DE102007028997A1 - Method for yellowing inhibition - Google Patents

Abstract

The invention relates to anti-yellowing polyamide-containing materials having a surface finish containing carbodihydrazide, a method of finishing and the use of appropriately prepared polyamide-containing materials.

Description

The The invention relates to highly yellowing-resistant polyamide-containing materials with a surface finish, the carbodihydrazide contains a method of equipment and the Use of appropriately prepared polyamide-containing materials.

polyamides have a sufficient number for a variety of applications high weather and age resistance. If desired, can in outdoor applications by a special coloring such as soot with the resistance still be further enlarged.

A Dyeing with soot easily avoids this in plastics often occurring problem of yellowing - she do not eliminate it. This becomes particularly significant if you do not want a very dark color of the finished plastic part is interested. In such cases, a yellowing, caused either by oxidative aging processes or already by the thermal treatment during the manufacturing process negatively noticeable.

One typical thermal treatment process in this context is thermofixing, in which the product concerned with hot water, Steam or dry heat subjected to a heat treatment is thereby shrinking, causing a later undesirable Dimensional change is prevented. Temperatures of 200 ° C and about it are quite common here.

One Another method is the Molden, in which the materials used by the heat of a (press) tool (ie Contact heat) are brought into a corresponding shape. This Method is used, for example, in the production of Brassieres.

The Yellowing does not only occur with untreated or optically brightened polyamide-containing material, which depends the type is usually yellow-white or milk-white.

Also in dyed polyamide-containing material - a Staining is usually with acid or metal complex dyes scored - this problem occurs. When colored Materials changes due to the yellowing of the original Color nuance in an undesirable manner.

Next a yellowing in the course of thermofixing or Moldens practice also various aggressive compounds such as nitrogen oxides (NOx), Ozone or chlorine-containing oxidants have a negative impact the weather or age resistance polyamidehaltiger Materials out.

Around Therefore, to suppress this problem of yellowing are various adjuvants have been developed. In this context It is especially important to note that some textiles, such as Brassiere or stockings, directly on the skin be worn and possibly used chemicals after the application have sufficient skin compatibility have to. Even for carpets, for example, is a health Safety of the chemicals used is desirable, since here too direct skin contact can take place.

EP 0 436 470 B1 describes in this connection a photochemical stabilization of dyed polyamide fiber materials by the use of various complexes of bisazomethines, acylhydrazones, semicarbazones or thiosemicarbazones of aromatic carbonyl compounds with copper as the central metal. The use of the toxic heavy metal copper, however, makes corresponding textile auxiliaries not only environmentally friendly but also health-friendly aspects of concern.

In JP 60-81370 describes a process for treating textile products of polyamide fibers or polyamide fiber blends which have been dyed with acidic or metal-containing dyes. The dyed textile products are treated with an antioxidant from the group of carbazides or hydrazines, in particular 1,6-hexamethylenebis (N, N-dimethylsemicarbazide) and adipic dihydrazide [ADH].

WO 2006/045721 A1 describes predominantly dicarboxylic acid bis-hydrazides, and of these in particular ADH, for improving the aging stability of undyed, optically brightened or natural or synthetic polyamide fiber materials dyed with reactive or disperse dyes, with the exception of metal complex dyes.

adversely in the last two procedures is in particular the fact that for a sufficient yellowing inhibition a relatively large Amount of textile adjuvant must be used. From the relative low water solubility of the excipient results another limitation.

The Object of the present invention was therefore a better effective antioxidant available for yellowing inhibition to deliver. Furthermore, the inventive Antioxidants significantly lower environmental and / or harmful Own properties. Both factors are natural also mutually, because an increased effectiveness implies yes, especially the use of a smaller amount of the antioxidant, which is usually a significantly lower environmental and / or health burden entails.

In A first embodiment of the invention is to Basic task solved by a polyamide-containing Material with a surface finish that Carbodihydrazide [CDH] contains.

Under Surface equipment within the meaning of the present Invention is a refinement of the relevant material understand, where the CDH in contrast to a surface coating also be located on the inner surface of the material can (caused for example by diffusion of the CDH under the equipment conditions).

surprisingly It was found that the yellowing inhibition by the Use of CDH compared to today's industry standard ADH is partly exceeded many times over.

