DE2438723A1 - PROCESS FOR DRY TRANSFER OF ORGANIC COMPOUNDS ON TRACKS - Google Patents

Description

CIBA-GEIGY AG, CH-4002 Basal

2438723 [subsequently submitted I Case 1-8938 / +. "ÜL / - ^ ^&

GERMANY

Process for the dry transfer of organic see compounds on goods platforms

The invention relates to a process for the continuous, dry transfer of organic compounds, in particular chemicals, to webs of air-permeable organic materials, characterized in that preparations are applied to a carrier (1) which contain at least one at atmospheric pressure above 80 ⁰ C in the vapor state merging compound, optionally one below

509810/0730.

Contain 25O ° C stable binding agent and / or a solvent, and optionally dries;

(2) the loaded carrier with the side to be treated of the air-permeable material web made of organic material in this way brings into contact that · the carrier and the material web move together, lying on top, synchronously;

(3) carrier and web, optionally with application of mechanical pressure at least alternately depending on a heat treatment of at least 80 ⁰ C of the support side and a suction effect by the web side, optionally combined with a second heat treatment of at least 8O ⁰ C from the support side, subject, and this treatment continues or repeated until the said compound is transferred to the material web to be treated, the material web being drawn in in one or more lanes, so that the same web section runs through the same heat-suction cycle one or more times; and

(4) separates the treated web from the carrier.

The one required for the method according to the invention The carrier is preferably endless, but it can also be adapted to the webs of organic material to be treated be, i.e. cut into pieces. As a rule, the carrier is inert, i.e. it has no affinity for the the preparation containing the compound to be transferred. The carrier can be an airtight or preferably

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act wisely to an air-permeable carrier.

It is expediently flexible, preferably spatially stable tape or a sheet or film that is heat-stable. Breathable straps with endless surfaces are e.g. perforated or porous.

A wide variety of materials can be used to manufacture these carriers, e.g. metal, plastic, Glass, paper or textile fibers. Suitable supports are, for example, those made of optionally perforated or porous Metal strips (steel, aluminum, copper), metal fiber fleeces, possibly perforated or porous plastic films, Glass fiber nonwovens or fabrics, airtight or perforated or porous paper, textile fiber nonwovens or fabrics, -knit or felting.

Perforated paper, aluminum or steel strips, steel fiber fleeces, Glass fiber fabric, optionally perforated plastic films, in particular those made of polyester or polytetrafluoroethylene and textile fiber nonwovens such as polyester or polyamide fiber nonwovens. ·

There are also carriers with plastic coatings in the form of "" '' perfected films "" in Consideration, e.g. coatings made of polyvinyl resins, ethyl cellulose, Polyurethanes or polytetrafluoroethylene.

The verfahrcnsgernäss verwendbarenvZubereitungen, in addition to the transferred onto the web of compounds, at least one below 25O ⁰ C stable .bin

5098 10/07 30

ZkW 2

demittel, water and / or an organic solutioni contain.

Synthetic, semi-synthetic and natural resins are suitable as binders, both polycondensation as well as polyaddition products. In principle, all can be used in the paint and printing ink industry Binders are used. The binders serve the compounds to be transferred to the treated area of the To hold the carrier. At the transfer temperature, however, they should not melt or react with themselves, E.g. networking and sharing the connection to be transmitted. Preferred: are those binders that, for example Dry quickly in a stream of warm air and form a fine, expediently non-sticky film on the carrier. Suitable binders that are soluble in water include: alginate, tragacanth, carubine (from locust bean gum), Dextrin, etherified or esterified plant mucilage, carboxymethyl cellulose or polyacrylamide and as in organic Solvent-soluble binders, cellulose esters, such as nitrocellulose or cellulose acetate, and in particular Cellulose ethers, such as methyl, ethyl, propyl, isopropyl, benzyl or hydroxyethyl cellulose, as well as their mixtures.

Organic solvents which are water-miscible or water-immiscible, or solvent mixtures with a boiling point at atmospheric pressure below 150 ^° C., preferably below 120 ^° C., can be considered as organic solvents. It is advantageous to use aliphatic, cycloaliphatic or aromatic carbon

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Hydrogens such as toluene, cyclohexane, petroleum ether; lower Alkanols, such as methanol, ethanol, propanol, isopropanol, Esters of aliphatic monocarboxylic acids, such as ethyl or propyl acetate; aliphatic ketones such as methyl ethyl ketone and halogenated aliphatic hydrocarbons, such as perchlorethylene, trichlorethylene, 1,1,1-trichloroethane or * 1,1,2-trichloro ^, 2,1-trifluoroethylene., Particularly preferred Solvents are lower aliphatic esters, ketones or alcohols such as butyl acetate, acetone, methyl ethyl ketone, ethanol, isopropanol or butanol, as well as their mixtures, e.g. a mixture of methyl ethyl ketone and ethanol in the ratio of 1: 1. The desired viscosity of the printing pastes can then be achieved by adding the named binders with a suitable Solvent adjusted.

The weight ratio among the individual components of the preparation used for the pretreatment can can be very different and lies e.g. for the on the fiber material compounds to be transferred within 0.1 to 100 percent by weight, for the binder within 0 to 30 percent by weight, for the solvent or solvent mixture within 0 to 99.9 percent by weight, based on the total weight of the preparation. On the auxiliary

Carriers can contain 1 to 100 g, preferably 15 to -40 g, per m Carrier of the connection to be transferred to the fiber material v / ground.

