DE1519495A1 - Process for coloring or printing plastic films - Google Patents

Description

Dr. V, / Schalk
Dipl.-: ..or W? Rfh

sANDoz A.o. Dip: --.-.- .. Γ, -, η ,, ^ 1519495

Basel Pr.V. .- ^, vOvvarzfk _Case 1946

- ■ @) .Tir-'vbi ·} a. Main

Size Eschenheimer Sfr. $ 3

Process for dyeing or printing plastic rolls

The invention relates to a method for dyeing or printing of plastic films, characterized in that one with impregnated a dye preparation containing a dye, water ■ ■ and contains a water-soluble salt of a higher molecular weight fatty acid.

Under plastic sheeting, ie. under non-textile moldings especially films and plates made of polyurethane, Polyester, vinyl chloride or vinylene chloride foils can.

These can contain fillers or be reinforced by fiber materials, for example by fibers made from natural or regenerated cellulose, cellulose acetates, polyesters, synthetic or natural polyamides or acrylonitrile polymers. The process for dyeing or printing the synthetic leather ^{coated with foamed polyurethane products has become known under the name w} Corfam ("Polyester fiber reinforced urethane material" ie. A polyurethane film reinforced with polyester fibers).

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BATH

The aqueous dye preparations have the advantage that they can be used on pouring machines without addition, or practically without addition, of thickeners and / or film-forming binders. They result in extremely stable cast films. Ψ the aqueous dye formulation can also be by immersion, squeezing, rolling, brushing, spraying or printing listed on the plastic are introduced.

All known leather dyes can be used, in particular mono-, dis- or triazo dyes, metal complex dyes and reactive dyes which are relatively soluble in water, for example those of which at least 0.2 g are soluble in one liter of water. It has been shown that metal complex dyes in particular can be fixed very well on the plastic films and therefore do not bleed out in water. Suitable dyes are, for example, those from y French patents 1.073.728j I.O79.I52; I.IO3.828;

I.138.773; l ^f .318.843 or from the French additional patent specification 64596. The amounts of dye used are generally 0.1-60 g / liter.

Higher molecular weight fatty acids for the purposes of the invention are saturated and preferably unsaturated higher molecular weight aliphatic ^ carboxylic acids, the approximately 7 to 28 and especially 12 to 18 carbon atoms contain. Salts are made from oleic acid with particular advantage

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and ammonia or such organic amines are used which are volatile at room temperature or at moderately elevated temperatures, which results in advantageous back network values for pigment finishing. This promotes good film build-up and in no way adversely affects the wet fastness properties of the finishing film. The dyeings or finishes obtained with oleic acid salts can be embossed or calendered particularly well. Corresponding salts of blown and unblown fatty acids, such as, for example, castor oil fatty acids ™, are also suitable. As is known, blown fatty acids are natural, unsaturated fatty acids treated with atmospheric oxygen at elevated temperature, such as higher molecular weight aliphatic carboxylic acids with at least one olefinic double bond. The artificial leathers dyed with their help are also easy to equip. In addition, the dyes can be dissolved in them very well at room temperature. These salts are used in amounts between approximately 0.5 and 300 g, and in particular between 5 and 150 g, per 1 liter of preparation. Advantageous to use a dye composition which additionally contains' a water-miscible, boiling between 50 ° and 200 ⁰ C organic solvent.

Water-miscible organic solvents necessary for the process are suitable are, for example, non-ionic, nitrogen-containing, organic solvents and their mixtures, preferably amines or amides, such as acid amides, amino alcohols, alkyl

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■ v- SAD ORfQiNAL

amines, etc. "also urea and a derivative or heterocytilisphe nitrogenous compounds, e.g. formamide, methyl formamide, Ethylformamide, Dimethylformamide, Dlaethylformamide, Acetamide, Urethane, Ethanolamine, Diaethylformamide, Dlaethylformamide, Acetamide, Urethanes, ethanolamine, diaethanolamine, triaethanolamine, diaethylaminiaethanol, Thiourea and its derivatives, guanidine and its derivatives, monoisopropylamine, dibutylamine, morpholine,

