the time which passes until the voltage of a fabric electrostatically charged with 100 volts falls to 50 volts~
The surface resistance of the polyacrylonitrile fabric is 1016JQ/lOOcm2 before the treatment and lOllQ llO0 cm2 after the treatment, which corresponds to a 10000-fold reduction of the surface resistance.
Before treatment the fabric has a half life period of 300 seconds, whereas after treatment this falls to only 5 seconds.
Similar results are obtained with the compounds of the 1~56~;57 formulae (51), (53) and (55).
Example 4 The compound of the formula (54) is slop padded as oily, viscous liquid on an endless, airtight po1yester carrier so as to give an application o~ l.2 g/m . Slnce the carrier is airtight, it is necessary for the application means (17) and (18) of ~igure ~I to be so posl~loned that th~ activated side o~ the endless carrier can be brought into contact with the web of material to be treated. In divergence from figure II, the apparatus consis~s of 2 units each comprising 6 rollers of 50 cm diameter. The lst., 2nd,l 4th. and 5th.
rollers of each unit, in the direction of travel of the carrier, are in the form of heating cylinders which are heated to 180C and the 3rd. and 6th. rollers of each unit are sustion cylinders which are each heated with infrared heaters to 200G.
A polyester fabric (150 g/m2) is then fed into the apparatus.
The fabric ru-ns once through the apparatus synchronously with the carrier at a speed of 60 m/minO and is subsequently separated from the carrier. The treated polyester fabric is tested for its electrostatic properties as indicated in Example 3. As reported in Example 3, the treatment reduces the surface resistance by lO,000-fold. Before the treatment the polyester fabric has a half life period of 290 seconds ~0565S7 and after the ~eatment this falls ~o only 1 second.
Similar results are obtained with the compounds of the formulae (49) and (50).
A polyamide fabric (100 g/m ) is fed into an apparatus similar -~o that illustrated by figure II, except that it consists of
~565S7 can be cut into pieces. As a rule ~he carrier i9 inert, i.e.
i~ possess~ no a~finity for the preparation that contains the compound to be transferred. The carrier can be air-permeable or, preferably, airtight.
Desirably, the carrier is a flexible, preferably thre~-dimensionally stable ribbon or web or a foil which is stable to heat. Air-permeable carriers with continuous surface are e.g. perorated or porous.
The carriers can be made ~rom a wide variety of ma~erials, 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), met fibre fleeces, perforated or porous plastic sheets, glass fibre fleeces of glass cloths, air~ight or perforated or porous paper, nonwoven fabrics, woven or knitted textiles or felts.
Examples of materials which have proved particularly suitable are paper, aluminium, or steel strips which can be perforated or unperforated, glass cloths, plastic sheets which can be perforated or unperforated, in particular those of polyester or polytetrafluoroethylene, and nonwoven fabrics, e.g. webs of polyester or polyamide fibres.
Also suitable are carriers with plastic coatings in the form of perforated or unperforated films, e.g. coa~ings of polyvinyl resins, ethyl celluloseJ polyure~hanes or poly-~056557 tetrafluoroe-thylene.
In addition to the compounds which are transferred to the material web, the preparations used according to the invention can contain at least one binding agent which is stable below 250C, water and/or an organic solvent.
Suitable binding agents are synthetic, semi-synt-hetic or natur~l resins, both polycondensation and poly-addition products being possible. In eff~ct, it is possible to use all binding agents conventionally used in the paint and ~rinting ink industry, The binding agents are used to fix the compounds to be transferred at the treated area of the carrier. But at the ~ransfer temperature they should not melt, react with each other, i~eO crosslink, and shoul~
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. Exampl~s 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, pxopyl cellulose, isopropyl cellulose, benzyl cellulose or hydroxyethyl cellulose, and mixtures thereo~.
Suitable organic solvents are those that are mis-cible or immis~ible with water or solvent mixtures with a boiling poin~ at normal pressure belbw 150C, preferably below 1~0C. It is advantageous to use ~liphatic, cyclo-~liphatic or aromatic hydrocarbons, e.g. toluene, cyclo-hexane, petroleum ether; lower alkanols, e.g. methanol, ethanol, propanol, isoprop~nol, esters o aliphatlc mono-carboxylic acid, e.g. ethyl acetate or ethyl propylate;
aliphatic ketones, e.g. methyl ethyl ketone and halogenated aliphatic hydrocarbons, e,g. perchloroethylene, trichloro-ethylene, l,l,l-trichloroethane or l,1,2-trichloro-2,2,1-B trifluorocthylene. Particularly preferred solvents are ~s~
aliphatic esters, ketones or alcohols, e.g. butyl acetate, c acetone, methyl ethyl ketone, ethanol, isopropanol or butanol and mixtures thereof, 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 solvent or solvent mixture within 0 to 99.9%, based on the total weight of the pre-~ S 65S7 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 m2.
The preparations used according to the invention can be manufactured eOg, by dissolving or finely dispersing in water and/or an organic solvent a compound which is trans~erred to the fibrous material a-t atmospheric pressure and at temperature above 80C, 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 continously, for example by spraying, coating or, preferably, by printing it over part of or over the entire surface. Principa71y when using paper carriers and those made of stainless steel, it is possible to use the most diverse printing methods3 e.g, relief printing (e,g, book printing, flexoprinting), intaglio printing (e g. roller printing), silk-screen printing (e.g. rotary screen printing, flat-screen printing) or electrostatic printing.
It is also possible to apply organic compounds by 2~ themselves direct, i.e. without the addition o bînders and solvents, by spinkling, spraying, pouring, slop padding or with a doctor blade.
A particular embodiment of the present process consists in applying the organic compound in pattern form to a web o~
material, e.g. by printing it, or instead of a complete web, 1~)56~57 applying ~ut pieces of the carrier to the fibrous material to be treated. These patterns are obtained by punching or cutting suitable segments into the carriers cited herein-above.
A~ter the preparations have been applied to th~
carrier they may be dried, e.g. in a wanm current of air or by infrared radiation, if appropriate with recovery o~
the solvent employed. But i~ the organic compounds to be trans~erred are applied direct by themselves, ~hen such a drying is unnecessary.
