DE4207110A1 - Polycationic polymer preparations - useful for (pre)treatment of hydrophobic substrates such as organic high polymers, glass and metals - Google Patents

Abstract

A water-dilutable prepn. (I) is claimed, contg. (a) a heat-fixable polycationic polymer which forms at least colloidal solns. in water, contg. basic amino or imino gp(s). with N-bonded H atom(s) or an acid adduct thereof, and (b) a water-soluble lactam. Also claimed is a process for (pre)treating (II), by applying (I) to the substrate and heating. Also claimed is the use of such treated substrates as substrates for further processing, pref. dyeing with anionic or nonionic dyes, esp. with direct dye(s), using a polycationic fixing agent (k) contg. (k1) a soluble cationic polymer consisting of polymer (a1) (see below), pref. precondensed with (a6) a resin-forming opt. etherated N-methylol cpd. (pref. a N-methylol deriv. of an opt. cyclic urea) and (k2) a resin-formed, opt. etherated N-methylol cpd. with methylol-linked basic N atom(s) (pref. opt. etherated tri- to hexa-methylolmelamine) or an acid adduct thereof; the fixing process is carried out under acid conditions at at least 80 deg.C., pref. using a catalyst for crosslinking when using N-methylol cpds.. Also claimed are substrates treated by this process. The invention enables "difficult" substrates (esp. glass, metal, aramid fibre etc.) to be treated, esp. dyed and then fixed to give intense, fast colours; fibres treated with (I) are less prone to disintegration or to prodn. of dust during processing, and have improved dimensional stability. USE/ADVANTAGE - Used as a (pre)treatment agent, esp. for organic high polymers, glass and metals (II) (claimed).t a

Description

It has been found that certain polycationic polymers (as defined below in combination with water-soluble lactams (as described below) are surprisingly good for affinity-enhancing or treatment of substrates, in particular of hydrophobic substrates, which in themselves only are insufficiently or not at all dyeable from an aqueous liquor, and that the substrates (pre-) treated with it then in a simple manner and in high Yields and fastnesses can be refined - especially dyed. After treatment with certain fixatives, as described below, can improve the properties of the refinements (especially yield and real units) can also be improved.

The invention relates to the use of the products mentioned for (pre) be treatment of substrates or the new preparations and their use as (Pre) treatment agent, the treatment of the substrates thus equipped with other finishing agents and also post-treatment with fixer and the new fixatives.

A first subject of the invention are preparations which can be diluted with water, which by content

• (a) an at least colloidally soluble in water, fixable in heat ren, polycationic polymers, the at least one basic amino or Imino group with at least one nitrogen-bound hydrogen contains atom or an acid adduct thereof,

and

• (b) a water soluble lactam

Marked are.  

The polycationic polymers (a) are at least colloidally soluble in water Lich, d. H. they form in a concentration of 3 g / l in distilled Water real or colloidal solutions. They are polycationic, i. H. they contain several amino groups (primary, secondary and / or tertiary) and / or ammonium groups (quaternary ammonium groups and / or protonated ami nogroups), wherein the molecule has at least one basic amino or imino group with at least one nitrogen-bound hydrogen atom or Contains acid adduct. The polymers (a) can be heat-fixed, d. H. when applied to a substrate, they can be heated form insoluble equipment at temperatures above room temperature.

The polymers (a) are primarily those with a high cationic Charge density (especially in protonated form) and are preferred aliphatic. Preferred are (a) aliphatic polycationic polymers, wherein at least 50%, advantageously at least 80% of the heteroatoms stick are atoms (the rest, if any, are preferably acidic) atoms of matter); the distances between the heteroatoms, especially between the nitrogen atoms in at least 50 mol% of the polymer, especially in at least 80 mol% of the polymer, primarily in the entire polymer, are advantageously at most 5 carbon atoms, preferably at most 3 Carbon atoms.

