EP2347050A1

EP2347050A1 - Multifunctional, responsive functional layers on solid surfaces and method for the production thereof

Info

Publication number: EP2347050A1
Application number: EP09775746A
Authority: EP
Inventors: Oliver Marte; Martin Meyer; Murray Height
Original assignee: HeiQ mATERIALS AG
Current assignee: HeiQ mATERIALS AG
Priority date: 2008-07-15
Filing date: 2009-07-13
Publication date: 2011-07-27
Also published as: CN102165114A; WO2010006457A1; CN102165114B; CH699127A2; US20110250409A1; CH699118A1

Abstract

A multifunctional, responsive functional layer (5) on a substrate, particularly textiles, paper and plastic materials, comprises at least one first and a second functional component (1, 2), of which at least one of the second functional components (2) meets the chemical-functional and constitutional requirements for responsive behavior and thereby can be reversibly switched by an outer stimulus. The first and second functional components (1, 2) differ with respect to the intrinsically specified properties thereof and are matched to each other, wherein at least one of the functional components on the substrate (3) is present as a physical-chemical compound. The invention further relates to methods for producing the multifunctional, responsive functional layer (5), which enable the combination of functions, such as moisture management, soil release, antistatic, hydrophobicity, hydrophilicity, oleophobicity, controlled release, and conductivity.

Description

Multifunctional, responsive functional layers on solid surfaces and methods of production

The invention relates to multifunctional, responsive functional layers on solid surfaces according to patent claim 1 and to a method for producing the same according to patent claims 18 to 20.

The production of multifunctional layers on solid matrices such as textile, paper and plastic materials is becoming increasingly important and is the subject of current research and development projects. Various combined functional examples such as e.g. Flame-retardant and dirt-repellent or non-iron and antistatic etc. are already in practical use and are also described in the specialist literature [1].

In the list below are the documents, on the basis of which the state of the art is explained below:

[1] S. Duquesne et al., Multifunctional Barriers for Flexible Structure, (2007), p. 39-43,

63-71, 109-124, Springer Berlin, Heidelberg, New York

[2] http://en.wikipedia.org/wiki/Phase_Change_Material

[3] St. Galler Tagblatt, Friday, June 6, 2008

[4] V. Papaefthimiou, R. Steitz, G.H. Findenegg, Responsive Polymer Layers, Chem.

Our Time, (2008) 42, 102-115

[5] J. Rühe, M. Ballauf, M. Biesalski et al., Polyelectrolyte brushes, Adv. Polym. Be

(2004) 165, pp. 79-150

[6] M. Motornov, R. Sheparovych et al., Stimuli Responsive Colloidal Systems from

Mixed Brush-Coated Nanoparticles, Advanced Functional Materials (2007) 17, p. 2307-

2314

[7] D. Hegemann, M.H. Hossain, D.J. Balazs, Nanostructured plasma coatings to obtain multifunctional textile surfaces, Progress in Organic Coatings 58 (2007) p. 237-

240 [8] M. Weder, A. Satir, W. Federer, When Clothes Adapt to Man,

Swiss Federal Laboratories for Materials Testing and Research, Media Information,

Dübendorf, September (2002)

[9] W.D. Schindler, PJ. Hauser, Chemical Processing of Textiles, CRC Press (2004), p.

87-96, Boca Raton Boston New York Washington, DC

[10] F.D. Evans, H. Wennerström, The Colloidal Domain, Wiley-VCH (1999) p.

606-608 New York

[1 1] H. Mollet, A. Grubenmann, formulation technology, p. 47-55, Wiley-VCH Verlag

(2000) Weinheim, New York

[12] M. Tanaka, E. Sackman, Polymer-supported membranes as a mode of the cell surface, Nature (2005) 437, pp. 656-663

[13] A. Janshoff, C. Steinern, Transport across artificial membranes on an analytical perspective, Anal. Bio. Chem. (2006) 385, pp. 33-51

[14] R. v. Klitzing, Intemal structure of polyelectrolyte multilayer assemblies, Phys.