Depending on the sublimation behaviour of the compounds to be trans~erred, the treated s~de of the carrier and, if this latter is air-permeable, the untreated or treated side of the carrier, is then brought into intimate contact with the surface of the web o~ material to be treated and carrier and web are together subjected to a heat treat ment of at least 8QC and preferably 100C to 220C, in particular 150C to 200C. Particularly good results are obtained with temperatures of 180C to 220C.
According to the invention, this heat treatment is combined with a vacuum treatment in that the carrier/web sandwich which moves in the same direction and at the same speed is alternately heated and subjected to suction. While suction is being exerted, it is also possible to heat simul-taneously. The vacuum is so regulated that as lit~le of the ~56S57 substance to be trans~erred as possible is carried away by the current of air. This heating/suction cycle is repeated until the agents have been transferred from the carrier to the web of material.
A suitable apparatus for carrying out the process according to the invention consists of at least one hea-ting cylinder and one suction cylinder, preferably of a series of altogether 2 to 20, in particular ~ to 16, heating and suction cylinders into which the web oE materîal to be treated can be fed in one single layer or in several layer~.
If the web is fed in a single layer, it is therefore sub-jected to 2 to 20, preferably 4 to 16, heating and suction treatments. The se-ries of heating and suction cylinders can advantageously be grouped in units of e.g, 6 cylinders each. NorMally, one heating cylinder alternates in each case with one suction cylinder. But depending on the subli-mation behaviour of the compounds to be transferred, the number of suction cylinders can also be reduced in proportion to the number of heating cylinders by e.g. connecting one or possibly two suction cylinders after every second, third or sixth heating cylinder. An arrangement in which only 1 to 2 suction cylinders are connected after a series of 2 to 18 or 19 heating cylinders has also proved suitable.
Depending on the unit, the web of material ~o be treated can be fed in as a single layer or in several layers, e,g.
singly in a first unit and in several layers in a second unit.
The heating cylinders can be heated electrically or with heated liquids, e g. oil, or with gas, so that the surface temperature of the cylinder is desirably about 170C
to 220C. The vacuum action of the suction cylinder can be suported in addi-tion by e.g. a heat radiator on the opposite side. Such suction cylinders are normally wrapped in felt.
The material input depends on the desired application form o~ the finishing agents. The application to the carrier can be effected on each side individually or on both sides;
but if a carrier which is impermeable to air is used, only ; the single sided application is desirable. The application of the finishing agents can be carried out on the desired side or on both sides by appropriate conveyance of the ; carrier web. If as superficial a deposit as possible of the ; finishing agents is desired, only a single layer is fed in or if several layers are fed in, ~he material is first brought into contact with the carrier. The penetra-tion of the entire material is improved if each freshly introduced layer of material is fed into the machine e.g. as 4th. or 5th. layer, in other words having no direct contact with the carrier. The penetration of the material with the finishing agents is then effected according to the countercurrent principle. This multiple passage of the material through _ g _ ~56557 the suction/heating cycle makes it possible to compensate for high treatlnent temperatures by longer treatment times.
Preferably, the process according to the invention is carried out with 1 to 10, in particular with 1 to 5, layers. If series of heating and suction cylinders are grouped in several units, the number of these layers can be varied in the diEferent unl~s.
The heat treatment which may be combined with the suction treatment can be effected in various ways, e.g.
by means of a heating plate, a current of warm air, a heated backing roll or, in particular, by infrared radiation.
A further advantage of the process according to the invention is that it is possible to operate with very high speeds on account of the large amount of material fed in. For example, it is possible to carry out the process with running speeds of up to 100 m/min. 9 e,g. 20 to 90 m/min.
or, in particular, 20 to 50 m/min At a transfer time of about 30 seconds and with 5 layers of material, for example, the speed is 90 m/min. In contradistinction thereto, running speeds of only 2 to 3 m/min, are attained using known transfer processes.
By appropriate choice of the carrier structure (e.g.
woven fabric, nonwovens, grained paper) and of the material feed, i.e. lighter, or heavier contact pressure or no pressure at all on the carrier/web sandwich, it is possible to pro-i~ S 65 57 ~uce deslred cal~nder ~ffec~s on the material to be treated.
Suitable air-permeable, organic material that may be treated according to the invention is principally organic but above all textile fibrous material. The fibrous material can be in the most diverse forms of processing, e.g, yarn, especially in piece form, or example woven or knitted ~abrics or non-wovens, The material can be dyed in the con-ventional way, printed or finished be~ore or af~er the treat~
ment according to the invention.
The ~ibrous material itself can be of natural, regenerated man-made or, above all, synthetic man-made fibres.
Examples o~ natural fibres are in particular those of wool or celluloseJ e.g. cotton, linen, hemp or ramie, and examples of regenerated man-made fibres are those of viscose. Pre-ferably, textile materials containing syn~hetic 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 1/2-ace~ate and cellulose triacetate, synthetic polyamide ~ibres, e.g~ those of poly-~-caprolactam (nylon 6)~ polyhexamethylene-diamine adipate (nylon 66), poly-~-aminoundecanoic acid (nylon 7), polyurethane or polyolefin ~i~res, eOg. poly-propylene fibres, acid modified polymides, e g. polyconden-l~S~iSS~
sation procl~lcts of ~,4'-diamino-2,2'-dipl~enyl-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 with aromatic dicarboxy-sulphonic acids, e.g. polycondensation products of ~-caprolactam or hexamethylenediammonium adipate with potassium-3,5-dicarboxybenzenesulphonate, or acid modi-~ied 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, 2g2-bis-(~-sodium sulphopropoxyphenyl)-propane or 3,5-di-carboxybenzenesulphonic acid or sulphonated terephthalic lS acid, sulphonated 4-methoxybenzenecarboxyiic 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, primarily, linear polyester fibres, especially of polyethylene glycol terephthalate or poly-(1,4-cyclohexane-dimethylol)-terephtllalate.
If the material is of acrylonitrile copolymers, the acrylonitrile proportion is desirably at least 50% and preferably at least 85% by weight of the copolymer. Other 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 aI~ide or styrenesulphonic acids.
