DE1901882C - Process for improving the wet fastness and abrasion resistance of dyes and the adhesion of printing inks to hydrate cellulose casings - Google Patents

Description

4. The method according to claim 1 to 3, characterized in the context of the overall manufacturing process, characterized in that the diisocyanate is 4,4'-Me- 35 and the shell is made with relatively large Gethylene-bis (cyclohexyl isocyanate) or a long-chain, derived from the speed of passing through the dyebath, of a dimeric acid resembled the speed of dyeing aliphatic diisocyanate used. Textile products and yarn. It has to be

5. The method according to claim 1 to 3, characterized as quite difficult, the casings in marked, that you can evenly color the desired color tones as a polyepoxide, without water-soluble, polymeric reaction product from that strong in different areas of the shells Epichlorohydrin and that occur through the implementation of color fluctuations.

Adipic acid obtained with diethylenetriamine Attempts have already been made to use cellulose casings in the

Polyamide used. large-scale with vat dyes and

45 naphthol dyes to color. Some of them

Colorings achieved by large manufacturers with vat dyes are to a certain extent reproducible and relatively real. But the handling and

It is known that vat coloring is used as a substitute for natural sausage with after-coating artificial cellulose sausage casings from a 50 parts connected. More useful for staining Cellulose solution, e.g. B. viscose to produce. That of sausage casings as part of an overall process Sleeves are dyed, dried, printed and are naphthol dyes that are therefore used to produce then moistened again before plugging. The with from in numerous hues from red and yellow to Wurstemuision stuffed regenerated or hydrated sausage casings are used to make dark brown colored sausage casings cellulose casings are then smoked and smoked.

cooks. They come as transparent thin fiber sausage casings and unreinforced cellulose tubes or reinforced with a fiber insert as fiber sausage casings are therefore used in the present casings. The latter are described as being dyed with naphthol dyes, because of their dimensional stability, especially for thick ones, but other dyes such as Bolognese sausages and similar sausages can also be used. Naphthol dyes will be used, which are processed into packaged cut goods with the weight known to be due to the conversion of the naphthol. The cellulose used for numerous types of sausage with a true color salt is produced ^{: 1 |} en generally formed by ex-named aryldiazonium compounds. Si (trudge a viscose solution through an annular 65 slot nozzle in their substantivity differ greatly in a coagulating and regenerating bath. A measure of the degree of affinity that a tube made of regenerated or hydrate cellulose naphthol has for a substrate. From the USA. · Then by washing by-products and patent specification 3,383,443 ibt a two-stage naphthol

^ method known, with the cellulose casing unreinforced casing or fiber casing) first from the washing bath into an alkaline solution of a one-S Nhhl d d kiilih dh

through those in the

the the

adhesive strength of the Dn
on the other hand, very much more tight and hk fading lot

? _u f the substrate aui ο

wura

lem g

Sen Naphthols and then continuously through, on the other hand, was very much weaker and wua

Se aqueous solution of a single real salt has not yet been a satisfactory solution

will lead; the bath is made at a temperature below & ^ei £ ^nd . ^en · _{r hknow} that the abrasion or that

JO "C, preferably below 15" C, maintained and _can with it "st ^ ar ^ ^^^ ^3η _{η w} hen

a suitable acid-salt mixture, for example sodium ^from 8 ^{"before the} surface of the cellulose sausage casings

acetate-acetic acid, to a pH of 2.5 until the stained surface of the Le luiosewur

VffVt. The residence time of the casing in the io drying with a J ^ JiB MeJ ^ ™ ζ

Dimensions subject to abrasion or peeling of the paint, especially when re-moistening the casing before plugging. The pigment particles of not Lbstratgebundenen dye adhere due to the polar groups and similar surfaces he _akm forces at the CclTuWhullc and the WEI ao tean processing the CellulosehüUe can be worn loose Farhstoffteilchen, especially when _Sto the moistened envelope pfen with meat emulsion, or in handling the moist stuffed sausages. This is undesirable because the "5 clothes and hands ml sausage production employees will discolor the and the dye is difficult to remain removed from hands and clothes," J * ™ ίTrankert is and the films in the substrate verankrt "j J _eranfeuchten water dispersible wallowing At the _ vv of the shell through the tendrils of the ^ n

hence ^the _n ^D J "f ^ J ^ '^ J" och especially

f ^^^^^^ m ^ when stuffing by stretching uci

reinforced. _{dj wet}

It has now been gt geze since &"'<£ £ _son.