The preparations which can be used according to the invention are produced, for example, by treating the at atmospheric

Solves pressure above 80 ⁰ C to the fibrous material passing over the compound in water and / or organic solvent or feindispcrgiert, one below 25O ° C advantageously stable in the presence of binder. These preparations are expediently applied continuously to the inert, moving carrier, for example by spraying in places or over the whole area, coating or preferably by printing. A wide variety of printing processes can be used, such as letterpress printing (e.g. letterpress, flexographic printing), gravure printing (e.g. blindfold printing), screen printing (e.g. rotary printing, film printing) or electrostatic printing methods, especially when using paper substrates or those made of stainless steel sheet. It is also possible to apply organic compounds, in particular chemicals, in pure form, ie as such directly by sprinkling on, spraying on, pouring on, flapping on or knife-coating.

A special embodiment of the present The process consists in applying the organic compound in a pattern to a web of material, e.g. printing it on it or, instead of a closed web, apply cut-out patterns of the auxiliary carrier to the fiber material to be treated. These patterns are obtained by punching or cutting suitable cutouts in the above-mentioned auxiliary carriers.

509810/0730.

After the preparations have been applied to the carrier, they are dried, e.g. with the help of a warm .Air flow or by infrared radiation, if necessary with recovery of the solvents used. ' If the organic compounds to be transferred, in particular If chemicals are pure, i.e. applied directly as such, such drying is not necessary.

Then, the treated side of the support and, if the latter is permeable to air, brought the untreated or treated side of the support depending on sublimation to be transmitted compounds of the web surface to be treated in intimate contact and together to a heat treatment of at least 80 ⁰ C and preferably 100 to 220 ° C, in particular 150 to 200 ⁰ C, subjected. Particularly good results are obtained with temperatures of 180 to 22O ⁰ C. .

According to the invention, this heat treatment is combined with a vacuum treatment, in which the same Direction and synchronously moving "carrier-web sandwich" is alternately heated and sucked off, which are also heated at the same time during the suction can. The vacuum is set so that as little as possible of the substance to be transferred is carried away by the air flow. This heat-suction cycle is repeated as long as until the chemicals are transferred from the carrier to the "web".

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An expedient application for carrying out the method according to the invention consists of at least each a heating and suction drum, preferably from a series of 2 to 20, in particular 4 to 16 heating and Suction drums, whereby the web to be treated can be drawn in with one or more webs. With single-lane entry the web of material is thus subjected to 2 to 20, in particular 4 to 16, heat or suction effects. The series of Heating and suction drums can expediently, if the total number of heating and suction drums exceeds 6, in units of e.g. 6 drums each can be grouped. As a rule, the diameter of the heating and suction drums is 50 cm to 1 m. As a rule, 1 heating drum alternates with 1 Suction drum. Depending on the sublimation behavior of those to be transferred Connections, the number of suction drums can also be reduced in relation to the number of heating drums, e.g. by switching 1, possibly 2 suction drums after every second, third or sixth heating drum. Also an arrangement in which only 1 to 2 suction drums are switched on after a series of 2 to 18 or 19 heating drums have proven to be suitable. The material web to be treated can be single or multi-lane depending on the unit, e.g. single-lane in a first unit and single-lane in a second unit can be drawn in in multiple lanes.

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The cylindrical heating drums can be heated electrically or with heated liquids such as oil or with gas, so that the jacket temperature of the cylinder is expediently about 170 to 220 ° C. The vacuum effect of the suction drum can still e.g. be supported by a radiant heater on the opposite side. As a rule, such suction drums are with a Wrapped in felt.

The material feed depends very much on the desired form of application of the chemicals. The order! On the carrier can be done on each side individually or on both sides, with the air-impermeable carrier only the one-sided Order is appropriate. The application of chemicals can be carried out on the desired side by means of a suitable carrier web guide or on both sides. If you want the chemicals to be deposited as superficially as possible, only a lane is drawn in or, in the case of a low-lane draw-in, the incoming goods are first brought into contact with the carrier. The penetration of the entire material is better when the new incoming web is removed from the carrier, i.e. entered the machine as a 4th or 5th layer, for example. The penetration of the goods with chemicals then takes place after the countercurrent principle. -

This multiple passage of the goods through the heat ■ suction cycle enables high treatment temperatures to compensate for longer exposure times.

The method according to the invention is preferably used

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carried out with 1 to 10, in particular 1 to 5 layers. In case of series of heating and suction drums in several units are grouped, the number of these layers in the different units can be varied.

The heat treatment, which may be combined with suction, can be carried out in various ways, e.g. by means of a heating plate, a stream of hot air, a heated counter roller or, in particular, by means of infrared radiation.

Another advantage of the method according to the invention consists in that, due to the large material intake, the machine is driven at very high speeds can. E.g. it is possible with throughput speeds to work from up to 100 m / min, e.g. 20 to 90 m / min, or especially 20 to 50 in / min. For example, amounts to with a transfer time of about 30 seconds and 5 layers of material the speed 90 m / min. In contrast, with known transfer processes, throughput speeds of only 2 to 3 m / min.