These materials can also be used as blends with one another or with other fibres, e.g, blends of polyacrylo-nitrile/polyes~er, polyamide/polyester, polyester/viscose and polyester/wool, polyester/cellulose, in particular poly-ester/cotton, The preparations used according to the invention are applied to the carrier e.g. by spraying, coating, sprinkling or printing them over entire surface or over part of the surface.
When products in powder form are used, they are applied form a powder dispenser and products in paste form are applied with a doctor blade or an inclined plane. If the product is in dilute form, it can be applied by a slop pad roller or with a spray device.
The application of products in powder or paste form has the advantage that a binder need not be used s~multane-ously, for binders often lead to incrustations in the appara-tus. The cleaning of the carrier~ providing it is endless, can also be dispensed with. A special dissolving in a solvent and the specific pFoblems in connection therewith (solvent ~L05~;5S7 vapours) also do not arise.
The invention also provides the apparatus for carrying out the dry transfer process described hereinbefor~.
This apparatus comprises (a) a web-shaped carrier which advances in the longitudinal direction, (b) a means for applying organic compounds to the carrier, and following said means in the direction of ~ravel, (c) a sequence of at least one heating unit and one suction unit and optionally additional heating units which are combined with the suction unit, and (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, said apparatus being so constructed that carrier and web advance together synchronously, the one super~
imposed on the other, and are together transported to the heating and suction units, and, after the organic compound has been transferred from the carrier to the web at a temperature above 80D C, web and carrier are separated from each other, it being possible to feed the web into said apparatus in one or more layers simultaneously.
The apparatus of the present invention will now be iilustrated, 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 (1) and the treated web is shown at (2). The carrier to which the organic compound is to be applied is at (3), the means for applying organic compounds is shown at (4) while the carrier after the organic compounds '.~
- 14 ~
~S6557 'have been transferred to it is shown at (5). The web ~1) is fed via a roller (6) 'to the charged carL-l~r and the discharged carrier is led away via a roller (7); (~) is a heating unit in the form of a heatable cylinder, and (9) is a suction unit in the form of a suction cylinder. The source o~ the suction of the suction unit is show at (lo);
(11) is an additional heating unit; e.g. infrared heater, which may be combined with the suction device.
A preferred embodiment of the process according to the invention can be carried out in the apparatus illustrated in Figure II. The textile material to be treated is on roller (12) and is wound onto roller (13) after the compounds have been transferred to it. An endless carrier belt (14), which is advanced or driven by rollers (15) and (16) is an air-permeable carrier, e.g. a metal fibre fleece, a polyamide fibre web or a glass cloth. The compounds are applied at (18) by means of a sprinkler shute or roller. A doctor blade (17) ensures uniform application. Rollers (19), (21) and (23) are oil-heated with a surface temperature of 190 C to 210 C. Each of rollers (20) and (22) consists of a suction cylinder wrapped in felt, provided with suction means (24) and (25). Infrared heaters are show at (26) and t27). The application means (17) and (18) can also be located on the other side of the carrier, but this requires corresponding direction-changing devices for the carrier (14) in order that the application can still be effected from above,(28) is the means ta roller) for conveying the web of material (12) to the charged carrier (14) and (29) is the means ta roller) for transporting the treated web (13) away ~,. .~
3L~56557 `from the carrier (14).
Organic compounds which are converted into the vapour state at atmospheric pressure and above 80 C, especially at 100~ C to 220 C, are principally sublimable disperse dyes and, in particular, finishing agents.
By finishing agents are meant e.~. 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 can belong to the most diverse dyestuff classes. In particular they are monoazo, quinophthalone, methine and anthraquinone dyes, as well as nitro, styryl, a~ostyryl, naphthoprinone or naphthoquinone-imine dyes.
The commercial products of these dyes usually contain dispersants, i.e. a product with surface-active properties which maXes it possible or makes it easier to disperse these dyes in water. Dispersants are not necessary if anhydrous preparations are used.
Examples of sublimable disperse dyes which can be used acc-ordlng to the invention are :
~S~iS57 02N~ N c~l2cl~2~oH
C~19 (2~ ,CO~
~3) C1~3~CO-N~ N ~ N
~::}~3 (~) 02 ,Cll~Cl~20 5) ~21~ N - N ~ ~CH2cll20 Cl- c~i2 -~T2c~ Cl'l=C
C4]19~ `CN
(7) . ~13C~N - N - C - C C~13 - N02 HO ~ - ~
~56S5~
~8) O Nll.
~12 II I OCH
(9j ~ 3 IC~3 (lOj ~
O ~C~13 ~ .
(11) ~ O O-Cn~2~
~ (n ~ 3 or 4) - O ~H2 ~10 O ~ C~13 (12) [~
1C~56S5~
}~2~ p~-~
(14) ~ (n -- 1 or 2) ~I ~2 O Nll~
~15) N ~ S
(16) ~¢~
- H3C 3~4C2 CO ~H
0 ~11 (17) ~2~ C2H401 t)H
~6557 (1~) 1~12 H 0~1 1~
(1~) ~CO~ 2 C1~3 (20) Cl~ ~E ~OC}13 ~0~
~21) ~ ,0C1~3 O N1~2 - ' (22~ C27150 g~ ~ ~ `CN
Cl 3 ~23) 02N ~ ~ 3 - Ci ~12 H
~L056557 ~lN
(24) ~L~ ~ Br }~
C~3-~n2-C~12-C ~ CH3 ~ N ~ C ~ ~
- . 1, - . .
- . . ~ O ' ,:
(27~ 5C2 ~ N ~ '~ \N~I
~15C2~
, The preferred dirperse dyes are those of the formulae (2), (10) and (13).
~ The sublimable fluorescent brighteners can belong - ~to any desired class of brightener. In particular they are cumarins, benzocumarins, pyrazones, pyrazolines, oxazines, oxazolyl, thiazolyl, dibenzoxazolyl or dibenzimidazolyl ~OS6557 compoundss, and also naphthalic imides. ~xamples of subli-mable fluorescent brighteners which can be used according to the invention are:
113C ~ C - Cl~ = C~l - C ~ C113 (29) ~ ~C - C~-~ ~ Cll - C~
C}l~C~120M
. .