Chem. Chem. Phys. (2006) 8, pp. 5012-5033

[15] K. Glinel, C. Dejugnat, M. Prevot et al., Responsive polyelectrolyte multilayers,

Colloid Surf. A. (2007) 303, pp. 3-13

[16] C. Wu, S. Zhou, First Observation of the Molton Globule State of a Single

Homopolymer Chain, Phys. Rev. Lett. (1996) 77, pp. 3053-305

[17] W. Barthlott, C. Nohuis, Only what is rough becomes self-clean, technical

Rundschau No. 10, (1999) p. 56-57

[18] L. Feng et al., Petal Effect: A Superhydrophobic State with High Adhesive Force.

Langmuir Vol. 24, (2008), pp. 4114-4119

The examples mentioned in document [1], effects obtained by a coating, are permanently present. When using phase-change materials [2] (eg Micronal ^® PCM from BASF) in multifunctional layers, the heat-regulating effect triggered by these materials is reversible. The phase-change materials are microcapsules whose contents are, for example, an electrolyte or electrolyte mixture or low-melting polymers. During the phase change (solid / liquid or liquid / solid), heat is absorbed or released, allowing temperature control through the equipment made with Phase-Change Materials. In recent work [3] are eg protective blankets for horses which are both highly reflective and phase change materials in the

Coating included.

The literature describes further polymer materials that can be switched on and off reversibly by an external stimulus, so-called responsive

Polymeric materials, but not their use in multifunctional layers [4], [5],

[6].

The manufacturing principle of multifunctional layers on textiles used today consists in most cases in the mixing of at least two functional products or composites in an application liquor or in the sequential application of the functional products to the substrate to be treated. In the following, the term substrate will also be used to represent various solid-state arrays, such as e.g. Textile, paper and plastic or synthetic fiber materials used. Known methods of producing multifunctional layers, according to one of the aforementioned principles, are described in the following documents: a) Functional equipment with a one-step procedure [1]:

Antistatic, water, oil and dirt repellency, flame retardancy, iron-free etc. b) Sequential application of functional layers (two-step procedure): textile surface ¹ (WO 02/075038 A2).

Another very up-to-date process technology for the production of multifunctional layers is provided by plasma technology [1], [7].

Two of today's preferred combined functions are moisture and heat regulation on the human skin through clothing and its equipment. These functions have been extensively researched and discussed over the past decade [8]. For this purpose, functional models have been developed and implemented for various fields of application, which use a great many resources, from fiber material through fabric construction to the fabrication technology. Another noteworthy dual function is in the term 'Soil release' [9], which both the dirt repellency and the Wiederwashbarkeit sorbed dirt substances are required as functions.

Another multifunctional layer, which is particularly desirable for health and safety clothing and bed linen, includes dirt repellent and water repellent bactericidal and antistatic function.

Major disadvantages of all mentioned multifunctional layers are their production principle with the separately formulated functional products or composites and the very often limited compatibility with the other existing liquor ingredients.

Another disadvantage of the production of various multifunctional layers is the multistage nature of the process, wherein very cost-intensive process steps such as drying and condensing must be carried out at least twice.

The already mentioned technical disadvantages also include the very often limited washing and usage properties, especially in the case of functional layers on synthetic fibers and plastics. As these drawbacks become increasingly important, they are a major reason for the reluctant market acceptance. The main economic disadvantage lies in the high cost of the individual functional products with their more or less complex manufacturing techniques.

It is the object of the invention to develop on solid surfaces, in particular on textiles, to be applied, equipment-based multifunction principle and manufacturing process, which layer intrinsically fulfills at least two different functions. Examples of such functions are: Moisture Management, Soil Release, Antistatic, Hydrophobicity, Hydrophilicity, Oleophobia, Controlled Release, Conductivity etc.

Another object is the realization of high demands on the typical performance characteristics of the multifunctional layer, wherein the requirement for a high wash resistance is common to all multifunctional layers. The layer-specific properties are based on the individual functions to be fulfilled by the coating layer.