Also it is particularly unexpected that appropriate materials whose Surface equipment of this relatively small molecule with only one carbon atom but includes four nitrogen atoms, none Cause skin irritation to OECD 404 or sensitization to OECD 406.

in the For the purposes of the present invention, it must be in the polyamide-containing Material not necessarily an untreated or uncolored Act material. It's just as possible that it's a visual one brightened or with reactive, acid, or dispersion Metal complex dyes is dyed material.

preferred Optical brighteners include the following compounds: on Stilbene based compounds, especially alkylation products 4,4'-diaminostilbene-2,2'-disulfonic acid; Connections, at of the two heteroaromatic radicals via an ethylene bridge connected to each other; Coumarin derivatives, in particular with an amino group or an N-heterocycle instead of the amino group; 1,3-diphenyl-2-pyrazolines; Naphthalimides, especially N-methyl-4-methoxynaphthalimide; Compounds containing a fused aromatic and a heteroaromatic especially 2,4-dimethoxy-6- (1'-pyrenyl) -1,3,5-triazine.

preferred Dyes are common dyes for polyamides, in particular acid and metal complex dyes.

The polyamide-containing material can, in addition to natural polyamides, in particular wool and / or silk also contain synthetic polyamides.

Examples for synthetic polyamides in the context of the present invention are: polyamide [PA] 4, PA 5, PA 6, PA 11, PA 12, PA 6.6, PA 6.10, PA 6.12, PACM 12, polyaramides such as Nomex and Kevlar, copolyamides PA 66/6 and PA 11/12 as well as block copolymers of polyamides and others Polymers, in particular polyethers.

When other constituents of the polyamide-containing material are in addition to polyamides other polymers, in particular polyesters, polysaccharides, in particular Cotton and / or viscose, polyurethanes and / or polyolefins and also for polymers usual auxiliaries and / or effect substances such as antistatic agents, colorants, flame retardants, fillers, Nucleating agents, pigments, reinforcing fibers and / or Plasticizer possible.

The Polyamide-containing material according to the invention can in the form of fibers, nonwovens, mesh, woven or knitwear and as such also be further processed into secondary products.

In a second embodiment, the object of the invention is achieved by a Process for finishing surfaces of polyamide-containing material, characterized in that the carbodihydrazide dissolved or dispersed in a liquid is brought into contact with the surface and subsequently the liquid is removed.

The Carbodihydrazide solution or dispersion can by the Pull-out or in particular by padding method (also padding called) are brought into contact with the surface. The padding process offers in comparison to the exhaust process especially under environmental protection aspects great benefits as it usually manages with smaller amounts of solvent. In addition, it also ensures a more homogeneous application.

The Carbodihydrazide can in the process according to the invention be applied before staining or optical brightening. However, it is preferred if this application step of a possible Brightening and / or coloring is downstream, there only so that the antioxidant used is optimally utilized.

When Solvent or dispersant for the carbodihydrazide one sets advantageously in the process according to the invention Water. Water not only has high solubility for CDH and the other usual ones in the fleet contained additives, but also the advantage of a high environmental impact.

The Quantity of CDH in the fleet should be within a range of 0.1 g / L to 20 g / L, in particular from 0.5 to 10 g / L. Lower concentrations have the disadvantage that the CDH-containing liquor would have to be applied several times to the polyamide-containing material, to achieve the desired efficiency. higher Concentrations are for reasons of high effectiveness not mandatory.

Next Carbodihydrazide, the liquor used may be other common Process or effect chemicals, in particular wetting agents, plasticizers, oleo and / or hydrophobizing additives or thickeners contain.

To the application of the carbodihydrazide can still a heat-setting or followed by a molding step, wherein the antioxidant effect of the carbodihydrazide. It is possible that the fleet mainly constituting solution and / or dispersants in the course of these thermal processing steps which, of course, favors in so far is, as in this way the number of needed Reduce process steps. The solution and / or dispersing agent can also be previously in a separate Step away.

A Another embodiment of the present invention consists in the use of a solution containing carbodihydrazide or dispersion as a textile auxiliaries.

there In particular, it has been shown that CDH treated textiles on the basis of polyamide a very high stability the yellowing inhibition against thermal influences and / or oxidizing agents. Under thermal influences Here are in particular treatment method of polyamide-containing Understand materials at higher temperatures be performed, such as heat setting or Molden. Oxidizing agents are in particular nitrogen oxides, Ozone or chlorine-containing oxidizing agents.

embodiments

In In the following examples, the degrees of whiteness are in Berger units specified.