- ■ ·

Morpholine ethanol, etc., monohydric and polyhydric alcohols, ketones, Aldehydes, ethers, acetates, esters, glycols, polyglycols, glycol-methers, Glycol esters, alkylene halides, such as methanol, ethanol, propanol, isopropanol, acetone, methylene chloride, acetonylacetone, Formaldehyde, acetaldehyde, 1,4-diaethylene dioxide, methyl acetate, Ethyl acetate, monobutyl ether, methyl acetate, octyl acetate, dlaethylene glycol, Diaethylglycol, ethylene glycol diethyl ether, ethylene glycol, hexylene glycol, dimethoxytetraglycol, glycerine, dietethylene glycol monobutyl ether, Ethylene glycol monobenzyla ether, ethylene glycol mono-or -diaethyl ether, ethylene glycol acetate, ethylene glycol monoethyl ether acetate, Aethyleriglynolmonomethylether, Ethylen- ' glycolmonoaethylaetheracetat, Dip ropy lertely ^ ol, Ttj-t ^ aaethyH.enslycol, Triaethylene glycol, etc ..

The dihydric alcohols are particularly preferred. Of these Solvents will be about 5 to 980 g and especially 10 to 300 g, but preferably 20 to 200 g per liter of dye preparation are used.

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■ - 5 -

The dye preparations used can contain additional auxiliaries, e.g. other organic solvents, customary ones anionic or non-ionic wetting or dispersing agents, anti-foaming agents, synthetic resin dispersions and organic or inorganic Pigments. Liquid, saturated hydrocarbons, e.g. liquid petroleum fractions. They are used in amounts up to about 50 g per liter of dye preparation and especially from 1 to 20 g. Also serve as additional wetting or dispersing agents or protective colloids, such as polyvinylpyrrolidone Sulphonated castor oil or polyoxyethylenated castor oil are particularly advantageous Phenols, high molecular weight amines or alcohols, e.g. lauryl triglycol ether sulfate or oleyl eicosaglycol ether, or alkyl polyglycol ether-oxy-acetic acid. Of this, for example, 0.5 to 100 g and preferably 1 to 20 g can be used per liter of preparation. the Protective colloids can also be used as anti-foaming agents, e.g. in quantities of 0.5 - 20 g / liter.

The pH of these liquors or pastes is generally 7 to 10 and preferably 7.5 to 9 * 5. Their temperature can be normal or be elevated. The application can e.g. by brushing (plush), Rolling, spraying, pouring, e.g. with the help of a pouring machine, printing or especially by squeezing, advantageously with Help of rollers under pressure, whereby the rollers are under

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the level of the dye solution. The impregnated synthetic leather is advantageously squeezed off at room temperature and dried at an elevated temperature, e.g. up to 95 ° C and finished as usual

equipped. The dyeing can also be done at temperatures of 15-95 ° Cj are preferably carried out at 40-70 ° C.

The dyeing can also be done under pressure or vacuum, with the ) Pressure on the plastic film to be colored by two or more rotatable rollers is exercised. This squeezing or squeezing pressure is generally 0.1 kg per one running centimeter up to 50 kg with a roller radius of 0.5 to 100 cm, but preferably per running centimeter from 2 to 10 kg with a roller radius from 2 to 60 cm, the number of revolutions of a roller being 1 to 100 revolutions per minute. The impregnation or dyeing process can be improved by squeezing it off several times.

k The roller system, preferably consisting of a smooth surface, is made of stainless cast iron or chrome-plated, for example VpA steel or made of brass or heavy metal alloys manufactured.

The impregnated o4er-dyed leather is used in well-known catfish Room temperature or stored at elevated temperature uiia like tn>. loaned ready-made.

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The parts mentioned in the examples are parts by weight and the percentages are percentages by weight. The temperatures are in degrees Celsius specified.

B e i s ρ i e 1 1

A mixture is made of 31.5 parts of ricinoleic acid, which is commercially available under the name of ricinus oil fatty acid, 6.5 parts of morpholine, 2.5 parts of the auxiliary from Example 25 of French Patent No. 1,312,787, 30 parts Hexylene glycol, 20 parts of ethylene glycol, 5 parts of "Petrol", an odorless petroleum fraction, 2.5 parts of 25% aqueous ammonia solution and 5 parts of a 70% aqueous sorbitol solution. 75 parts of this mixture, which has a pH value of 8.8, are mixed with 2 parts of the dye from Example 1 of French patent specification I.O73.728 and 923 parts of water. "Corfam" (registered trademark) (polyester fiber reinforced urethane material, ie. A polyurethane film reinforced by polyester fibers) synthetic leather is impregnated with this liquor with a pH value of 9.4, pressed on the roller system, rinsed, squeezed again, dried and with Equipped with suitable film formers and pigments, optionally embossed, if necessary at elevated temperature. _;

089003 / T57 6

The dye is uniform in the cross-section of the artificial leather penetrated. The brown color obtained does not matter, it is scratch and scuff resistant, lightfast, perspiration resistant, rubfast, abrasive resistant, does not bleed and is formaldehyde, acid and heat resistant.