Through targeted selection of the carrier structure (e.g. Fabric, fleece, grained paper) as well as the material guidance, i.e. lighter or stronger or no contact pressure at all Trager web, can be on the material to be treated desired calender effects can be generated.

As an air-permeable organic material, wel-

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ches to be treated according to the invention comes first Line organic, but especially textile fiber material · into consideration.

The fiber material can be in various processing stages exist, e.g. in the form of yarn, especially in piece form such as woven, knitted or nonwovens.

The fiber materials can be conventional before or after the treatment by the process according to the invention colored, printed or finished.

The fiber material itself can be made from natural, semi-synthetic, or, above all, consist of fully synthetic fibers. Natural fibers are in particular those made of wool or cellulose to mention like cotton, linen, hemp or ramie. Examples of semi-synthetic fibers are those made of viscose. Textile materials containing fully synthetic fibers are preferably used.

As a fully synthetic fiber material that can be treated according to the invention, cellulose ester fibers, such as Cellulose-2 ^ and -triacet fibers, synthetic polyamide fibers, "e.g. those made from poly-i-caprolactam (nylon 6), polyhexamethylene diamine adipate (Nylon 6,6), poly-iJ-aminoundecanoic acid (nylon 7), Polyurethane or polyolefin e.g. polypropylene fibers, acidic modified polyamides, such as polycondensation products 4,4'-diamino-2,2'-diphenyldisulfonic acid or 4,4'-diamino--

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-2,2'-diphenylalkanedisulfonic acids with polyamide-forming starting materials, Polycondensation products from monoaminocarboxylic acids or their amide-forming derivatives or dibasic ones Carboxylic acids and diamines with aromatic dicarboxysulfonic acids, e.g. polycondensation products from 6-caprolactam or Hexamethylenediamraonium adipate with potassium 3,5-dicarboxybenzenesulfonate, or acid modified polyester fibers such as 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 sulfopropoxy) propane, 2,3 ~ dimethylol-1 ~ (3 ~ sodium sulfopropoxy) -butane, 2,2-bis- (3-sodium sulfopropoxyphenyl) -propane or 3,5-dicarboxyberizole sulfonic acid or sulfonated terephthalic acid, sulfonated 4-methoxybenzenecarboxylic acid or sulfonated Dipheny 1-4,4'-dicarboxylic acid should be mentioned.

However, it is preferably a fiber material made of polyacrylonitrile or acrylonitrile copolymers, or fully synthetic Polyamide fibers, preferably made of polyhexamethylene diamine adipate, and before

all about linear polyester fibers, especially made of polyethylene glycol terephthalate or poly (1,4-cyclohexanedimethylol) terephthalate. In the case of acrylonitrile copolymers, the acrylonitrile proportion is expediently at least 50% and preferably at least 85% by weight of the interpolymer. Usually used as comonomers other vinyl compounds, e.g. vinylidene chloride, vinylidenecyanide, vinyl chloride, methacrylate, methy! vinylpyridine, N-Vlny! Pyrrolidone, vinyl acetate, vinyl alcohol,

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Acrylamide or styrene sulfonic acids.

These fiber materials can also be used as mixed fabrics with each other or with other fibers, e.g. mixtures of polyacrylonitrile / polyester, polyamide / polyester, polyester / viscose, Polyester / wool, polyester / cellulose and especially polyester / cotton be used.

■ The preparations that can be used according to the invention are applied to the auxiliary carrier, for example by "full-area or partial spraying, coating, loading sprinkle or print.

In the case of powdery products, the application takes place e.g. from a spreading channel and pasty ^ products by means of a squeegee or an inclined plane. If the product is in diluted form, it can be e.g. be applied with a roller or with a spray device.

The powder or paste application has the advantage of that no binder needs to be used as well, which "can often lead to encrustations in the apparatus. Also unnecessary This is how the purification of the carrier, insofar as it is endless. A special dissolving in a solvent and that with it related specific problems (solvent vapors) also fall there.

The invention also relates to the device for carrying out the specified dry transfer method. This device is characterized in that it consists of

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(a) a web-shaped carrier, which is located in the Can move lengthways,

(b) a device for applying organic compounds to the carrier, then in the direction of travel,

(c) a sequence of at least one heating and suction unit each and, if necessary, additional heat aggregates, which are combined with the satellite aggregates are and

(d) one device each, which feeds the web of organic material to the loaded carrier and guides the treated web away from the carrier,

is constructed, namely in such a way that the carrier and web of material are supported together and move synchronously and together the heating and suction units are fed and after the transfer of the organic compound from Carrier on the web at above 80 ° C web and carrier are separated from each other and the device it enables the web to be drawn in in one or more layers at the same time.

In FIG. I, at (1) the web to be treated and at (2) the treated web, at (3) the web to be loaded Carrier; in (4) the device for applying organic compounds and in (5) the carrier is after Transfer of the organic compounds. At (6) the web is fed to the loaded carrier and at

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■ ■ ■ - 15. -

(7) the treated web is led away from the carrier.

(8) is the heating unit, which is designed as a heatable drum. (9) is the suction unit, which acts as a suction drum is trained. The suction source of the suction unit is indicated in (10). (11) is the additional heating unit, E.g. infrared heater, which is combined with the suction unit if necessary.