(A) is preferably chosen from the following polymers:

• (a ₁ ) reaction products of
  • (x ₁ ) cyanamide, dicyandiamide, guanidine and or biguanide, with
  • (x ₂ ) at least one primary or secondary mono- or polyfunctional aliphatic mono- or polyamine;
• (a ₂ ) precondensates of (a ₁ ) with
  • (x ₃ ) epihalohydrin or dihalohydrin;
• (a ₃ ) reaction products of (x ₂ ) with (x ₃ );
• (a ₄ ) reaction products of (a ₃ ) with
  • (x ₄ ) 1,3-diaminopropanol-2;
• or
• (a ₅ ) Homopolymers from
  • (x ₅ ) a mono- or di (meth) allylamine or co- or terpolymers
  • (x ₆ ) one or more mono- and / or di (meth) allylamines and optionally tri (meth) allylamine
• or mixtures of at least two of the polymers (a ₁ ) to (a ₅ ).

Polymers of the type (a ₁ ), (a ₂ ), (a ₃ ), (a ₄ ) and (a ₅ ) and mixtures thereof are e.g. B. in the German patent applications DE 32 16 913 A1, DE 33 30 120 A1, DE 34 22 822 A1, DE 36 22 840 A1 and DE 37 06 176 A1 be written. We expressly refer to the content of these published documents.

Particularly preferred polymers (a) are those of type (a ₁ ) as described in DE 33 30 120 A1 and especially (a ₂ ) as described in DE-OSes 32 16 913 A1 and 34 22 822 A1.

Lactams of aliphatic γ-, δ-, or ε-aminocarboxylic acids with 4-6 carbon atoms, including ε-caprolactam is particularly preferred.

Components (a) and (b) are advantageous in such relative amounts used that 0.1 to 10, preferably 0.3, per Val amine or imine in (a) up to 4 Val lactam (b) can be used.

The molecular weight of the polymer (or - for homopolymers - the recurring monomer unit) divided by the Amino or imino functionality understood, the amino or imino functionality the number of hydrogen atoms attached to basic amino or Imino groups in the molecule (or in the monomer unit), based on the non-protonated form, are present. A Val Lactam is here one mole of lactam divided by functionality, i. H. by the number Lactam groups in the molecule.

The pH of the preparations can vary within a wide range, for example  wise in the range of 4 to 14; the low for transport and storage preferred pH values, namely 4 to 8, preferably 5 to 8, wherein the pH if necessary by adding common acids, mainly mine ralic acids, especially sulfuric acid, can be adjusted.

Components (a) and (b) serve, in the presence of one another, in particular in combination with each other, for the treatment of substrates to make a change tion, d. H. Increase, the ability of the substrates ennobled (in particular to be colored) - essentially an increase in the affinity of the sub strate to the finishing agents - to evoke, or any Ver finishing (especially staining) on substrates that are otherwise made from aqueous medium cannot be refined (colored). The fiction Appropriate (pre) treatment of the substrates can also be used as a surface modification of the substrates or, if appropriate, as film formation on the substrate are referred to, because of the application of (a) and (b) containing Treatment liquors adhere to the surface of the reaction product ((a) + (b)) enriches, which adheres to the substrate and a refinement forms a medium-friendly layer.

Components (a) and (b) can be added separately to the treatment liquors be or can previously together with concentrated preparations be mixed. These aqueous concentrated preparations have been proven for example, a total content of (a) + (b) of 5-80% by weight.