^ hthe.t and Al ^ wA e ge of ^ ^

to which the ™, η bag especially _on damp and & ^ed ^ nHyoTO _d ° covers a water ^! film-forming

a di- or poly-

!! * ™ ^ _ά process abrasion ^ "" bond strength

«Yor

^ie ™ means _that you can print the hydrate cellulose with a vegetable gum, Na-

&> « Or poly- ^^ coating agent with olotJ ocyanate, polyepoxide, acylamide, polyester, polyhalide as crosslinking agent to t Dk des

The Wursthül.e ArFarben is dried for 30 Z

and printed. The application of the aniline print has ^ol y

been generally found to be unsatisfactory ctio en _W cil aniline inks only weakly on the

relatively moist surface of the hydrocellulose ^

adhere and in the event of improper pre-soaking and

The plugs of the sausage casings come off easily. Pressure- ^ Ug ^ ^

Oil-based inks, on the other hand, are used to a certain extent by printing inks

Successfully used because they ^{adhere better to strongly glycerol - the shells in} _and water-containing hydrate cellulose. They contain a pigment or a mixture of pigments, em 40 ^^

binding or solution halls drying by oxidation medium and one or more siccatives. Binders or solvents that dry by oxidation

are mainly drying, unsaturated animal, vegetable or synthetic oils that are exposed to the air 45 ^^ o

oxidize and polymerize to a thin film, ^ f "^

from which finally a firm and tough but flexible Chlorepox.d

samer film is, z. B. Linseed oil, tung oil (wood oil), H J

Perilla oil, oitizika oil, soybean oil, a synthetic track- dinendes petroleum based or chemically modified 50 one

drying oils, such as dehydrated Rhizmusol or new ones odorless drying animal oil.

Most of the drying oils used for printing inks are stand oils. When printing without Au ^ ⁱⁿ g ^{s e} ^ J ^ _{n D} sausage casings made of cellulose hydrate thereby 55G were run dan "^ verw moistening two problems. First, the ink must w.rd reduces the J ^ '^ _{f dn min.} To dry quickly so that they do not ^Au ^ ^h ^ soluble polymeric polyfunctional when touching sticks more and does not stick when the printed wit Wassert "^ P> _as coating agents sausage casing sections are aufcinandergestapclt? ^r 8 ^amschen _k ™ _"n ⁸ _are gelatin, egg albumin, and then to dry completely under exclusion 60 in_ hrage ^ κοπ, _Tragak anth or rubber to form a chemically and / or phy ^ fc" ^ f ^ "" kederivate Soluble cellulose ether, binding to the substrate, that is, to the clear shells ^ SvjcXtoc hydroxyethyl cellulose, carb or fiber hulls made from hydrate cellulose. The solution ^ SS ^ Natnumcdluloscxanthal,. The first problem was rather simple, since the oxyme hylcejui ° '., _{Lkohol BcvO} rzugl w.rd aul drying rate, i.e. the formation of a 6 ₅ ^ ÄreSartagSi price, its high viscosity drying, non-sticking surface layer, base ^ g "J are generally printed with appropriate Au selection of the S.kkative and har Li _b tion controls and / or can be accelerated, z. B.

ta ^ Networking Jen coating is implemented Thanks to the ^ ™ hydrateellulose, a new method can now ^ »J _{faifcen printed}

^{zufr Eden} _v '"V can aniline inks or similar ^^^ M

_{n- In} addition

and har Ocidtine.

The crosslinking agents that are applied to make the polyfunctional coating agent insoluble make, are compounds that have two or more reactive ^ uch different ones per molecule contain functional groups, namely diisocyanates, diisothiocyanates, polyepoxides, chlorine epoxides, Acid chlorides, acylamides, polyesters, polymeric ketenes, polyhalides, diimides, polyfunctional Nitriles and polyfunctional acid anhydrides. Examples of this are diisocyanate or diisothiocyanate of a dimer acid, 4,4'-methylene-bis- (cyclohexyl isocyanate) and 4,4'-methylenebis (cyclohexyl isothiocyanate); Butadiene diepoxide; the reaction product of epichlorohydrin and a Polyamide; Adipyl chloride and sebacyl chloride; Adipylamide and sebacylamide; Dimethyl sebacic acid ester, Dimethyl suberate; the diketene of a dimeric Acid; 1,6-diimidohexane; 1,6-dicyanohexane, tetracyanoethylene and pyromellitic anhydride.