A preferred form of the process according to the invention can be carried out on the apparatus outlined in FIG. II be performed.

The textile material to be treated is located on the roll (12), which is applied after the chemical transfer Roll (13) is wound up. The endless belt (14), which is guided or driven by rollers (15) and (16), provides an air-permeable carrier e.g. a metal fiber fleece, a polyamide fleece or a glass fiber fabric. At (17) the chemicals are applied by means of a scattering channel or Roller. (18) is a squeegee. Rollers (19), (21) and (23) are oil-heated and have a jacket temperature of 190 to 210 ° C. The rollers (20 and 22) are each a suction drum wrapped in felt, while (24) and (25) are theirs Sources of suction indicated. (26) and (27) are infrared emitters. (17) and (18), i.e. the application devices, can also be on the other side of the wearer, but what

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de deflection devices for the carrier necessary, so that the order is still carried out from above. With (28) the device is indicated, that feeds the web of material to the loaded carrier and with (29) the device is indicated that the treated web of material leads away from the carrier again.

Than at atmospheric pressure above 80 ⁰ C, in particular at 100 to 22O ° C, in the vapor state over solid organic compounds especially sublimable dispersion dyes and in particular chemicals may be mentioned.

Chemicals include, for example, optical brighteners and, above all, textile treatment agents. These include so-called pretreatment, textile finishing and textile protective agents.

The sublimable ones that can be used according to the invention

Disperse dyes can come from a wide variety of dye classes belong. In particular, there are monoazo, quinophthalone, methine and antraquinone dyes, as well as Nitro, styryl, azostyryl, naphthoprinone, or naphthoquinone imine dyes.

The commercial products of these dyes generally contain dispersants, i.e. a product with surface-active substances Properties that enable or facilitate the dispersion of these dyes in water. The content of Dispersing agent is used when using anhydrous preparations not mandatory.

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Examples of sublimable substances which can be used according to the invention Disperse dyes are;

NO,

, - N = N

N - CH ₉ CH ₉ -OH

OH

s ^ ₁

C Il J

H ^ CO ^^^

N = N

CLL

N = Ν

CH.

OH

Cl-CH ₂ -H ₉ C _x

COOCH ₁

_N _ // \> - CH = C

CN

N-C-C

U It

C N

HO 'V - CH,

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O KH,

O NH- / V>

243S723

0 NIL

OCH.

0 NHCH ₃

I I

0 NHCH,

0 NH

(η - 3 or 4)

0 N

HO O NH-CH

HoN

on 509810/0730

(14)

(η = 1 or 2)

O NIL

N-S

H ₃ CH ₄ C ₂ -CO-NH

OH

H ₂ N 0 .NH ₂

HO O OH

(19)

O NIL

CO-NH,

NH-ClL

509810/0730

(20)

-OH.

KO,

(21)

PClL

Ό KH,

(22)

(23)

N
CH

CH = C

Cl N = N-C-C-CIL

It II

.C N

H ₉ N ^ "N"
^ H

(24)

(25)

CH,

(26)

OH Il

09 ^ 10/07

H ₅ C ₂

The disperse dyes of the formulas (2), (10) and (13) are preferred.

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.The subl5.newable optical brighteners can be any Belong to brightener classes. In particular, it is coumarins, benzocoumarins, pyrazines, pyrazolines, oxazines, Oxazolyl, thiazolyl, dibenzoxazolyl or dibenzimidazolyl compounds, as well as naphthalic acid imides. Examples of according to the invention usable sublimable optical brighteners are:. · ■.

(28)

- ClI = CH -

/ CH,

(29)

'Ν;

^ C - CH - CH -

C ν

(30)

HC - CH

Il It Λ

-C C-C

CH ₃

C - CH ₀
ι £

ι J

C - CHo

ι

CHo

. (31)

HC - CH

, N

c-c

COOCH.

(32)

(33)

_CH =

HC - CH HC - CH

■ Μ

C-C

COOClL

CH-

J

-C - CIL

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(34) H ₃ COOC

-COOClL

(35)

-N

- COOCH.

(36)

(37)

N N

11 I.

C C

(38)

(39)

(40)

Cl

CH = CH --C

N- • Ν / ^ O ^ O

Υ "3 O = C C =

5098 10/07

(41) HoC -C =

N-

(42)

HC - CH

(A3) CH

CH ₃ -

HC - CH

ti It

-C C-

^ 3 (CH ₃ )

According to the invention, however, chemicals are preferred transfer.

As preferably up to 22O ° C, were on the organic material passing over chemicals especially textile finishing agents mentioned at atmospheric pressure above 80 ⁰ C, at 100; Textile protection agents, particularly biologically active protection substances, which give the textile material, for example, bacteriostatic and / or fungistatic and / or fungicidal properties and actual textile finishing agents, which give the textile material the desired effects, e.g. antistatic, oil and water-repellent, grip-improving or flame-retardant effects. The mentioned textile protection and / or finishing agents can .geviUnschtenfalls

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together with disperse dyes and / or optical brighteners, which at atmospheric pressure e.g. between 150 - 220 ° C change into the vapor state on the to be refined Material are applied.