Instead of the castor oil acid salt, the corresponding oleic acid salt or the ammonia salt of oleic acid can be used. The 10W parts "Petrol" can be replaced with equally good Erfol'g by 10 parts Lauryltriglycoläthersulfat or Oleyleikosaglycoläther.

Example 2

A mixture of 30 parts of oleic acid, 6 parts of morpholine, 2.5 parts of the auxiliary from Example 25 of the French U.S. Patent No. 1,312,787, 25 parts hexylene glycol, 25 parts Ethylene glycol, 6 parts of "Petrol", an odorless petroleum fraction, 3 parts of 25 # aqueous ammonia solution and 5 parts of a 70 # Sprbit solution. Of this mixture, which has a pH of 8.9, 75 parts with 3 parts of the dye of Example 1 of French patent I.073.728 and 922 parts of water mixed.

With this liquor with a pH value of 9.4, a plastic film as in Example 1 colored and finished as usual.

■ 0OS8Ö9 / -15 7.6.

The dye has penetrated deep into the synthetic leather. The received The brown coloration has the fastness properties listed in Example 1.

B e i s ρ i e 1 5

A mixture is prepared from 31.5 parts of oleic acid, 12 parts of one 25 # aqueous ammonia solution, 951.5 parts of water and 5 parts of the dye of Example 1 from French patent specification 1.110.281.

With this liquor with a pH value of 9.4, an artificial leather as in the example is made 1 described and treated further as described there.

The dye has penetrated deep into the synthetic leather. The red dyeing obtained has all the fastness properties listed in Example 1. (

B e i s ρ i e 1 4

A mixture is prepared from 16 parts of oleic acid, 1.5 parts of rinoleic acid, 12 parts of an aqueous ammonia solution, 4 parts of "Petrol", an odorless petroleum fraction, 953.5 parts of water and 15 parts of the dye of the example from German patent 582399 .

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With this liquor with a pH value of 9.5, an artificial leather like in
Example 1 described colored. The dye has penetrated deeply into the leather and the black dyeing obtained has all of the fastness properties listed in Example 1.

Example5

3 parts of the dyestuff from Swiss Patent 342.307, Example 4, are dissolved in 82S parts of water at 70 °, and the mixture is cooled
to about 20 °, 100 parts of oleic acid and 8 parts of a 25 # aqueous ammonia solution are added.

A plastic film, known under the protected brand name
"Corfara" (a polyurethane film reinforced by polyester fibers, known in the literature as "polyester fiber reinforced urethane material") is placed between 2 rollers, with a radius of 20mm,
which are ^ under the level of the dye solution, at
a pressure per running centimeter of 7 kg and three passages per minute, moved back and forth for 10 minutes.

After this time, the plastic film is in running water of 40 °, rinsed for 2 minutes and at the same pressure as. in the Stain for 1 minute by reciprocating between two Rollers squeezed.

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The plastic film is then placed on a filter paper and to remove any rinse water that may be present by stretching squeezed off again and then dried.

The dye penetrated the film deeply and uniformly; it is completely colored. The coloration obtained in this way is rich in color and has the properties mentioned in Example 1 *

The repeated repetition of the squeezing effect, i.e. the backward and allowing the film to move between the two rollers a very level coloring of the surface and the cross-section of the plastic film.

Ricinoleic acid, commercially available, can also be used in place of oleic acid under the name of castor oil fatty acid, can be used with just as good success.

The same good results are obtained if the dye I Preparation of 10 parts of "Petrol", an odorless petroleum fraction or just as many parts of lauryl triglycol ether sulfate or oleyl icosaglyeol ether are added.

The dye given in the examples can be replaced by a those dyes are replaced which have become known from the following patents; but it can also

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Mixtures of such dyes can be used.