The less reactive crosslinking agents) that interact with each other or with water at around room temperature do not react, are used in a mixture with the coating agent in aqueous solution. When drying at elevated temperatures to form the insoluble coating, some as Cases the coating is also cross-linked to the substrate. More reactive crosslinking agents are coming Application, this is how the Hydrated! ulose sleeve first passed through an aqueous solution of the coating agent and in a separate treatment then treated with the crosslinking agent.

According to one embodiment, the hydrate cellulose casings are thus coated with an aqueous solution of the coating agent *, which dissolved the crosslinking agent or dispersed, brought into contact and then dried at a temperature of up to 150 ° C.

The same desired effect is achieved if you first use the hydrate cellulose casings an aqueous solution of the coating agent in contact, lightly dried and then with the Treated crosslinking agent.

The crosslinking agent used is preferably 4,4'-methylene-bis (cyclohexyl isocyanate) or a long-chain aliphatic diisocyanate derived from a dimer acid or the water-soluble one, polymeric reaction product of epichlorohydrin and that obtained by reacting adipic acid with diethyl triamine obtained polyamide.

When carrying out the according to the present invention A clear, unreinforced casing or a fiber casing made of hydrate cellulose is usually used Way continuously produced, colored in the Gclstatus and then provided with the coating according to the invention. At least one of the washing baths, preferably after the dye baths, contains glycerine or other suitable plasticizers to coat the hydrate clhilose to make supple. The main thing is to improve the adhesive strength the printing color. so the coating in the first stage of a multi-stage printing unit or in a separate work stage combined with the overall printing process at the entrance to the printing unit or be applied completely separately in a pressure-dependent operation.

The stink of the job isn't particularly critical and .can be a few 11 to several 10 μ. After the coating has been applied and in-the-screen drying, anilimprint ink is obtained or oil-based printing ink applied in one or more operations, with multi-color printing the printing ink is dried between the individual operations. The printed cover is then air-dried. The anilimprint paints applied to the coated hydrate cellulose sleeve or oil inks stubbornly adhere to the shell during the subsequent treatment. They also do not peel off if the casing is immersed in water at 80 ° C for 10 minutes or even in boiling water Dipped in water or when stretched, such as when stuffing sausages.

Test procedure

The resistance to abrasion or discoloration of the casings treated according to the invention was rated with a corresponding test device (Atlas-CM-l-Crockmeter Atlas Electric Devices Company). The squares of the meter were wetted with water and rubbed over the sleeve with 50 revolutions at the maximum stop. Then the squares became visually compared with an untreated casing as a comparison.

You adhesive strength of the printing ink on according to the invention treated cellulose sausage casings was determined by taking printed sausage casing samples for 1 hour were placed in an 80 ° C water bath for a long time. A cellophane tape was then placed on top of the print applied and quickly withdrawn. The amount of ink adhering to the tape is a measure for the quality of the adhesive strength of the printing ink. An untreated sample was again used for comparison used.

The invention will now be explained in more detail with reference to the following examples. All specified quantities relate to weight, unless otherwise stated.

example 1

A fiber casing was continuously produced and dyed with light yellow-red dye, coated, heat-treated, printed and air-dried. For the continuous production of the fiber casing was Fiber paper passed on a Viskoscstrangpreßdüsc vcibci into a coagulating and regenerating bath. the Web speed was 12.2 m min; then the casing was washed through various and color baths led. After coagulation and regeneration, the casing was washed and then softened with glycerin; if there is excess from the coagulating-regenerating baths Acid was taken along, so the shell could by means of a premier / erization treatment through an I ", Oi ge Nalriumhylroxydlösung be performed.

The casing was passed through a naphthol solution at a speed of 12.2 m / min Veiweilzcit in the solution was 6 seconds. the Naphthol solution contained 0.5 to 200 u / l p-methoxyanilide (Naphthol AS-RL), 0.75 to f, 5 g / l Ethylcndiaminotetraacetic acid (or other chclating agent), an anionic wetting agent, and Sufficient sodium hydroxide for a 0.03 to 1.2N solution. Preferably was the naphthol solution kept in constant motion by beating air.