Example 1: Treatment of untreated polyamide

An undyed knitted fabric PA 6.6 was padded with an impregnating solution at 100% liquor pickup and dried for 30 s at 120 ° C, then in Example 1.A) for 45 s at 200 ° C heat-set or in Example 1.B) for 45 s at 210 ° C gemoldet recipe 1 2 3 4 5 6 7 8th 9 ADH (comparative example) g / L 1 2 4 8th CDH (according to the invention) g / L 0, 25 0,5 0 1 2 Whiteness measurement after drying 80 80 80 80 80 80 80 80 80 1.A) after thermofixing 48 53 65 66 66 67 71 75 77 1.B) after Molden 43 50 61 63 64 55 57 67 67

Example 2: Treatment of optically brightened polyamide

Polyamide 6.6 knitted fabric was lightened at a liquor ratio of 1:10 with 1.0% Tuboblanc ^® MA. The pH was adjusted to 4 with acetic acid, the treatment was carried out at 95 ° C and 30 minutes. Thereafter, rinsed hot and cold and dried at 120 ° C.

Subsequently was on the padder at 100% liquor pickup with the specified amount treated with antioxidant, taking the pH with acetic acid was set to 5. It was dried again at 120 ° C.

After thermofixing, basic white [GW] and fluorescence [F] are assessed. recipe 1 2 3 4 5 6 7 8th 9 ADH (comparative example) g / L 2 2 2 CDH (according to the invention) g / L 1 1 1 Whiteness measurement GW after drying 77 77 77 77 77 77 77 77 77 F after drying 76 76 76 76 76 76 76 76 76 2.A) GW after heat-setting 190 ° C / 45 s 62 70 74 2.A) F for heat setting 190 ° C / 45s 64 73 75 2.B) GW to Molden 210 ° C / 45 s 48 67 74 2.B) F to Molden 210 ° C / 45 s 51 69 74 2.C) GW to Molden 220 ° C / 45 s 25 61 72 2.C) F to Molden 220 ° C / 45 s 32 64 70

Example 3: Treatment of colored Polyamide (Molden)

Polyamide 6.6 knitwear was dyed at a liquor ratio of 1:10 with acid dyes. At the beginning of cold 2 g / L Sarabid EP and 0.5 g / L Meropan EF were initially added after 10 min 0.02% of a Bezanyl ^® -Säurefarbstoffes, after a further 10 min at 2 ° C / min to 98 ° C heated , Treated for 30 min at this temperature, then cooled to 60 ° C at 2 ° C / min and rinsed.

As dyes Bezanyl ^® Red E-3G 200 Bezanyl ^® Blue E2R 200 Bezanyl ^® Violet FB or Bezanyl ^® Orange N-GR were used.

To drying at 120 ° C were 0.5, 0.75 or 1 g / L CDH and as Comparative Example 1 or 2 g / L ADH in pad at 100% Fleet absorption applied, dried at 120 ° C and at 210 ° C in each case 30, 60 or 120 s gemoldet.

Result:

ADH and CDH worked very efficiently compared to the patterns without Antioxidant, 1 g / L ADH improved the result, good results was achieved only with 2 g / L ADH or the invention CDH already at 0.5 to 0.75 g / L. 1 g / L CDH worked best.

Example 4: Treatment of colored Polyamide (thermosetting)

The Treatment was carried out analogously to Example 3, but instead of Molden at 200 ° C and 210 ° C each 30 or 60 s heat-set.

Result:

With the hydrazides were well inhibited by the hue change. 1 g / L CDH scored the same, sometimes even slightly better results as the comparative example with 2 g / L ADH.

Example 5: Thermofixing of polyamide and subsequent dyeing

The Treatment was carried out analogously to Example 4, but was first the Antioxidant applied, then heat-set and dyed at the end.

The Result reflected the same tendency as in Example 4, 1 g / L CDH was comparable in effect or better than 2 g / L ADH.