The chemicals that can be used according to the invention are known in some cases or can be produced by processes known per se. They belong to the most diverse Classes at.

An example of a bacteriostatic protective substance is the compound of the formula

(45)

Cl HO

and as an example of a fungistatic protectant, the compound of the formula

(46)

CH ₀ CH ₀ OH

Cl

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and the formula

(47) ^c ll ^H 23 ^{C 0} °

Cl Cl

Cl

Cl Cl

called.

As an example of the compounds imparting grip-improving properties to the textile fabric Compound of formula

(48)

• CH ₉ CH ₉ OH

Examples of compounds imparting antistatic properties to the textile fabric are the compounds of the formulas

(49) (50)

Il

(51) (52)

V * ti

H ₂₃ C ₁₁ -CO- (CH ₂ CH ₂ O) ₇ H

509810/07 30

CH ₃ COO

₁₇ H ₃₅ CONH (CH ₂ ) ₃ N

^CH

SO ₄ CH ₃

(55)

t-jHoc L / ob

HN '

CH ₃ COO

I CH ₉ CH ₉ -OH

-N

'CH ₂ CH ₂ -OH

CH ₃ COO

The compounds of the formulas (54) and (56) are preferred

As examples of the textile material, water-repellent Compounds imparting properties are said to be the compounds of the formulas

(57)

(58)

C ₁₇ Ho ₁ -NCO

JL / *? J

C ₈ F ₁₇ CH ₂ CH-OC-CH = CH ₂

'"3

(59)

C ₀ FnCH ₀ -CH-OH oil / Z j

CH _n

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ο ο

M Il

(6 "O) C ₈ F ₁₇ CH ₂ CH ₂ OC

H ₃ COH ₂ C _{/ Νχ} .CH ₂ (61) NC CN

HoCOH ₉ CNN CH ₉ OCHo

CH ₂ OCH ₃

or hydrogen methyl polysiloxanes or dimethyl hydrogen methyl polysiloxanes called.

These are the dimethyl-hydrogen-ethyl-polysiloxanes preferred.

The following compounds can be used as flame retardants:
A) Methylenedioxybenzene compounds of the formulas

⁽⁶²⁾ - -

^C1 Wx

O OC ₂ II ₅

509810/073 0

(63)

^ -ο

• CH ₀

^Z "" 0

Br I

-ρ '

Il

■ \,

CH ₂ -P,

OC ₂ H

2

(64)

(65)

• 0-

. CH ₂ -CH-CH ₂ Br OC ₂ H ₅ Ο- " OC ₂ H ₅ ^ 2 "Jx
0 _? Br CH ₀ -CH-CPL
ν. / Z. ι < / Ϊ ^ir CH ₂ -Cl U

Phosphorus compounds of the formulas

(66)

Il 0

(67)

s OG ₂ Il ₅ ^ ^OC 2 ^H 5

COOCH,

509810/073

COOCIU

OCH ₃

OCH

0-C ₂ H ₅

OC ₂ H ₅

^0C 2 ^H 5

CH ₃ O-

, OC ₂ H ₅ OC ₂ H ₅

Cl-

/ Λ

* ■ Il

II
2 ^H 5

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C) Phosphorus compounds of the formulas

^r Br Br 0

Il Il

(74) VCH ₂ -CH-CH ₂ -O-) 2 P

Br Br 0. 0 CH ₃

(75) I.

Br 0

(76) VCH ₂ -CH-CH ₂ -O-) ₂ P-OH

/ Br Br 0

ItI Π

(77) VCH ₂ -CH-CH ₂ -O-) ₃ P

The compounds of the formulas (75) and (77) are preferred.

D) Halogen compounds of the formulas

■ ■ Br Br

(78) Cl-U-CiI-CII ^ -O-CK ₂ -O-GK ₂ -CH-CH ₂

CH ₉ OH

Br
I.
OXi ₉ - Br
I.
CiI- CH ₂ -C Br
^tcil 2 Br
-ClI -CO-N

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Cl. Br Br

(SQ) CH _n -CH ,. ''

Yyx yyy

(81) CH ₂ -CH-CH ₂ -O-CO-

Br Br (82) CH ₂ - CII CH ₂ -O-CO- CH-COOH CLI

Br Br (83) CH ₂ -Ci-I-CO-KH-CH ₂ OH

Cl Br Br (84) CH ₂ -COO-CH ₂ -CH-CH,

Br Br (85) CH ₂ -CH-CO-NH ₂

The compounds of the formulas (83) and (84) are preferred.

E) Halogen compounds of the formulas

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BATH ORIGINAL

Br

0-CIU-CH-CH ₀ -Br

'2, Br

(88)

Br

Br - C V - OCH «- CH - CiL

Br Br Br

(89)

Br Br Br Br

(90)

Br / CO.

Br- « ^x ) CO '

Br Br

(91)

(92)

Br

Br -

Br

Br · CIL

Br-

f / W

OH

Br Br

509 8.10 / 07 3

When choosing the organic compound (s) and in particular the textile finishing agent (s), the desired effects and the temperature at which these compounds are transferred to the organic material without decomposition are taken into account. Preferred compounds are those which transfer temperatures between 100 and 22O ° C, in particular 150 to 200 have ⁰ C. In order to achieve several Ausrlisteffekte in one operation, textile finishing agents are preferably used with transfer properties that are as similar as possible, ie
those which have similar transfer temperatures ^{which do not differ by more than 20 ° C.}

With those given in the following examples
Percentages are percentages by weight.