The one impregnated with the naphthol color component Shell was then at a speed

of 12.2 m / min and a dwell time of 12 to rubbing and stretching noticeably dye and pressure-14 Seconds with a solution of a true color salt.

drawn. This solution contained a true color salt. In other experiments, the same as above became essential Excess over the stoichiometrically written coated and primed shell with required amount, based on the naphthol in a yellow printing ink and partly on it the shell. The solution preferably contained 12 g / l of a blue oil-based printing ink printed and Echtrot AL, a compound of the formula each with an untreated printed

Fiber sheath compared. In all cases they were

O ν = NT ^ coated covers the uncoated covers

'! ! ίο with regard to staining and abrasion of the printing ink

\ ^ / consider. . .

; ' ^b Example 2

In this example, clear, wide, continuous

Clear, unreinforced casings made from regenerated cellulose

15 produced in the usual way and according to Example 1 '

Q coated, with the difference that the gelatin content in the solution increased from 0.75 to 1.5%

and was with 2 to 20 g / l acetic acid and 15 to 5 g / l was. The viscose was as usual through a

Sodium acetate to a pH of 2.5 to 5.9 annular slot nozzle with a. speed buffered. In addition, the solution contained a speed of 4.6 to 13.8 m / min in a regeneration and

small amount of a commercial dispersant, coagulating bath extruded, the ammonium sulfate, Na-

a chelating agent, e.g. B. ethylenediaminetrium sulfate and sulfuric acid. With some

tetraacetic acid. and 15 to 20 g / l sodium chloride,. Coagulating and regenerating baths were tried

In order to separate the bleeding of the naphthol into the solution, the coagulating bath was in the first place impede. The real color salt solution became a salt bath and the regeneration bath in the first place

Temperature below 20 ° C, preferably at about 10 line an acid bath. The envelope became for removal

up to 15 ° C. washed from acid, salts and by-products

Then the casing was successively replaced by a and, if necessary, by a diluted soda

Hcißwasserbad and then passed through a brine bath sodium sulfide to sodium polysulfide solution out from the last wash bath to newly to 30 different ^about entrained excess acid

Remove accompanying potatoes. Eventually the neutralize.

Shell made soft, coated according to the invention, then the shell was successively according to

heat-dried, printed and air-dried. Example 1 by a naphthol bath and a real salt

A satisfactory coating solution corresponds ^ ^a pulled d.

held in aqueous solution 0.75 percent by weight 35 The unreinforced hydrate cellulose was colored

Gelatin, 10 ⁰ / o glycerine and 0.5 percent by weight of shell practically under the same reaction conditions

Polyepoxide. that appears as a reaction product of epichloride and at the same concentrations

hydrin and one by reacting adipic acid naphthol and true color salt like the fiber casing. With

polyamide obtained with diethylenetriamine as o-methoxyanilide (Naphthol AS-OL) in the Naphschwach Amber colored liquid with 10% solid 4 ° tholl solution and real orange RDN, a compound

material content, d = 1.026, viscosity = 30 cP at 25 ° C of the formula (Brookfield), pH 5.0 and N content (Kje! - N = N

dahl) = 12.8 ° / n (solids basis) has been obtained. !

This solution was made by immersion as a thin '

Layer on several pieces of dyed fiber casing 45 ~

(Regeneral cellulose, reinforced with hemp fiber paper) F ₃ C

applied and dried.

Part of the coated shell became a reddish-orange color with regard to color abrasion or coloration on the test device in the true color salt bath Atlas-CM-1-Crockmeter, as described above, obtained in 50 tones, available in stores as fawn or fawn checks and draws with a non-coated colored one

Envelope compared. It was found that the coating then produced as above

layered shell much less paint came off than or coating solution as a thin layer on dii

of the uncoated shell, which is applied under the test clear hydrate cellulose shell and ge

conditions rubbed off strongly. 55 dries. Parts of the colored and coated envelope

Thereupon the coated area was de-marked with regard to staining or peeling

white oil-based basic printing ink, namely color tested and colored uncoated

compared to a mixture of pigment, metal-containing dry casings. It turned out that this be