. HC - C~l C~13 CII3 (30) ~ r- C C - C~ ~ ~ C - Cl~2 ~ C - C113 \=~/ ~S' ~ o~ CH3 C~l3 71C - CH N~y~ ,COOCH3 (31) ~ C~s~C -.
H3 ~ C - CH = CH ~ cooc~i3 C~
HC - CH HC - C~l ~N ~,'~ C - C~I
(33) ~ C~O~C- C~s~C - C~O ~ C~13 , ' .
h3CoOC ~ ~ N & ~ C~l=C~ C ~ ~ _CCOC~3 - : . .
~156557 ~35) Cl ~3c N N~ COOC~l3 N 1~1 (36) ~3~H- CH
S02~NH~C~H1 7 N (C2H5 ~ ~
(37) ~ ~ND ~æ
(38) C1~3CH CH - C ~3 (39) ~N
~N~
O -- C C -- ~
(40) - - C~3 .
~0 56 5S7 111 - C~l f ~
(42) ~ N~C C '' ~N
(~3~ C~l C~3 - C ~ C - C C - C ~ ~ (CH3)3 ' ~ ~ S~ ~O
(~4) CH3 N
Cl~3 ~ C 0~ C = C~ ~ 0 ~ \C(CH ) According to the invention howevPr, preferably ; finishing agents are transferred. As finlshing agents which are transferred to the organic material at atmospheric pressure and at a temperature above 80C, preferably at 100C to 220~C, 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 imp~rt to the textile material the desired effect, ' 105~;S57 e.g~ antis~atic, water repellent, handle-improving or flame-resistant effects. The cited textile protective and/or finishing agents can, if desired, be applied to the material to be finis'.ing together with disperse dyes and/or fluorescent brighteners that are converted into the vapour state at atmos-pheric pressure and at temperatures between e.g, 150C and 220~
The finishing agents which can be used according to the invention are known or they can be manufactured by processes which are known per se. They belong to the most diverse classes of chemi~-als.
As an example of a bacteriostatic pro~ective sub-stance there may be mentioned the compound of the formula (45) Cl - ~ - O ~
- Cl HO
lS and as example of a fungistatic protective substance the compound of the formula CH2CH20H (~
(40) LC12}l25- -C~2CH,OH
~L056~57 and of the ormula Cl Cl (~7) C11~123C ~ Cl Cl Cl An example of a compound that imparts handle-improving properti.es to ~he textile fa~ric is that of the formula ~ 12C~120H
(48) C17H35 CO \
CH2CH~OH
and examples of compounds ~hat impart antistatic properties to the textile fabric are those of the formulae (49) HO-(cH2cH20)7-ls o' (50) C~12-C-CO(CH2CH20)7C~3 (Sl) [H C -CO-I~H-C~2-CH2-cH2-N-cH3 ~ cl-l3c (52) ~I23Cll-CO-~cH2cH2 )7 .
~565S7 _ ` (~)/C2H5 (53) C17tl35CONl~(cl~2)3N \ C2 5 S~C~13 Q
. CH3 (S4) C I-l ~30 (C~12 C112 )8 - ; .
C17H35~ C ~ CH2 (55) \ ~3 / 2 CH3COO
HN
CH2C 1~20H .
r ~ _ G9 1, CH2C~2 r OH .
(56) ~12H25 N ~ CH3COO ~3 . CH2CH2-OH
The preferred compounds are those of the formulae (54) and ~56~. :
Examples of compounds that impart water repellent properties ~o the tex~ile material are those of the formulae . .
(57~ C17H35 Il , (58) C8F17C~12,C~-O-c-cl~-cH2 1, ~S~5~q (59) C8Fl7cH2-c~-oH
O O
) C8Fl7cl~2cEl2oc-c~'~=cll-c-o-c~l2cl-l2c8Fl7 H3COH~C \ f N ~ / CH~Coocl7~l3s (Gi) / N ~~ N \
H3COH2C C C1'120C1'13 ~C~12COOCl7'~-l35 C~12C1~3 or methylhydrogen polysiloxan~s or dimethyl methylhydrogen polysiloxanes.
The preferred compounds are the dimethyl methyl-hydrogen polysiloxanes.
The following compounds are examples of suitable flameproofing agen~s:
A) Methylenedioxybenzene compounds of the formulae ~ ~~r~ r~CH2 ~ CH = CH2 (62) CH ll l 2 O ~ ~ C2H5 CH~ - P
O\ OC2H5 ~16S57 Br ~OC21~5 --~C~I Cll Cl-12 p ~ OC 21~5 C~l -P
2 O~ o~.2~15 0 ~ 2 ~ 2 (~) C~2--O~W, ~ OC2 CH P
O~ OC2~5 CH2 -CH-CHzBr (65~ CH2 ~ C~12-Cl B) Phosphorus co-rnpounds of the formula~
(66)~3p/~)C2~5 -' , O OC2Hs (67)HO--~ ~ OC2H5 ~ O OC2~5 1.
~565S7 (6~) HO -~ 2 ~l ~ OC 11 (69~ ~10~3 2ll \ OCI~
COOC~13 ~IO
" .,., ~ ,. 0 02HS
(71) o OC2115 (72) CH30 ~_ CH -- p / 2 5 (73) Cl~
1~56557 C) Phosphorus compounds of the formtlla~
Br Br O
(74) C~2~Cll CH~--)2 P ~ C~12C~I~H
~r Br O . O C~13 (75) ~CU2-Cll~c~l2-O-)2P-o-c~2cll2 O C 2 ~Br Br O
, , . . 1 (76j ~ 1? C~ C~2-0-)2 P-OH
/
l~r Br O
, , (77) ~H2-CLI-cH2 )3 The preferred compounds are those of the formulae (75) and (77).
D) Halogen compounds of the formulae 13r Er - ~3r ~3r -(78) C'r~2- C;.l - C h O -- C,~1 - O CX - CIi- CII
, CH2~1 (79) CI~2-Cl'-CO ~ ~ .
Cl ~ Br Br , ~80~ C~l 2~ C ~2 ~ C~O--C'l~--Cf 1~ CLI~?