German patent specification 582,399 850,868 ti 68.187 French] he patent 798.1OT 1,068,784 Il ti 1,073,728 H Il 1,079,152 It It 1,097,852 Il It 1,094,633 Il Il 1,102,177 η Il 1,103,828 Il ti 1,107,888 It ti 1.110.28I It It I.134.742 It Il r. 138,773 If It 1,210,546 ti Il 1,221 * 621 η It 1,253 * 728 Il 11 ■ "1,257,407 ι » »I. 1 * 257 * 953 W. Il 1,338,613 Tt Il French Zusafczjpatenfcsehrift 64.5§6 dd Il Il

1-576

BATH ORIGINAL

French additional patent specification

μ η

American patent specification

75,033 75,771 77,594 77,754 78,104 2,120,799

The dye in the examples can, however, also be replaced by dyes which can form a chemical bond with the substrate, so-called reactive dyes. Such dyes carry e.g. halotriazinyl or halopyrimidyl radicals. These include, for example, the following dyes: "Procion-H" and "Procion-M" dyes, such as "Procion" (registered trademark) brilliant red 2 BS, known from "Chemisches Centralblatt" 1961, page 12453, "Procion" (registered trademark) brilliant orange GS, known from "Angewandte Chemie", 73, page 126 (196I) or "Procion" (registered trademark) brillantblau-RS, known from "Helvetica Chimica Aeta ", 44 (1961) page 1123, or by so-called" Cibacron "dyes (registered trademark) j these dyes are also known from the "Collection of Czechoslovac chemical Publication" 25, (i960) Pages 2794-2797 or from Ulimann, 14 (1963) page 618. However, so-called "Remazol" dyes (registered trademark) can also be used are like them from "Collection of Czechoslovac chemical Publication "2 £, (1962) pages 272-274 are known.

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1.51 9 A 9 5

called "Laevafix" dyes (registered trademark) they made them from "Collection of Czechoslovac chemical Publication" £ 2, (1962) page 274-275 are known or reactive dyes from the French patents Nos, 1.318.843; 1,319,429; I.332.76O.

Examples

A mixture of 15 parts of blown castor oil fatty acid with the acid number 100, 3 parts of morpholine, 1.25 parts of a compound of the formula 01eyl- (QC ₃ H ^ J ₁₀ OC ₂ H ^ COONa, 15 parts of hexylene glycol, 10 parts of ethylene glycol, 2 , 5 parts of "Petrol", an odorless petroleum fraction, 1.25 parts of 25 # strength aqueous ammonia solution and 2.5 parts of a 70 # strength aqueous sorbitol solution 37 parts of this mixture, which has a pH of 8.8 mixed with 2 parts of the dye of Example 1 of Swiss Patent 316,754 and 927 parts of water.

A plastic film, known under the protected brand name "Corfam" (a polyurethane film reinforced with polyester fibers, known in the literature as "polyester fiber reinforced urethane material") is between 6 rollers, with a radius of 30 mm, which are located under the level of the dye solution a pressure per centimeter of 10 kg and eight passages per Minute while moving back and forth for 2 minutes.

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After this time, the plastic film is in running water of 5-0 °, rinsed for 20 seconds and at the same pressure as with the Staining for 30 seconds by reciprocating between two rollers squeezed.

The plastic film is then placed on filter paper and stretched again to remove any rinse water that may be present squeezed off and dried afterwards. ™

The dye penetrated deeply and evenly into the film! it is completely colored. The orange to burgundy color is rich in color »no matter, scratch and fire resistant, light and rubbing fast> formaldehyde, acid, sweat and heat resistant »

The multiple repetition of Ausquetscheffektes> d ^ h, the back and / or forth movement of the film between the rollers eriööglieht like a very level dyeing the surface and the cross section of the plastic film, or * dös

Example 7

A mixture of 31 parts of blown castor oil fatty acid is added the acid number 100, 6 parts of morpholine, 2.5 parts of the auxiliary from Example 25 of French Patent No. 1312787, 20 parts of hexylene glycol, 50 parts of ethylene glycol, 3 parts of "Petrol", an odorless petroleum fraction, 2.5 parts of 25 # aqueous ammonia solution and 1 part of a 70 # aqueous sorbitol solution. from this mixture, which has a pH of 8.8, is 75 parts with 4 parts of the dye of Example 1 of the French patent 1 107 888 and 889 parts of water mixed.

A plastic film, known under the protected brand name "Corfam" (a polyurethane film reinforced with polyester fibers, known in the literature as "polyester fiber reinforced urethane material") is placed between 4 rollers, with a radius of 4-0 mm, which are located under the level of the dye solution, at a pressure per centimeter of 8 kg and five passages per minute, moved back and forth for 1 minute.