Possible substrates for the (pre) treatment according to the invention both hydrophilic substrates and especially hydrophobic substrates in Consider, primarily natural, semi-synthetic or fully synthetic organic high polymers and inorganic substrates, especially glass or metal. As organic high polymers, for example, natural ones modified fiber materials may be mentioned, e.g. B. natural che polyamides (wool, silk or leather), optionally modified Cellu loose (cotton, linen, hemp, jute, sisal, viscose rayon and cellulose peace tate) and fully synthetic substrates, for example polyamides, polyesters, Polyurethanes, polyalkylenes (especially polypropylene), types of polyimide fibers, Poly (ether ketones), poly (ether ether ketones) and polyphenylene sulfides. There are especially the more hydrophobic substrates, i. H. those with a water intake less than 5%, particularly glass, metal and highly crystalline polymers. The substrates can be in any  suitable for the respective application process, manageable form be find, e.g. B. as a film, film, powder or fiber. Are particularly suitable the treatment agents according to the invention for application to fiber mate rial, including primarily the fibers made of metal, glass or highly crystalline Linen high polymers, such as aramid fibers (primarily meta-aramids made of poly -isophthalamide or para-aramide from poly-terephthalamide), polyimide fiber types, polypropylene fibers, highly crystalline polyester fibers and others aromatic polymers (e.g. poly (ether ketones), poly (ether ether ketones), poly - (p-phenylene sulfide) and the like), alone or as a mixture with one another and / or with natural fibers. Of particular note the otherwise very difficult to dye and highly crystalline aramid fibers as well Fiberglass. Application to the substrates mentioned is appropriate netsten by applying an aqueous liquor to the substrate closing fixation by heat treatment. On the substrates mentioned, in particular the preferred fibrous substrates, which in one in the Textile industry may otherwise be in the usual form, e.g. B. as loose fibers (also flock), filaments, threads, strands, bobbins, fabrics, knitted fabrics, tufting goods, velvet, felts, nonwovens or semi-finished or finished goods, can (pre) treatment agents according to the invention by conventional Impregnation processes are applied, for example by dipping, Padding, watering, spraying or by order of the fleet using a Doctor blade, an air knife or by foam application or by Be to press. Depending on the chosen application method, substrate and desired Effect can be the content of components (a) and (b) in the treatment fleet fluctuate widely, e.g. B. in the range of 2 to 200, advantageously 5 to 100, preferably 10 to 40 g of the total components ((a) + (b)) per Liters of aqueous liquor. The pH of the liquor is pre-determined for the application partial to values in the range from 6 to 14, preferably 9 to 12, in particular special 11 to 12 set (if necessary using conventional Alkali, especially sodium or potassium hydroxide or of tertiary Amines). The liquors or components (a) and (b) are advantageous applied in such concentrations or in such application quantities that 0.4 to 30, preferably 1 to 15 wt .-% of components (a) + (b) in total can be applied together with the substrate.

The impregnation with the liquors can be carried out at normal temperatures Lich at temperatures in the range of 10-60 ° C and the impregnated Goods can then undergo the heat treatment required for fixation  will be thrown. The heat treatment takes place primarily at temperatures of at least 80 ° C, in particular at least 90 ° C, advantageously in tempera tur range from 90 to 240 ° C, preferably from 120 to 200 ° C, the temperature temperature range of 160 to 190 ° C is particularly preferred. Depending on the chosen The temperature, the nature of the substrate and the quantity applied can Treatment time vary, e.g. B. from 20 to 200 seconds, mainly 30 to 180 seconds, generally in a time of 30 to 60 seconds sufficient fixation has already been achieved.

The substrates treated in this way can, if desired, with any of the usual Chen finishing agents, especially anionic, cationic, amphoteric or non-ionic, in particular non-ionic or anionic Ver processing agents are further treated, primarily with dyes or op table brighteners or other finishing agents, such as those e.g. B. used for equipment before assembly, z. B. Anti statics, sewability agents, plasticizers, roughening agents etc., all of which However, the substrate treated according to the invention is particularly suitable for dyeing sentence finds. Any dyes and optical brighteners can be used ders are used with anionic and non-ionic character, for. B. as described in the "Color Index" under the names Acid Dyes, Direct Dyes, Mordant Dyes, Reactive Dyes, Disperse Dyes, Pigments and Fluorescent Opti cal brighteners are defined, especially dyes with direct colorant character (as is particularly the case in the "Color Index" under the Be drawing "Direct Dyes" are defined) and pigments (as they in particular are defined in the "Color Index" under the name "Pigments", and preferably in aqueous dispersed form) are preferred. These other products, especially the dyes, can be ordered according to your needs usual methods can be applied from an aqueous medium, e.g. B. after Pull-out dyeing methods or impregnation processes, the impregnation process ren (in particular analogous to those listed above) are preferred. The coloring besides the dyes, other additives can be added if desired included, e.g. B. thickeners, leveling agents, wetting agents. Depending on Fleet absorption capacity of the substrate can change the dye concentration Fleet and the application method can be selected and controlled. The The dyes can be fixed at temperatures similar to those for the above (Pre) treatment described.