In the case of cobalt naphthenate, alkyd resin and hardener, the shell is coated with a soft layer to prevent the color from coming off

for the resin such as cellulose acetate butyrate opposed in a 60 considerably greater resistance than di

drying oil, such as linseed oil, wood oil, etc., printed on untreated comparison sample. Then di

and dried for 6 days. The coated shell could then be dried and put on a white

Printed sausage casing for 10 minutes in boiling primer with a fat printing ink, e.g. Legs

Immersed in water and printed on yellow printing ink as if it were plugging. The imprint was

be dried without the dye or print 65 for about 4 days; then the envelope could

paint peeled off. A fiber casing without the was immersed in boiling water for 10 minutes

Coating of the process according to the invention can be colored and stretched as in the case of plugging, without there

and then printed, so when boiled in water, paint came off or the printing ink peeled off

Was an unreinforced shell without the invention Post-treatment dyed in the same way and then printed, so went when boiling in water, Noticeably rubbing and stretching off a lot of dye and printing ink.

Example 3

In this example, a coating compound is used. which contains a natural plant resin as a coating polymer, used to protect clear regenerated cellulose casings from staining or peeling of the dyes or printing inks. The aqueous coating solution produced contained 1.0 "n water-soluble polymeric polyepoxide according to Example 1, 1, ⁰ /» tragacanth or gum arabic and 10 "/ i» glycerol. It was used to coat a clear, unreinforced hydrate cellulose casing according to Example 2.

As already described, wide cellulose sausage casings were produced by passing viscose through a annular slot nozzle with a speed of 4.6 to 13.8 m / min, in some cases up to 23 m / min, was extruded into a regeneration and coagulation bath, the ammonium sulfate, sodium sulfate and contained sulfuric acid. ' In some records, the coagulating and regenerating baths were separated, the coagulating bath primarily the salts and the regenerating bath primarily the Contained acid. The coagulation tube was removed from acids, salts and by-products by washing freed and, if necessary, passed through a dilute sodium hydroxide bath to remove any Neutralize acid from the last wash bath. Then the shells were one by one Naphtholhad and a true color salt bath performed, as already described in the previous examples. It was produced under essentially the same reaction conditions and at the same concentrations worked on naphthol and true color salt as before. A reddish yellow shade (in stores referred to as amber) was made using o-methoxyanilide (Naphthol AS-OL) in the naphthol solution and real orange GGD, a compound of the formula

F ₃ C -, - CF ₃

Achieved in the true color salt bath The aftertreatment solution prepared above was spread over several pieces clear hydrate cellulose shell applied as a thin layer and dried. The treated cellulose casing was tested together with untreated comparison samples in the Atlas-CM-1-Crockmeter with regard to staining or peeling of the color. How In the previous examples, very little color came off the treated casings the untreated casing samples, however, had a great deal of color.

The coated casings were then dried and colored with a bold printing ink, e.g. B. printed the blue printing ink used in Example 1. For comparison, an uncoated cover was printed in the same way. The difference in dye and ink abrasion under the same conditions as in the previous examples was evident. In comparison with the untreated sample, the coated casings showed a pronounced resistance to staining and a significant improvement in the adhesive strength of the printing ink.

In other experiments, the white and yellow printing ink already used was applied to the coated one Cover applied. For every attempt was

ίο conducted a comparison test. Under the same test conditions was the difference in dye and ink rub-off between the coated and the uncoated shell noticeably. The coated shell showed against the uncoated comparison sample a noticeable persistence over the rubbing off and a significant improvement in the adhesive strength of the printing ink.

Example 4

In this example, clear (unreinforced) casings and fiber casings were made on a technical system dyed, coated and printed to the effectiveness of being carried out on an industrial scale To examine coating method according to the invention.

The effectiveness of the coating process according to the invention has been demonstrated in several tests a commercially available dyeing system and a commercially available printing system. The manufactured

The coating solution was an emulsion of 0.5 "0 Diepoxidvernetzungsmittels with an epoxy number 661, 1.0 ° / o gelatin, 12.5 ¹ Vo methyl ethyl ketone, 0.5 '/ 0 Polyoxyäthylensorbitantristearat with' 20 of polyoxyethylene in the molecule and 85.5% water.