~L056557 }~r ~3r ~81) C~2 C~l C''2 2 ~ Br (~2) Cl-2-C}l-C~12~0 CO-C~-C~I-COOI~
, Br Br `.
~83) Cll2-c;-l-co~ c~l2oH
Cl l~r Br (84) ~ C~l2-coo-c~2-cH-cH2 ~r Br (85) C112-C~-CO~
The preferred compounds are those of the formulae (83) and (84).
E) Halogen compounds o~ the formulae Cl . ~ 1 (86) Cl ~~~ ~ SH
.`'-- ' ~\
Cl Cl Br (~7 ) Br ~ O- CIT2 - Cl-l- CH~, - Br Br Br Br (8~) Br~-- OCf!2~ Cll~ C~12 ~r ~ Br Br Br Br Br \_~ ~/
~89) Br Br Br CO
\ / ~O' (90) Br~--CO
.- ~' >~
Br Br Br (91) Br--~ OH
~ ' ~r Br CEl ~/
(92~ Br--~ \~ OH
~ .
Bx Br 1~56~i~7 l~hen choosing the organic compound or compounds and especially of 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 S are transferred to the organic material without decomposi-tion. Preferred compounds are those having transfer tempera-tures be-tween 100C and 220C, in particular between 150C
and 200C. To attain several finishing effec~s in one procedure, it is preferable to use textile finishing agents with as similar transfer properties as possible, i,e. those with similar transfPr temperatures that do not differ by more than 20C.
~n the following E~amples which illustrate the invention, the percentages are by weight.
1~56SS7 _a~
Dim~thyl methylhydrogen polysiloxane (viscosity 20-~0 cst at 25C) is applied with a slop pad roller to an endless carrier of glass cloth t7 g/m ~.
The side to be treated of the carrier advanclng at a speed of 20 m/min. is brought lnto contact with the web o~ poly-ester/cotton (50:50) popL1n (140 g/m2), which has pr~viously been sprayed with 0~2% o~ ZrOCl~ (catalyst) and whlch ad-vances at the same speed as the carrier, in such a manner -that carrier and web of material are together transported synchronously with the one superimposed the other.
Carrier and web of material are then fed into an apparatus as described in figure II. The lst,, 2nd. and 5~h. cylinder~s (cf. (19), (21) and (23) in figure II) are heating cylinders lS of 90 cm diameter and with a temperature of 190C. The 2nd.
and 4th, cylinder (cf. (20) and (22) in figure II) are suct-ion ~ylinders of the same diameter.
After the first passage, the web of material is fed a second time into the apparatus, so that there are always 2 layers of web in the apparatus (an inner one dir~ctly on the carrier, the outer one in connexion with the inner one but separated from the carrier).
After the entire web of material has run twice through the apparatus on each o~casion, web and carrier are separated from each other. A rleaning of the carrier is unnecessary 105~5~i7 since only pure substance is applied.
The finished polyester/cotton poplin has values of 80 to - 100 in the AATCC Spray Test 12-1966, whereas a comparison sample which was not finished has valwes from O to 20, This ~est for evaluating the water repellent properties of textiles specifies values in the range from O (minimum) to 100 (maximum).
Similar results are obtained with the compounds of the formulae (57), (58), (60) and (61), but without spraying the a~ric with a catalyst, e,g. zirconium oxychloride, before treating it.
Example 2 40 g of one of the yellow, blue or red dyes of the formulae (2) 3 (10) or (13) and 100 g of ethyl cellulose in 860 g of a methyl ethyl ketone/ethanol mixture (weight ratio 1:1) are ground for 5 hours at 20C in a sand mill and dispersed to form a homogeneous printing ink, Paper carriers are then printed with one of these inks so as to give a dye application of 0.5 to 4 g/m2 aft~r the sol-vent has been evaporated at 20C. One of these printed paper carriers together with a polyester fabric (120 g/m2) is fed in a single layer into an apparatus similar to that illust-rated in figure II, The paper carrier is adapted to the length of the web of material to be dyed, The apparatus 1~565S7 comprises 2 units the irst of which, in the direction of ~ravel of the carrier, consists of 6 rollers and the second unit of 4 rollers, The 1st, 3rd. and 5th, roller of the firs~ unit and the 1st and 3rd. roller of the S second unit are heating cylinders of 50 cm diameter which axe heated to 215C, The 2nd,, 4th. and 6th~ rollers of the first unit and the 2nd, and 4th. roller o the second unit are suction cylinders wrapped in felt of S0 cm diameter on which the paper carrier is heated from the reverse side to 220C with an infrared heater during the suc-tion cycle, Carrier and web of material pars once at ~he same speed through the apparatus at a speed of 60 m/min. and are subsequently separated.
A polyester fabric which is dyed a deep, level yellow (or blue or red) is obtained in this way, - Example 3 The compounds of the formula (56) are slop padded as 50%
solution in ethanol to give an application of 5 g/m2 on an endless carrier consisting of a polytetrafluoroethylene web.
This carrier is a component of an apparatus similar to that of figure II, except that it consists of only 4 rollers of which the 1st, and 3rd., in the direction of travel of the carrier, are heating cylinders with a diameter of 50 cm and are heated to 140C, whereas the Znd, and 4th.
~ 5 ~ 5 5~
roller are suction cylinders of 50 cm diameter which cannot be heated.
A polyacrylonitrile fabric (130 g/m2) is then fed into the apparatus. After the fabric has passed once through the 4 rollers it is fed 4 more times into the apparatus and on each occasion the freshly introduced web is removed ~rom the carrier, i.e. i~ passes into the appara~us as 2nd. and 3rd., ~th and 5th. layer. The fabric is subsequently separa-ted from the carrier so that 5 layers of fabric having a total length of about 12 metres are always in the apparatus. ~he 5 layers of abric move synchronously with the carrier at - a speed of 90 m/min. Carrier and fabric are subsequently separated.
The electrostatic proper-ties are tested by measuring the surface resistance in ~ /lOOcm2 and the half life period indicates the time which passes until the voltage of a fabric electrostatically charged with 100 volts falls to 50 volts~
The surface resistance of the polyacrylonitrile fabric is 1016JQ/lOOcm2 before the treatment and lOllQ llO0 cm2 after the treatment, which corresponds to a 10000-fold reduction of the surface resistance.