If desired, the refined substrates, especially the dyeings, can be post-fixed with a polycationic fixing agent (k), e.g. B. with the products (a ₁ ), (a ₂ ), (a ₃ ), (a ₄ ), (a ₅ ) as described above, or especially containing a preparation
(k ₁ ) an at least colloidally soluble polycationic polymer which is a polymer (a ₁ ), as defined above, optionally precondensed with (a ₆ ) an N-methylolver compound capable of resin formation
and
(k ₂ ) an N-methylol compound capable of resin formation with at least one methylol-bonded basic nitrogen atom or an acid adduct thereof,
where (k ₁ ) and (k ₂ ) may have partially reacted with each other and (a ₆ ) and (k ₂ ) may be the same or different from one another.

As components (k ₁ ) known products can be used, for. B. reaction products of polycationic polyamines and N-methylol compounds as described in German Offenlegungsschrift DE 31 05 897 A1. The nitrogen-bonded methylol groups in (a ₇ ) can optionally be etherified, e.g. B. with C _1-4 alkyl, preferably with methyl; however, the methylol groups are particularly preferably not etherified.

As components (a ₆ ) are preferably N-methylol derivatives of an optionally cyclic urea, especially those as described in DE 31 05 897 A1, on pages 7-9. Cyclic urea derivatives, especially N, N'-dimethylolethylene urea, N, N'-dimethylolpropylene urea, N, N'-dimethylol-4,5-dihydroxyethylene urea and N, N'-dimethylol-5-hydroxypropylene urea, especially dimethylylene dihydroxy, are particularly preferred is preferred.

Component (k ₂ ) is preferably an N-methylol derivative of a melamine, in particular tri- to hexamethylolmelamine, which can optionally be etherified with methyl. The (k ₁ ') and (k ₂ ') containing preparations (k) are also the subject of the invention, where (k ₁ ') is a precondensate from (a ₁ ) and (a ₆ ), as described above and (k ₂ ') Is an optionally etherified tri- to hexamethylolmelamine.

100 to 400 parts by weight of component (k ₂ ) are advantageously used per 100 parts by weight of component (k ₁ ).

The aftertreatment with (k) for postfixing is advantageously carried out from aqueous medium. The content of (k), in particular components (k ₁ ) and (k ₂ ) in the post-fixing liquor is expediently chosen so that an application amount of 0.2 to 20, preferably 0.5 to 10% by weight is achieved in the squeezing effect achieved. % (k), in particular the sum of (k ₁ ) + (k ₂ ), based on the substrate, is applied. The applied products can be fixed under acidic pH conditions, advantageously in the pH range from 3.5 to 5, preferably 3.5 to 4, the pH being set using customary acids (for example organic acids or Lewis acids) can be. The crosslinking of component (k ₂ ) with component (k ₁ ) is advantageously carried out in the presence of a catalyst, in particular with such catalysts and with such catalyst amounts, based on (a ₁ ), as described in DE 31 05 897 A1. The impregnated goods can be fixed by heat treatment in a manner analogous to that described above, a shock drying process being particularly suitable, primarily in the temperature range from 100 to 200 ° C., preferably 170 to 190 ° C.

According to the inventive method, treatment with the inventions (Pre) treatment agents according to the invention, especially on the very difficult or otherwise impossible to color substrates such as the highly crystalline organi high polymers and the glass fibers or metal fibers, an affinity achieved an increase or even an affinity, so that they esp especially a dyeable substrate and, like others, otherwise lighter treatable substrates can be refined, in particular colored. If particularly high fastness properties are desired, using the An increase in fastness properties can be achieved according to the invention.

In particular, color-intensive and true dyeings on substrates such as Glass or metal or highly crystalline high polymers, especially sol chen with an aromatic character, in particular aramid fibers, where the particular substrates, especially physical Properties that are practically unaffected while on certain th substrates, e.g. B. glass fibers, he other desired properties can be held, e.g. B. reduced tendency to fray, to dust  when cropping or editing, and improved dimensions stability.