After this time, the plastic film is in running water of 40 °, rinsed for 1/2 minute and at the same pressure as with the Dye squeezed for 15 seconds by moving back and forth between two rollers.

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The plastic film is then placed on a filter paper and to remove any rinse water that may be present by stretching again squeezed off and dried to the chile.

The dye penetrated the film deeply and evenly; she is completely colored. The yellow coloration thus obtained is rich in color, no matter, scratch and scuff resistant, light and rubbing fast, formaldehyde, acid and heat ■ resistant.

The repeated repetition of the squeezing effect, ie. the outward and allows the film to be moved between the rollers, a very level coloring of the surface and the cross-section of the Plastic film. '-'

The synthetic leather can be made using the same procedure at a temperature dyed from about 50 °, the artificial leather the same: good Has properties.

The aid from French patent no. 1 312 787 may can just as easily be replaced by a sulfonated fatty acid ester, e.g. by the sulfonated oleic acid butyl ester ...

BATH 0980 9/15 75: ■

Claims (24)

1579495 Pat e η I. A method for dyeing or printing plastic films, ^ characterized in that it is impregnated with a dye preparation which contains a dye, water and a water-soluble salt of a higher molecular weight fatty acid. II. The plastic films colored by the process according to claim I. Subclaims 1. The method according to claim I, characterized in that polyurethane films are dyed or printed. 2. The method according to claim I, characterized in that polyester foils are dyed or printed. 3 »Method according to claim I, characterized in that vinyl chloride or vinylidene chloride films are dyed or printed . 4 ·. Method according to dependent claim 1, characterized in that polyurethane film reinforced with synthetic polyamide fibers colors or prints. 0 09809 / 5 · The method according to dependent claim 2, characterized in that a polyester film reinforced with synthetic polyamide fibers colors or prints. 6. The method according to dependent claim ~ 5, characterized in that a vinyl chloride or vinylidene chloride film reinforced by synthetic polyamide fibers is dyed or printed. _ 7 · The method according to dependent claim 1, characterized in that a polyurethane film reinforced by polyacrylonitrile fibers colors or prints. 8. The method according to dependent claim 2, characterized in that a polyester film reinforced with polyacrylonitrile fibers colors or prints. 9. A method according to dependent claim 5, characterized in that ä be enhanced by polyacrylonitrile vinyl or Vinylidenchloridfolie dyeing or printing. 10. The method according to dependent claim 1, characterized in that a polyurethane film reinforced by polyester fibers
colors or prints. 009809/1576 11. The method according to dependent claim 2, characterized in that a polyester film reinforced by polyester fibers is dyed or printed. 12. The method according to dependent claim 3, characterized in that one reinforced by polyester fibers vinyl chloride or Vinylidene chloride film dyes or prints. 13. The method according to claim I, characterized in that plastic films made from foamed polyurethane products colors or prints. Ik. Process according to claim 1, characterized in that the salt of a higher molecular fatty acid used is a salt of a blown fatty acid. 15. The method according to claim I, characterized in that the salt of a higher molecular weight fatty acid is a salt of a Unblown fatty acid is used. 16. The method according to claim I, characterized in that a salt of oleic acid and ammonia is used. 17. The method according to claim I, characterized in that one is a salt of oleic acid and a volatile organic Amin starts. 009809/1576 18. The method according to claim I, characterized in that pan uses a salt of ricinoleic acid. 19. The method according to claim I, characterized in that one eine.Farbstoffzubereitung begins, which additionally contains a water-miscible, boiling between 50 ° and 20Q ⁰ C organic solvent. 20. Method according to claim I, and dependent claim 19, thereby characterized -that one uses a glycol as an organic solvent begins. 21. Verfahrcm iraoh claim T, characterized in that .the preparation also contains liquid, saturated hydrocarbons contains. 22. The method according to claim I, characterized in that ^ the preparation is applied to the plastic film with the aid of a casting machine. 23 * Method according to claim I, characterized in that the dye off preparation in the absence of a thickening agent is used. BATH
009809/1576 ^BA 24. The method according to Pa-fceritaneprucli I, characterized in that that one works under pressure or vacuum, 25 · The method according to dependent claim 24, characterized in that that the pressure is applied to the plastic film to be colored two or more rollers are exercised, . ■ - "S ft HD OZ A.G. ' ί ' 1. , 009803 / 157S