Before treatment the fabric has a half life period of 300 seconds, whereas after treatment this falls to only 5 seconds.
Similar results are obtained with the compounds of the 1~56~;57 formulae (51), (53) and (55).
Example 4 The compound of the formula (54) is slop padded as oily, viscous liquid on an endless, airtight po1yester carrier so as to give an application o~ l.2 g/m . Slnce the carrier is airtight, it is necessary for the application means (17) and (18) of ~igure ~I to be so posl~loned that th~ activated side o~ the endless carrier can be brought into contact with the web of material to be treated. In divergence from figure II, the apparatus consis~s of 2 units each comprising 6 rollers of 50 cm diameter. The lst., 2nd,l 4th. and 5th.
rollers of each unit, in the direction of travel of the carrier, are in the form of heating cylinders which are heated to 180C and the 3rd. and 6th. rollers of each unit are sustion cylinders which are each heated with infrared heaters to 200G.
A polyester fabric (150 g/m2) is then fed into the apparatus.
The fabric ru-ns once through the apparatus synchronously with the carrier at a speed of 60 m/minO and is subsequently separated from the carrier. The treated polyester fabric is tested for its electrostatic properties as indicated in Example 3. As reported in Example 3, the treatment reduces the surface resistance by lO,000-fold. Before the treatment the polyester fabric has a half life period of 290 seconds ~0565S7 and after the ~eatment this falls ~o only 1 second.
Similar results are obtained with the compounds of the formulae (49) and (50).
A polyamide fabric (100 g/m ) is fed into an apparatus similar -~o that illustrated by figure II, except that it consists of
3 units. Each of the first two units through which the fabric passes compris~s 6 rollers of 50 cm diameter. The ~irst 5 rollers, in the direction of travel, are in the -form of heating cylinders which are heated to 190C. The 6th and last rollers of each of the two units are suction cylinders which cannot be heated. The third unit through which the fabric passes after the first two consists of 4 rollers of 50 cm diameter, the first three of which, in the direction of trave~, are heating cylinders which are heated to 195C
and the last is a suction cylinder which cannot be heated.
An endless polyester sheet which is impermeable to air is used as carrier in the first two units and an air-permeable polytetrafluoroethylene web is used as carrier in the third unit.
Dibu~yl tin dilaurate (catalyst) is slop padded as 10% solu-tion in ethanol onto the carrier of the first two units to give an application of 1 g/m . Since the carrier is imper-meable to air, it is necessary for the applications means
and the last is a suction cylinder which cannot be heated.
An endless polyester sheet which is impermeable to air is used as carrier in the first two units and an air-permeable polytetrafluoroethylene web is used as carrier in the third unit.
Dibu~yl tin dilaurate (catalyst) is slop padded as 10% solu-tion in ethanol onto the carrier of the first two units to give an application of 1 g/m . Since the carrier is imper-meable to air, it is necessary for the applications means
- 4~ -~056557 to be positioned as in Example 4.
A dimethyl methylhydrogen polysiloxane with a molecular weight of 1350 to 1400 and a hydrogen silane content ~mea-sured by spli~ting of of hydrogen directly bonded to silicon) of 314 ml/g is slop padded onto the carrier of the third unit so as to give an application of 10 g/m ~
The polyamide fabric is then fed into the apparatus ln such a manner that it passes only once through the first two units but 4 times through the third unit. The fabric which is freshly run into the third unit has no direct contact with the carrier and passes into the third unit consequently as 2 nd., 3rd. and 4th. layer, so that theLe is always one layer of fabric in the first two units and 4 layers of fabric in the third unit, these layers having a total contac~ leng~h of about 23 metres. The carrier and single layer of fabric in the first two units and the carrier and the 4 layers of fabric in the third unit all advance synchronously at a speed of 25 m/min. After it has passed through the third unit, the fabric is separated from the carrier.
The polyamide fabric is tested for its water repellent pro-perties in the following spray test:
Woven samples of fabric, 2~ cm in length, are wetted with 500 ml of water. Any drops adhering to the fabric are removed and the moist sample~ weighed. The weight increase as index of the water repellent effect is reported in % of the dry ~ C~56~57 fabric. The weight increase o~ an untreated polyamide com-parison sample is 80 to 90%, but of a treated polyamide fabric it is only 10%.
Example 6 S One of the compounds (75) or (77) i9 slop padded as oily, viscous liquid onto an endless carrier consisting o a polytetrafluoroethylene web and forming part of the apparatus described in ~xamp].e 3, so as to give an application of 25 g/m .
A polyester fabric (150 g/m2) is then fed in S layers into the apparatus as described in Example 3~ The speed at which the carrier and fabric advance synchronousiy is 80 m/min.
on using compound of the formula ~75) and 60 m/min. on using the compound of the formula (77~.
After the fabric has been separated from the carrier, the former is tested for its flame resistance, in comparison with untreated fabric, by the DOC 3-71 test. The test is also repeated after several household washes at 40C in a liquor containing 4 g/l of a commercial light duty detergent, The results are summarised in Table I.
56~;i57 Table I
Polyester after before af~er after after after fabric treat- treat- 1 2 10 20 me~ Lt men _ wash wash was hes washes TL CT TL CT TL¦CT TL CT TL CT TL CT
__ ~ . _ __ _ treated with the compound 6 10 4 2 ~5 6 6 13 5 1 ¦ mula (75) _ __ _ . _ _ _ treated with the compound 7 2 ~5 1 6 4 6 4 4 1 mula (77) _ _ untreated ¦ 12 22 _ 4 9 10 25 419 *) 28 -~) burns TL - tear length in cm CT = combustion time in seconds Similar results are obtained with the compounds of the formulae (62) to (74) and (76)~
The above flameproofing test, DOC FF 3-71 ("Children's Sleepwear Testl'), is ~arried out as follows:
A dimethyl methylhydrogen polysiloxane with a molecular weight of 1350 to 1400 and a hydrogen silane content ~mea-sured by spli~ting of of hydrogen directly bonded to silicon) of 314 ml/g is slop padded onto the carrier of the third unit so as to give an application of 10 g/m ~
The polyamide fabric is then fed into the apparatus ln such a manner that it passes only once through the first two units but 4 times through the third unit. The fabric which is freshly run into the third unit has no direct contact with the carrier and passes into the third unit consequently as 2 nd., 3rd. and 4th. layer, so that theLe is always one layer of fabric in the first two units and 4 layers of fabric in the third unit, these layers having a total contac~ leng~h of about 23 metres. The carrier and single layer of fabric in the first two units and the carrier and the 4 layers of fabric in the third unit all advance synchronously at a speed of 25 m/min. After it has passed through the third unit, the fabric is separated from the carrier.