In the following examples, the parts mean unless otherwise noted ben, parts by weight and the percentages by weight. Parts by weight are available to parts by volume such as g to ml. The temperatures are in degrees Celsius give. The dyes specified in the application examples are han standard products.

example 1

• a) 103 parts of diethylene triamine and 84 parts of dicyandiamide are heated to 100 ° C. At this temperature, an exothermic reaction with ammonia elimination begins, the temperature is allowed to rise to 150 ° C. The reaction product is kept at 160 ° C for 6 hours to complete the reaction and then at about 90 ° C with 193 parts of water. The resulting suspension is cooled to room temperature and adjusted to a pH of 7.5 while cooling with about 59 parts of 96% strength sulfuric acid.
  100 parts of this solution are further diluted with 425 parts of water and 15.5 parts of epichlorohydrin are gradually added while stirring at room temperature. The reaction mass is then heated to 50 ° C. and kept at this temperature for one hour with stirring. The solution is cooled to room temperature and neutralized by adding about 1 volume part of sodium hydroxide solution 30%. A clear, light yellow solution is obtained. This product is now adjusted to 50% solids content by vacuum distillation.
• b) The 50% preparation is with caprolactam, in a ratio of 100 parts Polymer according to Example 1a) to 100 parts of caprolactam, stirred.

Examples 2-7

According to the information in Example 1, the following compounds (as salts) manufactured with different proportions:  

Example 8

• a) A glass fabric of 240 g / m ² is mixed with an aqueous liquor containing 100 g / l of a mixture of 66.6 parts of the 50% product according to Example 1a) and 33.4 parts of caprolactam (mixed together according to Example 1b )) impregnated, etc. adjusted to pH 11.0 with NaOH. The impregnation is done on a 2-roll pad with a squeezing effect of approx. 30%. It is immediately 60 seconds. Dried and fixed at 180 ° C (one-step shock process).
• b) The material treated in this way is now continuously dyed in a padding process (2-roll pad, 30% squeezing effect) and the like. The following metal complex direct dyes are used in these examples: pad-dry dyeing, each with 40 g / l, with black 80 g / l, drying 90 ′ ′ 120 ° C.
  CI Direct Yellow 98,
  CI Direct Yellow 162,
  CI Direct Red 83,
  CI Direct Red 83: 1,
  CI Direct Red 261,
  CI Direct Violet 66,
  CI Direct Blue 77,
  CI Direct Blue 90,
  CI Direct Blue 251,
  CI Direct Green 69,
  CI Direct Brown 240,
  CI Direct Black 118,
  CI Direct Black 117.

You get deep, brilliant shades with good fastness properties.

• c) In order to further improve the light and rub fastness, is in a further stage containing an aqueous liquor
  100 g / l of the catalyst-containing active substance from Example 1 of DE 31 05 897 A1 and
  80 g / l tetramethylol melamine
  padded at pH 3.8 (adjusted with acetic acid) to a squeezing effect of 30%, and dried and fixed at 180 ° C. for 1 minute. The colorings achieved on glass result in above-average light fastness.

Example 9

A fabric made of 100% crystallized meta-aramid fibers (poly-isophthalamide - Nomex) of 280 g / m ² is washed with an aqueous liquor containing 100 g / l of the product according to Example 1b) and the pH of which is adjusted to 11 with NaOH 2-roll paddle with a squeezing effect of 60%, continuously impregnated and dried and fixed at 180 ° C for 30 s.

The substrate pretreated in this way is subjected to the padding process (2-roll pad, Squeezing effect 60%) with 40 g / l C.I. Direct Red 83 continuously imprinted niert and dried at 120 ° C for 90 s.

The colored substrate is then described as in Example 8c) - but with a squeezing effect of 60% - treated with fixative.

You get a rich color with good fastness properties.

Analogously to the dye mentioned in Example 9, the following dyes can be used:
CI Direct Violet 47, 66,
CI Direct Green 27, 31, 65, 67,
CI Direct Red 80, 95, 207,
CI Direct Yellow 39, 50, 98,
CI Direct Brown 103, 111, 113, 200,
CI Direct Black 62, 117, 118,
CI Direct Blue 77, 79, 90, 217, 251,
CI Reactive Violet 23,
CI Reactive Blue 23, 79,
CI Acid Blue 80, 113, 225, 297,
CI Acid Red 301, 399,
CI Acid Orange 156,
CI Pigment Yellow 14, 83,
CI Pigment Orange 34,
CI Pigment Red 112, 210, 101,
CI Pigment Violet 23,
CI Pigment Blue 15,
CI Pigment Green 7,
CI Pigment Black 7,
(CI pigments dispersed in water).

Claims (24)

1. Water-dilutable preparation characterized by a content of

• (a) an at least colloidally soluble, heat-fixable, polycationic polymer which contains at least one basic amino or imino group with at least one nitrogen-bonded hydrogen atom or an acid adduct thereof,

and

• (b) a water soluble lactam.