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example 1

By means of a saddle roller, an end

Loose chemical carrier made of glass fiber fabric 7 g / m Diine thyl-Hydrogenmethyl-Polysiloxan (Viscosity 20-40 csT at 25 ° C).

The 2u treated side of the 20 m / min.

moving carrier is made of polyester

Cotton (50/50) poplin (140 g / m), which has previously been sprayed with 0.2% ZrOCIr, (catalyst) and moves at the same speed as the carrier, brought into contact in such a way that the carrier moves and move the material web together, lying on top, synchronously.

The carrier and web are then introduced into an apparatus as indicated in FIG. II. The 1st, 3rd and 5th drums (see (19), (21) and (23) in Figure II) are heating drums of 90 cm. Diameter and have a temperature of 190 ^° C. The 2nd and 4th drums (cf. (20) and (22) in FIG. II) are suction drums with the same diameter.

After a first pass, the web is drawn into the apparatus a second time, so that there are always 2 layers The web of material is in the apparatus, with the second layer coming to lie away from the carrier.

After the entire material line has been

5098 10/0730.

rature is over, the line of goods and the wearer are separated from each other separated.

Since only pure substance is applied, there is no need to clean the carrier.

The polyester-cotton-poplin finished in this way has values of 80 to 100 in the AATCC spray test 12-1966, while a comparative sample that was not equipped shows values from 0 to 20.

This test for testing the water-repellent properties of textiles gives values in a range which extends from 0 (minirnun) to 100 (maximum).

Similar results are obtained with the compounds of the formulas (57), (58), (60) and (61), where one There is no need to spray the fabric with a catalyst such as zirconium oxychloride prior to treatment.

509810/0730

Example 2

40 g of one of the yellow, blue or red dyes of the formulas (2), (10) or (13) are mixed with 100 g of ethyl cellulose in 860 g of a methyl ethyl ketone-ethanol mixture (weight ratio 1: 1) for 5 hours 20 ⁰ C ground in a sand mill and dispersed to a homogeneous printing ink.

Paper carriers are then printed with one of these inks in each case in such a way that a dye layer of 0.5-4 g / m ^{2 is formed after the solvent has evaporated at 20 ° C.}

A paper carrier printed in this way is provided with a

Polyester fabric (120 g / m) pulled together in one lane in an apparatus similar to that shown in FIG. The paper carrier that is adapted to the length of the polyester web to be dyed is used as the carrier. Furthermore, there is the apparatus consists of 2 units, of which the first unit consists of 6 rollers in the direction of travel of the carrier and the second unit Unit consists of 4 rollers. The 1st, 3rd and 5th rollers of the first unit and the 1st and 3rd rollers of the second unit are heating drums with a diameter of 50 cm, which are heated to 215 ° C. The 2nd, 4th and 6th rollers of the first unit as well the 2nd and 4th rollers of the second unit are made of felt

509810/0 7 30

wrapped suction drum of 50 cm diameter on which the paper carrier is heated from the back to 220 ° C by means of an infrared heater during the suction cycle.

The carrier and material web run through the apparatus synchronously once at a speed of 60 m / min, and are then separated from each other.

In this way, a dyed polyester fabric is obtained, that has an intense, level, yellow (or blue or red) color.

509810/0730

Example 3

Ordered on an endless carrier made of a felt made of polytetrafluoroethylene, the compounds of the formula (56) are padded on as a 50% ethanol solution _}

that an edition of 5 g / m is created. "

This carrier is part of a similar apparatus as shown in Figure II. The apparatus exists but from only 4 rollers, the 1st and 3rd Eeiζtrummeln lying in the direction of the carrier one diameter of 50 cm and are heated to 140 ° C, while the 2nd and 4th rollers are designed as suction drums with a diameter of 50 cm are. These suction trays cannot be heated.

Now a polyacrylonitrile fabric (130 g / m)

drawn into the apparatus. After the fabric has run through the 4 VYes for the first time, it will do 4 more times drawn into the apparatus, with the newly arriving web being removed from the carrier, i.e. as the 2nd or 3rd, 4th and 5th lane enters the apparatus. Then the fabric is separated from the carrier, so that there are always 5 layers of fabric, which correspond to a total length of approx. 12 m are in the apparatus. The 5 lanes of the fabric move in the process synchronous with the carrier at a speed of 90 m / min. Then the carrier and fabric are separated from each other separated.

509810/0730

To test the electrostatic properties, the surface resistance in SX / 100 era and the half-life decay times in seconds are measured under standardized conditions (22 ° C. and relative humidity of 30%). The half-life decay time indicates the time it takes for the voltage of 100 volts of an electrostatically charged tissue to drop to 50 volts.

The surface resistance of the polyacrylic fabric

is 10 before treatment and 10 after treatment

11 2
10 _Q / 100 era, which corresponds to a 10,000-fold reduction in the surface area.

Before the treatment, the polyacrylic fabric has a half-life disintegration time of 300 seconds after the treatment the latter drops to only 5 seconds.