The object of the invention is achieved by the use of bipolar and / or arnphiphilic compounds suitable for barrier, in particular for membrane formation, in combination with responsive compounds to be switched by a stimulus or polymers, which together form a multifunctional, responsive functional layer. According to the invention, the property of the multifunctional, responsive functional layer as an overall system or at least one of the functions must be reversibly switchable (responsive) by an external stimulus. The responsive property of the multifunctional, responsive functional layer can be predetermined by one, several or only by the combination of at least two functional components. Due to the geometric arrangement of the barrier layer (also referred to as membrane or boundary layer) and the responsive polymer layer on a solid matrix resulting from separation assembly [10], as well as the chemical combination of the barrier layer with the responsive polymer layer, the overall system, ie the multifunctional, responsive one, responds Functional layer, to an external stimulus according to the properties of the responsive polymer. With the application of different chemical-functional and constitutional compounds for the construction of multifunctional, responsive functional layers, their geometric differentiated arrangement in the layer is also specified. This results in self-dynamics by assembling, due to the prevailing interface forces in such a way that, for example, the responsive polymer layer on the substrate or the solid matrix and the membrane or barrier structure forming compound or the polymer forms the air-oriented layer. In this sense, the responsive polymer layer and the barrier layer behave cooperatively with respect to their properties.

Chemically-functional compounds have reactive groups such as amino, hydroxy, carboxyl, carbonyl, epoxy, isocyanate groups; Constitutional features of the compounds are those which are distinguished by their physical or structural properties, such as bipolarity, planarity or chirality.

Responsive polymer layers are characterized by an 'answer' to an external stimulus (also called a trigger). Hence the term 'responsive', whose origin in Latin is responder = answer. Responsive behavior means that the stimulus-induced system change is reversible and repeatable.

The invention will be explained in more detail with reference to the figures. Show it: Fig. 1 Schematic structure of a multifunctional, responsive functional layer with two functional components, one of which is reversibly switchable by an external stimulus.

2 Schematic structure of a multifunctional, responsive functional layer with two functional components, wherein the lipophilic functional component sits on the responsive functional component and the temperature forms the external stimulus.

FIG. 3 Schematic structure of a multifunctional, responsive functional layer with two functional components, wherein the lipophilic functional component sits on the responsive functional component and the moisture content forms the external stimulus.

1 shows the schematic structure of a multifunctional, responsive functional layer with two functional components, one of which is reversibly switchable by an external stimulus.

On a substrate 3, or a solid surface or a solid matrix, there is a first functional component 1, which is physically-chemically bonded to the substrate 3. A second functional component 2 is located next to the first functional component 1 and is also physically-chemically connected to the substrate 3. The second functional component 2 consists of a responsive, polar polymer component, on which water molecules 4 are attached. The first functional component 1 consists of a hydrophobizing polymer. First and second functional components 1, 2 form a responsive functional layer 5, or a finishing layer, whose responsive behavior is explained below. In this functional layer, the responsive and hydrophobicizing polymer components 1, 2 are isolated from each other in an isolated manner due to the phase separation forced during application and fixation. While the hydrophobing functional component 1 forms largely rigid chains to the gas phase (air) by means of assembly, the chains of the responsive functional component 2 are greatly stretched with increasing water content, resulting in a hydrophilic layer dominance of the responsive functional layer 5. Water molecules 4 'located in the gas phase are deposited on the responsive functional component 2, which is indicated by an arrow 6. This hydrophilic layer dominance is at a normal temperature in front.

An increasing temperature causes an increasing dehydration and deswelling of the responsive functional component 2 ', or of the responsive polymer, wherein the stretched chains collapse or wrinkle. The previously bound water molecules 4 evaporate and a new access of water molecules 4 'is considerably more difficult, which is indicated by the arrow 6'. The responsive functional component 2 'retreats next to the hydrophobing functional component 1', with which now the substantially rigid chains of the functional component 1 'or of the hydrophobicizing polymer dominate the surface of the functional layer 5'.

The external stimulus is the temperature with which the hydrophilicity or the hydrophobicity of the surface of the functional layer 5, 5 'is reversibly switchable. This is indicated by a double arrow 7.

The barrier or the barrier layer will be described below. Bipolar monomers and polymer compounds are capable of forming interfacial structures, particularly membrane layers, from micelles and / or vesicles by assembling on solid or liquid surfaces. Depending on the polarity of the surface (hydrophilic or hydrophobic) on which the micelle or vesicle spreads, the thermodynamically induced separation leads to a vice versa directed (hydrophobic or hydrophilic) orientation with respect to the air [11], [12], [13 ]. Behavior comparable to micelles or vesicles, for example, shows bipolar compounds emulsified in water and amphiphilic polymers after application to a solid matrix. Typical examples of such compounds are specially formulated fat-modified (C ₃ -C ₂₄ , preferably C ₈ -C ₁₈ ) formaldehyde, polyacrylate and polyurethane resins and fluorocarbon resins (C ₂ -C ₁₂ , preferably C ₄ -C ₈ ), whose backbones are also, for example Acrylic or urethane based. Further possibilities are the use of metal salts of higher fatty acids (C ₃ - C _24, preferably C ₈ - C ₁₈₎ and, for example, polysaccharides or quat groups containing compounds esterified fatty acids (C ₃ - C _24, preferably C ₈ - C _18).