2. A preparation according to claim 1, wherein a) an aliphatic polycationic Polymer is wherein at least 50% of the heteroatoms are nitrogen atoms and in at least 50 mol% of the polymer the distances between the nitrogen atoms at most 5 carbon atoms, preferably at most 3 carbon atoms. 3. Preparation according to claim 1 or 2, wherein a)

• (a ₁ ) a reaction product of
  • (x ₁ ) cyanamide, dicyandiamide, guanidine or biguanide, with
  • x ₂ ) a primary or secondary mono- or polyfunctional aliphatic mono- or polyamine;
• (a ₂ ) a precondensate of (a ₁ ) with
  • (x ₃ ) epihalohydrin or dihalohydrin;
• (a ₃ ) a reaction product of (x ₂ ) with (x ₃ );
• (a ₄ ) a reaction product of (a ₃ ) with
  • (x ₄ ) 1,3-diaminopropanol-2

or

• (a ₅ ) a homopolymer
  • (x ₅ ) a mono- or di (meth) allylamine or a co- or terpolymer
  • (x ₆ ) one or more mono- and / or di (meth) allylamines and optionally tri (meth) allylamine

or a mixture of at least two of the polymers (a ₁ ) to (a ₅ ). 4. Preparation according to one of claims 1 to 3, characterized in that (b) is ε-caprolactam. 5. Preparations according to one of claims 1 to 4, containing per val amine or imine in (a) 0.1 to 10 val lactam (b). 6. Aqueous preparation according to one of claims 1 to 5, with a pH in Range from 4 to 14, preferably 5 to 12. 7. Concentrated preparation according to one of claims 1 to 6 with a Total (a) + (b) content of 5 to 80% and pH 5 to 8. 8. Use of the preparations according to one of claims 1 to 7 as (Pre) treatment agent. 9. Use according to claim 8 for organic high polymers, glass and Me tall. 10. Use according to claim 9 for fiber material made of glass or highly crystalline linen fiber-forming high polymers. 11. Process for the (pre) treatment of organic high polymers, metal or Glass, characterized in that a pre-containing (a) and (b) applied according to one of claims 1 to 7 on the substrate and the substrate treated in this way is subjected to a heat treatment. 12. The method according to claim 11 at pH 6 to 14, preferably 9 to 12. 13. Use of the substrates treated according to claim 11 or 12 as white tere substrates for finishing, preferably dyeings with anionic or non-ionic dyes.   14. Use according to claim 13, characterized in that with min stains a direct dye. 15. The method according to any one of claims 8 to 14, particularly claim 13 or 14, characterized in that with a polycationic fixer medium (k) post-fixed. 16. The method according to claim 15, characterized in that a preparation containing poly cationic fixative (k)
(k ₁ ) an at least colloidally soluble polycationic polymer which is a polymer (a ₁ ), as defined in claim 3, optionally precondensed with (a ₆ ) an optionally etherified N-methylolver compound capable of resin formation, and
(k ₂ ) an optionally etherified N-methylol compound capable of resin formation with at least one methylol-bonded basic nitrogen atom, or an acid adduct thereof,
used, where (k ₁ ) and (k ₂ ) may have reacted partially with each other and (a ₆ ) and (k ₂ ) may be the same or different from one another. 17. The method according to claim 16, wherein (a ₆ ) is an N-methylol derivative of a possibly cyclic urea and (k ₂ ) is an optionally etherified tri- to hexamethylolmelamine. 18. A preparation which is suitable as (k) in the process according to claim 17 and is characterized by a content of the components (k ₁ ') and (k ₂ '), where (k ₁ ') is a precondensate from (a ₁ ) and (a ₆ ), (k ₂ ′) is optionally etherified tri- to hexamethylolmelamine and (a ₆ ) is as defined in claim 17. 19. The method according to claim 16, 17 or 18, characterized in that fixed under acidic pH conditions and at temperatures of 80 ° C. 20. The method according to claim 19, characterized in that, at Ver use of N-methylol compounds, a catalyst for crosslinking  of these connections. 21. The method according to one of claims 8 to 17, 19 and 20 treated substrates.