Similar results are obtained with the compounds of the formulas (51), (53) and (55).

509810/0730

Example 4

The compound of the formula (54) is padded as an oily, viscous liquid onto an endless, airtight polyester support in such a way that an amount of 1.2 g / πΓ is created. Since the carrier is airtight, the application device (17) and (18) of FIG. II in the present case must be attached in such a way that the loaded side of the endless carrier can be brought into contact with the material web to be treated. In a departure from FIG. II, the apparatus consists of 2 units with 6 rollers each with a diameter of 50 cm. The 1st, 2nd, 4th and 5th roller in the running direction of the support of each unit are formed as heating drums, which are heated to 180 ⁰ C, while the 3rd and 6th roller of each unit are formed as Saugtroivuiel, each be heated ^{to 20O 0} G with infrared radiators.

Now a polyester fabric (150 g / m) is inserted into the

Apparatus retracted. The tissue passes through the S3n.ichron apparatus with the carrier once at one speed of 60 m / min and is then separated from the carrier.

The polyester fabric is tested for its electrostatic properties as indicated in Example 3.

As indicated in example 3, the loading

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act of surface resistance by 10,000 times. Before the treatment, the polyester fabric has a half-life of 290 seconds, that after the treatment drops to just 1 second. ·

Similar results are obtained with the compounds of formulas (49) and (50).

509810/0730

Example 5

A polyamide fabric (100 g / ni) is through a

similar apparatus as shown in Figure II was drawn in. However, the apparatus consists of 3 units. The first two units, which the fabric passes through first, consist of 6 rollers each with a diameter of 50 cm, of which the first 5 are designed as heating drums in the running direction that are heated to 190 ° C. The last and sixth rollers of the two units are, however, designed as suction drums that cannot be heated. The third unit which passes through the tissue by these two units, consisting of rollers 50 h era diameter, of which the three first are formed in the running direction as heated to 195 ⁰ C and heating drums as the last non-heatable suction drum. An air-impermeable endless polyester film serves as a carrier in the first two units, while the third unit has an air-permeable felt made of polytetrafluoroethylene as a carrier.

On the carrier of the first two units will be

Dibutyltin dilaurate (catalyst) 10 7 _o ethanolic

Solution puffed up in such a way that a layer of 1 g / m 2 is created. Since the carrier is impermeable to air, the application device must be attached as indicated in example 4.

509 810/07 30.

A dimethyl-hydrogenmethyl-polysiloxa, whose molecular weight 1350 to 1400 and silane hydrogen content (measured by splitting off those directly bonded to the silicon Hydrogen) is 314 ml / g, so padded that an edition of 10 g / m is created.

The polyamide fabric is now drawn into the apparatus in such a way that it only contains the first two units once, whereas the third unit runs through 4 times, with the newly arriving lanes in the third Unit removed from the carrier, i.e. as the 2nd, or 3rd and 4th lane in the third unit, so that there is always 1 layer Fabric in the first two units and 4 layers of fabric in the third unit are having a total contact length of correspond to approx. 23 m. The carrier and the single-lane fabric move in the first two units as well the carrier and the 4-panel fabric in the third unit all synchronously at a speed of 25 m / min. To the third unit separates the fabric from the carrier.

The polyamide fabric is tested for its water-repellent properties using the following spray test:

25 cm long, woven fabric samples are sprinkled with 500 ml of water to remove adhering drops and weighs the wet sample. The weight gain as a measure

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the water repellent effect is given in % of the dry fabric.

This is for an untreated polyamide fabric reference sample 80 to 90 7o, while the treated polyamide fabric shows a weight increase of only 10%.

509810/0730

Example 6

On an endless carrier as part of the apparatus described in Example 3, consisting of a felt Polytetrafluoroethylene becomes one of the connections Formulas (75) or (77) as an oily, viscous liquid like this

puffed up so that a layer of 25 g / m is created.

A polyester fabric (150 g / m) is now as in

Example 3 indicated 5 lanes drawn into the apparatus. The speed at which the carrier and the fabric move synchronously is 80 m / min when using the Compound of formula (75) and 60 m / min, when using the compound of formula (77).

After the fabric has been separated from the carrier, it is tested in comparison with untreated fabric for its flame resistance according to the DOC 3-71 test. The test is also repeated after multiple washes at 40 ^° C. in a liquor containing 4 g / l of a commercially available mild detergent.

The results are compiled in Table I below:

509810/073 0

Table I.

polyester
tissue before
Be
hand
lung BZ To
Be
hand
lung BZ To
1
Laundry BZ To,
2
Washes BZ To
10
Washes BZ To
20th
To wash BZ Treated with
.the connection
of formula (75) Tbsp Tbsp 10 Tbsp 2 Tbsp 6th Tbsp
6th 13th Tbsp 1
1 Treated with
the connection
of formula (77) 6th 2 4th 1 4.5 4th 6th 4th 5 28 Untreated 22nd 7th 3.5 9 6th 25th 4th 19th 4th 12th 4th 10 *)

*) burns

EL = tear length in cm
BZ = burning time in seconds

Similar results are not obtained with the connections of formulas (62) to (74) and (76) are achieved.