The polyamide fabric is tested for its water repellent pro-perties in the following spray test:
Woven samples of fabric, 2~ cm in length, are wetted with 500 ml of water. Any drops adhering to the fabric are removed and the moist sample~ weighed. The weight increase as index of the water repellent effect is reported in % of the dry ~ C~56~57 fabric. The weight increase o~ an untreated polyamide com-parison sample is 80 to 90%, but of a treated polyamide fabric it is only 10%.
Example 6 S One of the compounds (75) or (77) i9 slop padded as oily, viscous liquid onto an endless carrier consisting o a polytetrafluoroethylene web and forming part of the apparatus described in ~xamp].e 3, so as to give an application of 25 g/m .
A polyester fabric (150 g/m2) is then fed in S layers into the apparatus as described in Example 3~ The speed at which the carrier and fabric advance synchronousiy is 80 m/min.
on using compound of the formula ~75) and 60 m/min. on using the compound of the formula (77~.
After the fabric has been separated from the carrier, the former is tested for its flame resistance, in comparison with untreated fabric, by the DOC 3-71 test. The test is also repeated after several household washes at 40C in a liquor containing 4 g/l of a commercial light duty detergent, The results are summarised in Table I.
56~;i57 Table I
Polyester after before af~er after after after fabric treat- treat- 1 2 10 20 me~ Lt men _ wash wash was hes washes TL CT TL CT TL¦CT TL CT TL CT TL CT
__ ~ . _ __ _ treated with the compound 6 10 4 2 ~5 6 6 13 5 1 ¦ mula (75) _ __ _ . _ _ _ treated with the compound 7 2 ~5 1 6 4 6 4 4 1 mula (77) _ _ untreated ¦ 12 22 _ 4 9 10 25 419 *) 28 -~) burns TL - tear length in cm CT = combustion time in seconds Similar results are obtained with the compounds of the formulae (62) to (74) and (76)~
The above flameproofing test, DOC FF 3-71 ("Children's Sleepwear Testl'), is ~arried out as follows:
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 piece~q of fabric are then conditioned in a sealed container over ~0565~7 silica gel for 30 minutes and subsequen-tly subjected to the actual flameproofing test in a combustion chamber. The pieces of fabric are each ignited wi~h a methane gas flame for 3 seconds in the vertical position.
The test is considered as having been passed i:E the acerage charred zone is not more than 17.5 cm in length and no single sample exhibi-ts a carred æone of over 25,4 cm in length and ~he lndividual smouldering times are not longer than 10 seconds, Example 7 The procedure as described in Example 6 is carried out except that the compounds of the formulae (83) or (84) are applied with a doctor blade to the carrier so as to give an applica-tion of 36 g/m2.
A polyam`ide fabric (130 g/m2) is fed into the apparatus in S
layers as described in Example 3J The speed at which carrier and fabric advance synchronously is 60 m/minO
After the fabric has been separated from the carrier, the former is tested for its flame resistance, in comparison with untreated fabric, by the DOC 3-71 test (cf. Example 6).
The results are summarised in Table II
- 4~ -105~;55'7 Table II
polyamide fabric combustion tear length time in sec. in cm _ treated with the compound of the 4 5,5 formula (83) _ treated with the compound of the 4,5 5 formula (84) _ _ _ untreated 30 burns away . . completely _ Similar results are obtained with the compounds of the formulae (78) to )82) and (85).
The test is considered as having been passed i:E the acerage charred zone is not more than 17.5 cm in length and no single sample exhibi-ts a carred æone of over 25,4 cm in length and ~he lndividual smouldering times are not longer than 10 seconds, Example 7 The procedure as described in Example 6 is carried out except that the compounds of the formulae (83) or (84) are applied with a doctor blade to the carrier so as to give an applica-tion of 36 g/m2.
A polyam`ide fabric (130 g/m2) is fed into the apparatus in S
layers as described in Example 3J The speed at which carrier and fabric advance synchronously is 60 m/minO
After the fabric has been separated from the carrier, the former is tested for its flame resistance, in comparison with untreated fabric, by the DOC 3-71 test (cf. Example 6).
The results are summarised in Table II
- 4~ -105~;55'7 Table II
polyamide fabric combustion tear length time in sec. in cm _ treated with the compound of the 4 5,5 formula (83) _ treated with the compound of the 4,5 5 formula (84) _ _ _ untreated 30 burns away . . completely _ Similar results are obtained with the compounds of the formulae (78) to )82) and (85).
Claims (16)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the continuous, dry transfer of organic compounds to webs of air-permeable organic materials, which comprises (1) applying to a carrier preparations which contain at least one compound that is converted into the vapour state at atmospheric pressure and at a temperature above 80° C, (2) bringing said carrier into contact with the side of the air-permeable web of organic material to be treated in such a manner that web and carrier advance together synchronously, the one superimposed on the other, (3) subjecting carrier and web alternately to at least one heat treatment of at least 80° C applied from the carrier side and one suction effect applied from the web side, which latter may be combined with a second heat treatment of at least 80° C
applied from the carrier side, and continuing or repeating this treatment until the compound has been transferred to the web, which is fed in one or more layers, so that the same section of the web passes through the same heating/suction cycle one or more times, and (4) separating the treated web from the carrier.
applied from the carrier side, and continuing or repeating this treatment until the compound has been transferred to the web, which is fed in one or more layers, so that the same section of the web passes through the same heating/suction cycle one or more times, and (4) separating the treated web from the carrier.