Another amphiphilic class of compounds are block polymers containing both hydrophobic and hydrophilic segments. The hydrophobic segments are often silicone and fluorocarbon resin based; the hydrophilic preferably polyoxyethylene and polyoxypropylene based. The amounts of the mentioned compounds Textiles are 0.1-5%, preferably 0.2-2.0% of the active substance, based on the dry weight of the textiiguts to be finished. The mentioned classes of compounds are used in part for the hydrophobization of textile fiber materials and fabrics. The barrier layers produced by fabric assembling with such compounds on fabric surfaces fulfill the majority only one equipment-specific function, namely a hydrophilization or hydrophobing of the textile material. By fixing the bipolar barrier-forming compound (monomer and / or polymer) on solid or liquid surfaces, their orientation possibility is limited by the rigidity of the orienting molecular chains and their proximity to the solid-state matrix. This in turn results in loss of effects.

This disadvantage is overcome by the incorporation of e.g. Spacers between the solid-state matrix and the barrier layer significantly improved. Such barrier layers, in particular membrane layers with 'spacers' to the solid matrix are referred to as tethered membranes' [11], [12].

According to the invention, responsive polymers are used as spacers that can be reversibly switched by external stimuli between differently shaped polymer states (e.g., stretched or creased form of the polymer).

Corresponding, described in the literature, the triggering trigger triggers are physical and / or chemical, layer extrinsic factors such as temperature, pH, electrical charge and moisture. Other stimuli triggering the switching process are the ionic strength of an electrolyte solution or that of the polymer surface itself [4], [12], [13].

Depending on the design and the task to be fulfilled, the responsive functional layers according to the invention can be switched by mechanical forces in the range from 10 ^-7 Newton (N) to several Newton (N), as well as by electromagnetic waves (electromagnetic radiation) of very different spectral ranges and their strength. As examples, the light of a certain wave range and its intensity is mentioned.

The factors mentioned may occur during use of the materials provided with responsive functional layers, such as washing, storage, Ironing, drying, cleaning, etc. Other extrinsic, stimuli provoking situations are stress (blood pressure, sweat, etc.), high temperatures, oil and chemical contact.

At the same time, additional functionalities can be generated by incorporating a spacer layer. Very important are e.g. that of a water reservoir between the solid-state matrix and the hydrophobically dominated barrier layer, for example, or that of an antistatic and / or antimicrobial function.

Examples of responsive polymers are polyethylene oxide and polypropylene oxide derivatives and their copolymers, ethoxylated and propoxylated polysaccharides, polyacrylamides or polyacrylates, and polyelectrolytes, such as e.g. ionic polysaccharides, acrylamides or acrylates.

The relative amounts used are 0.05-5.0%, preferably 0.1-2.0% of the active substance, based on the dry weight of the textile material to be finished.

In addition to the preferred one-step procedure for the production of multifunctional, responsive functional layers according to the inventive principle, a two-stage or multistage production process [14], [15] can also be practiced, even if the additional costs are accepted. Such an operation is appropriate, for example, in the construction of a bilayer structure for realizing a high reversible water storage capacity, thereby achieving a high degree of heat regulation. In such a case, first the responsive spacer layer is applied by an impregnation process, while the barrier-forming functional component or the functional composite is subsequently applied on one or two sides. As one-sided application techniques, for example, patting, spraying and doctoring are available, while the two-sided application is preferably carried out by dipping. The one-sided or two-sided barrier coating application is based on the intended use of the textile material. In one-sided barrier layer application, the tissue side opposite the barrier layer is hydrophilic and able to absorb water as a liquid phase. In a two-sided barrier layer application, water transport into the hydrophilic responsive functional layer takes place predominantly via the gas phase. 2 shows the schematic structure of a multifunctional, responsive functional layer with two functional components, wherein the lipophilic functional component sits on the responsive functional component and the temperature forms the external stimulus.