This coating solution was placed in a coater coupled with a Young printing press and applied to clear hydrate casings and fiber casings. The case was made with the Application machine after dyeing and drying

4a coated according to Example 2, being passed under a dry lamp and then into the Young press, in which a first printing ink, e.g. B. the white greasy oil paint used in Example 1 was applied. In these tests, the sausage casing with the coating applied after dyeing was printed in the first half of each test and the sausage casing without a coating was printed in the second half of each test. After drying, which is necessary for the printed

so layered fiber casings 2 days and for the printed coated unreinforced casings 4 days lasted, the coated casings were under the test conditions of the previous examples excellent color fastness and the printing ink adhered also excellent An analysis of the elongation curve of the coated casings versus the corresponding uncoated casings showed that the Change in the elongation properties could be neglected. Neither was any detrimental

Changes in the casings as a result of the coating or the applied printing ink were observed.

Example 5

In this example, various different emulsion-like coating compositions are used used to protect the colored covers from the Farhc and the adhesive strength dei Improve printing ink on printed sleeves / u.

A satisfactory coating emulsion, which contained an isocyanate as a crosslinking agent, consisted of 2 ¹ Vo of spray-dried product obtained by reacting neutralized viscose (US Pat. No. 3,291,789) with chloroacetic acid, 0.1% water-resistant isocyanate of a long-chain aliphatic dimer acid and 0.015% alkylphenoxy (ethyleneoxy) ethanol, dissolved in water.

Another satisfactory coating emulsion used formaldehyde as a crosslinking agent. Formaldehyde can then apply when the pH of the aqueous solution is <7, preferably 1 to 3 as a crosslinking agent (instead of DDI 1410 in the above formulation). With the aid of an ion exchange column, the pH was adjusted to this value before the coating solution was applied.

Another useful coating emulsion contained epichlorohydrin as a crosslinking agent. It consisted of 0.75% gelatin, 0.1 ° / o of epichlorohydrin, 10 '/ 0 89.15 ⁰ Glycerin and Zn water.

The clear unreinforced casings and the fiber casings were dyed according to Example 2 and with one of these three coating compounds coated. All coated casing samples showed in the Test on the Atlas-CM-l-Crockmeter improved resistance to the peeling of the Color compared to the untreated control covers.

Several pieces of the coated casings were put on an anilimpring press in different passes printed using various types of common anilox inks. Aniline inks generally consist of a resin and a pigment, dissolved in an alcohol-free ester or in 3Ii Methyl ethyl ketone. In these attempts, polyamide-based, acrylic-based and used on a nitrocellulose basis.

After printing, the print was allowed to dry; A comparison test with an uncoated shell was carried out for each printing ink. The difference in coloration and adhesive strength of the printing ink under the test conditions according to Example 1 was considerable. The coated casings showed a significantly greater resistance to the peeling of the ink and a significantly better adhesive strength of the printing ink than the untreated comparison samples.

Example 6 _So

In this and the following examples, the coating of the cellulose casings is used for improvement the color fastness and adhesive strength of the printing ink explained in a 2-step process.

Clear regenerated cellulose sausage casings were made passed through a 1.5% gelatin solution in order to achieve a gelatin coating on them. The coated casings were dried and then passed through a saturated solution of phosgene in benzene. The casings were then dried at 105 ° C. in a stream of hot air. During the On drying, the phosgene crosslinked the gelatin coating and made it insoluble in this way.

The coated casings were then tested on the Atlas-CM-1-Crockmeter and showed a significantly improved resistance to staining compared to untreated, colored comparison samples. In the same way, when the coated covers were printed with lithographic or aniline printing inks, the adhesive strength of the printing ink on the coated cover was significantly improved compared with the untreated comparison samples.

Example 7

Clear regenerated cellulose sausage casings were coated in a 1.5% gelatin solution with a gelatin coating provided, partially dried and then through a saturated solution of oxalyl chloride in Ether led. The casings were then dried in a stream of hot air at 105 "C; during the On drying, the oxalyl chloride crosslinked the gelatin coating and made it insoluble.

The coated casings tested on the Atlas-CM-1-Crockmeter showed a marked improvement Resistance to staining compared to the dyed but uncoated Sample. After the coated covers have been printed with lithographic or aniline printing inks It was found that the adhesive strength of the printing inks was also markedly improved compared with the uncoated comparison samples.