Example 6: NO _x - yellowing

A product of 40% of PA 6/60% elastane ^® with a base White of 81 Berger units was padded with antioxidant at 50% wet pickup, and once adjusted without pH adjustment and once with citric acid to a pH of 5.5 was then dried at 120 ° C each.

The NO _x fastness was tested according to EN ISO 105-G01 "NO _x gasification heavy" and assessed by gray scale (1 worst, 5 best). recipe 1 2 3 4 5 6 7 8th 9 ADH (comparative example) g / L 10 20 10 CDH (according to the invention) g / L 10 1 5 10 pH adjusted to 5.5: x x x x x NO _x gasification heavy grading 2 2-3 3 4 3 3-4 3-4 4 4-5

Result: CDH was many times better than ADH.

Example 7: Storage stability and Effect stability of aqueous CDH

It was analogously to Example 1 instead of pure CDH 10 times the amount a 10% solution used previously 2 months at Room temperature was stored.

All Results are in the range of Example 1, d. H. a 10% solution of CDH was sufficiently storage stable to settling and achieved at appropriate use concentration in the textile application the same effect.

Example 8: Sensitization and skin irritation

One untreated raw ash PA 6.6 was cleaned in acetone, then Washed thoroughly with water and dried. After that 3.75 g / L CDH were padded at 100% liquor pickup and at 120 ° C dried. Subsequently, at 200 ° C for 30 s gemoldet. The product was based on sensitization to OECD 406 and skin irritation tested according to OECD 404.

The Result was "non-sensitizing" and the primary Skin irritation index (Primary Skin Irritation Index - PSI) was 0, so not irritating to the skin.

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• - EP 0436470 B1 [0010]
• - JP 60-81370 [0011]
• WO 2006/045721 A1 [0012]

Claims (20)

Polyamide-containing material with a surface finish, which contains carbodihydrazide. Material according to claim 1, characterized characterized in that the polyamide-containing material is dyed, uncolored or optically brightened. Material according to one of the claims 1 or 2, characterized in that the polyamide-containing material natural polyamides, in particular wool and / or silk contains. Material according to one of the claims 1 or 2, characterized in that the polyamide-containing material contains synthetic polyamides. Material according to one of the claims 1 to 4, characterized in that the polyamide-containing material other polymers, especially polyesters, polysaccharides, polyurethanes and / or polyolefins. Material according to one of the claims 1 to 5, characterized in that it is in the form of fibers, nonwovens, Mesh, woven or knitted fabric is present. Process for finishing surfaces of polyamide-containing material, characterized in that that dissolved or dispersed in a liquid Carbodihydrazid brings into contact with the surface and then remove the liquid. Process according to claim 7, characterized characterized in that the carbodihydrazide solution or dispersion by exhaustion or in particular by padding method on the Surface applies. Method according to one of the claims 7 or 8, characterized in that the carbodihydrazide is present but especially after staining and / or optical brightening applied. Method according to one of the claims 7 to 9, characterized in that a polyamide-containing material used, which natural polyamides, especially wool and / or silk. Method according to one of the claims 7 to 9, characterized in that a polyamide-containing material which contains synthetic polyamides. Method according to one of the claims 7 to 11, characterized in that a polyamide-containing Material that contains other polymers, in particular polyesters, Contains polysaccharides, polyurethanes and / or polyolefins. Method according to one of the claims 7 to 12, characterized in that as a polyamide-containing Material fibers, nonwovens, mesh, woven or knitted fabric uses. Method according to one of the claims 7 to 13, characterized in that as a solution or Dispersant for the carbodihydrazide water used. Method according to one of the claims 7 to 14, characterized in that one uses a fleet, the amount of 0.1 g / L to 20 g / L, in particular from 0.5 to 10 g / L, contains carbodihydrazide. Method according to one of the claims 7 to 15, characterized in that one uses a fleet, the usual process or effect chemicals, in particular Wetting agents, plasticizers, oleo and / or hydrophobizing additives or thickener contains. Method according to one of the claims 7 to 16, characterized in that the goods after treatment thermofixed with carbodihydrazide or moldet. Use of carbodihydrazide or one of these containing solution or dispersion as a textile auxiliary. Use according to claim 18 for the stabilization of Textiles against thermal influences and / or Oxidants. Use according to claim 19 for the stabilization of Textiles to nitrogen oxides, ozone or chlorine-containing Oxidants.