2. A process according to claim 1, which comprises the use of an air-permeable endless carrier.
3. A process according to claim 1, which comprises the use of a carrier consisting of a glass cloth, a steel fibre fleece, a perforated or a porous metal strip, a per-forated or a porous plastic sheet, or a fibre web.
4. A process according to claim 1, which comprises the use of organic compounds with transfer at temperatures of 100° C
to 220° C.
to 220° C.
5. A process according to claim 1, which comprises the use of textile finishing agents as organic compounds to be transferred.
6. A process according to claim 1, which comprises the use of a web of organic textile material as air-permeable web.
7. A process according to claim 6, wherein the textile material contains polyester, polyamide, polyacrylonitrile and/or cellulose.
8. A process according to claim 1, wherein the running speed of the web of material is 20 to 100 m/min.
9. A process according to claim 1, wherein the web is passed in one to ten layers.
10. A process according to claim 1, wherein the web of material is alternately subjected to 2 to 20 heat and suction treatments.
11. A process according to claim 1, in which the preparations applied to the carrier contain a binder which is stable below 250° C and/or a solvent in addition to the organic compound to be transferred.
12. A process according to claim 11, in which the pre-parations applied to the carrier are dried.
13. A process according to claim 1, in which the carrier and web are subjected to a heat treatment and a suction effect under mechanical pressure.
14. An apparatus for carrying out the process according to claim 1, which comprises (a) a web-shaped carrier which advances in the longitudial direction, (b) a means for applying organic compounds to the carrier, and, following said means in the direction of travel, (c) a sequence of at least one heating unit and one suction unit and (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 , said apparatus being so constructed that carrier and web advance together synchronously, the one superimposed on the other, and are together transported to the heating and suction units, and, after the organic compound has been transferred from the carrier to the web at a temperature above 80° C, web and carrier are separated from each other, it being possible to feed the web into said apparatus in one or more layers simultaneously.
15. An apparatus according to claim 14, wherein the web-shaped carrier consists of an air-permeable endless carrier.
16. An apparatus according to claim 14, which comprises additional heating units which are combined with the suction units.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH1206273A CH567621B5 (en) | 1973-08-22 | 1973-08-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1056557A true CA1056557A (en) | 1979-06-19 |
Family
ID=4379501
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA207,421A Expired CA1056557A (en) | 1973-08-22 | 1974-08-20 | Process for the dry transfer of organic compounds to webs of material |
Country Status (9)
| Country | Link |
|---|---|
| JP (1) | JPS5048286A (en) |
| BE (1) | BE819049A (en) |
| CA (1) | CA1056557A (en) |
| CH (2) | CH567621B5 (en) |
| DE (1) | DE2438723A1 (en) |
| ES (1) | ES429413A1 (en) |
| FR (1) | FR2245793B1 (en) |
| GB (1) | GB1465388A (en) |
| ZA (1) | ZA745375B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107128064A (en) * | 2017-05-12 | 2017-09-05 | 贵州鸿图彩印包装有限责任公司 | Wine box production gilding press |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4007003A (en) * | 1975-09-12 | 1977-02-08 | Armstrong Cork Company | Product and method of printing carpet with a transfer paper- II |
| DE2628676C2 (en) * | 1976-06-25 | 1982-02-04 | Kleinewefers Gmbh, 4150 Krefeld | "Device and process for continuous transfer printing of textile webs" |
| DE2638128B2 (en) * | 1976-08-25 | 1980-01-03 | Kleinewefers Gmbh, 4150 Krefeld | Device for the continuous dyeing of a textile web by sublimating the dye of a dye carrier |
| EP0455849B1 (en) * | 1990-05-08 | 1992-12-09 | POLYTREND GESELLSCHAFT FÜR POLYMERE WERKSTOFFE & OBERFLÄCHENTECHNIK MBH | Method and apparatus for transfer of a colour design to a plastic substrate or a decorated plastic substrate |
| GB2251209A (en) * | 1990-12-01 | 1992-07-01 | Brainstorm Ltd | Transfer by heating of sublimation ink from a carrier |
| EP0544019A1 (en) * | 1991-07-18 | 1993-06-02 | Erich Netzsch GmbH & Co. Holding KG | Process and apparatus for applying and incorporating dyes into a plastic-bearing substrate |
| DE102022117792B4 (en) | 2021-07-30 | 2023-11-02 | Duksung Co., Ltd. | Continuous printing apparatus using a vacuum suction roll and method thereof |
| US11660854B2 (en) | 2021-07-30 | 2023-05-30 | Duksung Co., Ltd | Continuous sublimation transfer method using a vacuum suction roller |
-
1973
- 1973-08-22 CH CH1206273A patent/CH567621B5/xx not_active IP Right Cessation
- 1973-08-22 CH CH1206273D patent/CH1206273A4/xx unknown
-
1974
- 1974-08-12 DE DE2438723A patent/DE2438723A1/en active Pending
- 1974-08-20 CA CA207,421A patent/CA1056557A/en not_active Expired
- 1974-08-20 FR FR7428569A patent/FR2245793B1/fr not_active Expired
- 1974-08-20 GB GB3657574A patent/GB1465388A/en not_active Expired
- 1974-08-21 ES ES429413A patent/ES429413A1/en not_active Expired
- 1974-08-21 BE BE147786A patent/BE819049A/en unknown
- 1974-08-21 ZA ZA00745375A patent/ZA745375B/en unknown
- 1974-08-22 JP JP49095610A patent/JPS5048286A/ja active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107128064A (en) * | 2017-05-12 | 2017-09-05 | 贵州鸿图彩印包装有限责任公司 | Wine box production gilding press |
Also Published As
| Publication number | Publication date |
|---|---|
| CH567621B5 (en) | 1975-10-15 |
| FR2245793A1 (en) | 1975-04-25 |
| GB1465388A (en) | 1977-02-23 |
| DE2438723A1 (en) | 1975-03-06 |
| BE819049A (en) | 1975-02-21 |
| ES429413A1 (en) | 1976-09-01 |
| ZA745375B (en) | 1975-08-27 |
| CH1206273A4 (en) | 1975-03-14 |
| JPS5048286A (en) | 1975-04-30 |
| FR2245793B1 (en) | 1976-12-31 |
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