Example 8

Clear regenerated cellulose sausage casings were passed through a 1.5% gelatin solution and provided with a gelatin coating. The casings were then partially dried and passed through a saturated solution of succinic acid chloride in ether. The casings were then dried in a stream of hot air at 105 ^° C .; the succinic acid chloride crosslinked the gelatin coating and made it insoluble.

When tested on the test device already mentioned, the coated casings showed compared to the uncoated colored casings have a significantly improved resistance to staining. In the same was true for the adhesion of the printing inks to those with lithographic or aniline printing inks printed, coated covers are noticeably stronger than the uncoated covers.

Example 9

Clear regenerated cellulose sausage casings were drawn through a 1.5% strength gum arabic solution and provided with a gum arabic coating. The coated casings were partially dried and then passed through a saturated solution of phosgene in benzene. The casings were then dried in a stream of hot air at 105 ° C .; The phosgene cross-linked the gum arabic coating and made it insoluble.

When testing on the Atlas-CM-l-Crockmeter the coated casings showed a significantly improved stain resistance compared to the non coated colored casings. Also the adhesive strength of the printing inks after printing lithographic or anilimprint inks were significantly improved on the coated sleeves over the uncoated sleeves.

Example 10

Clear regenerated cellulose sausage casings were drawn through a l, 5 ^o / o tragacanth, to provide them with a Tragakanthüberzug. the

13 14

Layered casings were partially dried resulted in a significantly improved color fastness of the .ind then by a saturated solution of oxalyl-coated shells against the uncoated rhlorid in ether. Then the casings were colored casings. Also the adhesive strength of the print dried in a stream of hot air at 105 ° C; inks on those with lithographic or anilinhei the oxalyl chloride cross-linked the tragacanth coated casings printed with printing inks Coating and made it insoluble. much stronger than on the uncovered Ver-Die Test the same test on the test device already mentioned.

Claims (3)

residual acid or salts from the coagulating patent claims: regenerating bath freed and with a softening 1. Method for improving the wet fastness maker, e.g. B. with glycerine, impregnated. if the and abrasion resistance of dyes and the shell tends to remove excess acid from the Adhesion strength of printing inks on hydrate, coagulating and regenerating baths cellulose casings, with the casings in the gel as a Vormerzerisierungsbehandhang by a state colored, provided with a coating and P / o sodium hydroxide solution. For printed, characterized in that fiber sleeves is a tube made of chamfered paper, the hydrate cellulose casings in front of the track - preferably a long fiber dumbbell paper, lying next to them nen and printing with an aqueous solution io led to the annular slot nozzle and mn the Impregnated and coated from gelatine, vegetable gum, viscose emerging from hydroxyethyl, cellulose, carboxymethyl cellulose, sodium cellulose from which in the coagulation and regeneration bath in losexanthate, polyacrylic acid or polyvinyl- the fibrous paper and on the outer surfaces alcohol covers and the coating agent with the paper hydrate cellulose as an essential one Forms diisocyanate or diisothiocyanate, poly-15 train. The finished fiber casing consists of 35 bis epoxy, chlorine epoxy, acid chloride, acylamide, 40% fiber paper and 60 to 65% hydrate cellulose Polyester, polymeric ketene, diimide or poly and plasticizer components. You will be in the same halide as difunctional or polyfunctional compounds like the unreinforced clear shells wetting agent to a water-insoluble over-washing freed of accompanying substances. train. 20 The production of colored sausage casings was 2. The method according to claim 1, thereby associated with difficulties for a long time. Although denotes that the hydrate cellulose, the casings are produced directly from hydrate cellulose, casings are in contact with an aqueous solution of the coating and therefore dyed with dyes which dissolve or contain the crosslinking agent, as it contains and dispersed for dyeing cotton brings and 25 rayon are used, it has not ^{proven to be expedient then at a temperature of up to about 150 0} C, the dyeing process for textile dries. products or yarn in the manufacture of 3. The method according to claim 1, thereby using colored hydrate cellulose casings. Tex indicates that the hydrate cellulose tiles are often in a separate working envelope first with an aqueous solution of 30 gear by immersion for a long time in Bringing coating agent into contact, lightly colored on sufficiently large dye vats. The f: rdries and then with the crosslinking agent generation of colored shells, in particular of treated. permanently or genuinely colored casings, however,