At DOC FF 3-71 ("Children's Sleepwear test") acts it is the following flame retardant:

"5 pieces of tissue (8.9 cm 25.4 cm) are in

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stretched a Pr'dfrahmen and dried for 30 minutes at 105 ⁰ C in a drying cabinet with circulating air. The pieces of tissue are then conditioned in a closed vessel over silica gel for 30 minutes and then subjected to the actual flame resistance test in a furnace. The tissues are ignited for 3 seconds each in a vertical position with a methane gas flame.

The test is passed if the average the char zone is no longer than 17.5 cm and not a single sample has a char zone greater than 10.4 cm and the individual afterburn times are no longer than 10 seconds. "

509810/0730

Example 7

The procedure is as in Example 6, but the compounds of the formulas (83) or (84) as such are doctored on in such a way that an edition of 36 g / m is created.

A polyamide fabric (130 g / m) is 5-ply in

the apparatus, as indicated in Example 3, retracted. the The speed at which the carrier and the fabric move synchronously is 60 m / min.

After separating the fabric from the carrier, each fabric is compared with untreated fabric for its flame resistance tested according to the DOC 3-71 test (see example 6).

The results are summarized in Table II below.

Table II

Polyamide fabric Burn time
in sec. Tear length
in cm treated with connection
of formula (83)
treated with connection
of formula (84) 4th
4.5 5.5
5
burns full
constantly from untreated 30th

5 0 9 810/0730

Similar results will be obtained with the connections of formulas (78) to (32) and (85).

509810/0730

Claims (18)

Claims 1. Process for continuous, dry. Transfer of organic compounds to material webs air-permeable organic materials', characterized in that that one on a carrier (1) preparations applied, the at least one at atmospheric pressure above 80 ⁰ C in the vapor state passing over organic compound, optionally below 25O ° C contain a stable binder and / or a solvent and optionally dried; (2) the loaded carrier with the side to be treated the air-permeable web of organic material in such a way that the carrier and web of material come into contact lying on top, move synchronously; (3) carrier and web gegebeneiifalls under application of mechanical pressure alternately at least one respective heat treatment of mindestetis 8O ⁰ C vo.n the support side and a suction effect from the Warenbahnsei'te forth, optionally combined with a second heat treatment of at least 80 ⁰ C of the carrier side, and this treatment continues or repeated until the said compound has been transferred to the web to be treated, the web being drawn in in one or more webs, 509810/07 30 so that the same web section has the same heat-suction cycle runs through one or more times; and (4) separates the treated web from the carrier. 2. The method according to claim 1, characterized in that that you have an air-permeable or a uses airtight endless carrier. 3. The method according to any one of claims 1 or 2, characterized in that there is an air-permeable carrier begins. 4. The method according to any one of claims 1 to 3, characterized characterized in that one has a carrier made of a glass fiber fabric, Steel fiber fleece, perforated or porous metal strip, perforated or porous plastic film or textile fiber fleece used. 5. The method according to any one of claims 1-4, characterized in that is used as the organic compounds, compounds which comprise Transfer temperatures of 100 to 22O ⁰ C. 6. The method according to any one of claims 1 to 5, characterized labeled that one as organic compounds 509810/0730 • · · - 53 - Compounds used, many transfer temperatures of 180 to 220 ° C. 7. The method according to any one of claims 1 to 6, characterized in that chemicals, in particular Textile finishing agents as organic compounds to be transferred used. 8. The method according to any one of claims Ibis'7, characterized in that that a web made of organic fiber material is used as the air-permeable web. 9. The method according to claim 8, characterized in that a web of organic textile material begins. 10. The method according to claim 9, characterized in that the textile material is polyester, polyamide, polyacrylonitrile and / or contains cellulose. 11. The method according to any one of claims 1 to 10, characterized in that the throughput speed of the material web up to 100 m / min. 5 0 9 810/0730 12. The method according to claim 11, characterized in that ' net that the throughput speed of the web is 20 to 50 m per minute. 13. The method according to any one of claims 1 to 12, characterized marked that the web is drawn in 1 to 10 lanes, 14. The method according to any one of claims 1 to 13, characterized characterized in that the material web is alternately subjected to 2 to 20 heat treatments and suction effects will. 15. According to the method of one of claims 1, to 14 treated organic material. 16. Device for carrying out the method according to one of claims 1 to 14, characterized in that that this out (A) a web-shaped carrier, which is in the Can move lengthways, (b) a device for applying organic compounds to the carrier, then in the direction of travel, (c) a sequence of at least one ¹ . Heating and suction unit and, if necessary, additional heating units, 50981070730 which are combined with the suction units und_ (d) each has a device that feeds the material web of organic material to the loaded carrier and removes the treated material web from the carrier, namely in such a way that the carrier and the material web come together lying on top synchronously and are fed together to the heating and suction units and after the transfer of the organic compound from the carrier to the Viarenbahn at above 80 ⁰ C, the web and carrier are separated from each other and the device allows the web in one or more layers move in at the same time. 17. The device according to claim 16, characterized in that the web-shaped carrier consists of an airtight or preferably an air-permeable endless carrier. 18. Device according to one of claims 16 or 17, characterized in that the heating and suction unit consist of rollers, which act as a heating drum and, if necessary, as a heating drum formed with additional heating units heatable and possibly wrapped with felt drum are. 509810/0730