On the substrate 3 is the second functional component 2, which is physically-chemically bonded to the substrate 3 and consists of a responsive, polar polymer component, on which water molecules 4 are deposited. The first functional component 1, namely a lipophilic component, is fixed physically-chemically on the responsive polymer component. The second functional component 2 is also referred to as a spacer polymer.

First and second functional components 1, 2 form a responsive functional layer 5, or a finishing layer.

If the substrate 3 is a garment or a fabric, the responsive functional layer 5 located thereon at normal temperature (no physical exertion) allows only a small water transport, which is indicated by a narrow arrow 8. During physical exertion and the associated increase in temperature allows the responsive functional layer 5 'excellent water transport, which is indicated by a broad arrow 9.

The external stimulus is the temperature with which the hydrophilicity or the hydrophobicity of the surface of the functional layer 5, 5 'can be reversibly switched or triggered. This is again indicated by the double arrow 7.

The functional layer 5 may also contain a plurality of first functional components 1 and a plurality of second functional components 2. It is by no means limited to a single first and second functional component.

By the single-stage application of bipolar, barrier-forming compounds with responsive polymer compounds as spacers on textiles, functional layers for moisture transport and heat regulation of body-worn textiles are produced according to the invention. The responsive polymer layer has the property of a water reservoir whose storage capacity is determined by the temperature. By using responsive spacer polymers, the properties typical for this layer must be switched on or off. Of particular importance in this case is the temperature as a trigger, which respon- sive polymers to their hydration or dehydration leads. The responsive polymer layer, when appropriately geared, will exhibit a significant and reversible change in the chain arrangement, which may vary from the stretched to fully nipped shapes.

According to this example, the use of a responsive polymer is of interest, which binds water at lower body temperatures (<30 ^° C.) and precipitates water at higher temperatures as a result of increasing insolubility [16]. Since the released water evaporates more or less quickly according to the prevailing conditions and energy is withdrawn from the system due to the evaporation enthalpy to be expended, cooling of the textile and thus of the skin is the consequence.

The functional layers produced in this way on two sides show to the outside, e.g. In the case of textiles worn close to the body, the skin has a hydrophobically dominated and therefore dry behavior. The water released by transpiration from the body is mainly transported via the gas phase into the spacer layer, stored and, depending on the temperature conditions, without noticeable moisture on the skin, released very quickly to the environment.

By varying the mass ratios between the hydrophobically dominated barrier polymer and the hydrophilic-dominated responsive polymer in the dispersion / emulsion applied to a solid matrix, a miscibility gap can be formed by removal of the homogeneous phase (eg water) during the layer fixation. Such miscibility gaps can also be formed by other stimuli such as electrical charges or electrolyte. Due to the miscibility gap, the polar dominated, amphiphilic polymer forms water-transporting polymer bridges, comparable to the transmembrane proteins in biological membranes. Another special feature of this functional layer according to the invention is the predominance of low to medium relative humidity (<80%) hydrophobicity, which means an extremely water-repellent property, and at higher relative humidity (> 80%) increasing hydrophilicity, which is excellent leachability of dirt means. By incorporating micro- and / or nanoparticles into the functional layer or into the composite, responsive, self-cleaning surfaces are to be produced. Both in the described and in the following application form, l_otus [17] and petal effect [18] layers are intrinsically present, wherein the moisture or the corresponding water content of the functional layer is the trigger for switching the respective function. SoM release functional coatings based on this principle show high effect levels.

Another application of this principle is that of a water collector. In this case, for example, the hydrophilic-dominated responsive polymer is immobilized on several μm-sized particles (eg SiO ₂ ) and dispersed in water together with the hydrophobic membrane polymer and corresponding dispersants. By taking place after the application of drying occurs phase separation to form hydrophilic condensation nuclei. These are capable of sorbing water from the gas phase with decreasing ambient temperature on one side (top side) of the textile material and transported as a liquid phase through the present due to the phase separation bridges of polar polymer associates on the back or drain on the top of the fabric allow. Here it leads to the formation of drops and can be used, for example, as drinking water. As the temperature increases, the responsive polymer is rehydrated to revert to the hydrophobic domain. Application examples include camping, watering crops and using as a military survival kit.

FIG. 3 shows the schematic structure of a multifunctional, responsive functional layer with two functional components, wherein the lipophilic functional component sits on the responsive functional component and the moisture content forms the external stimulus.

On the substrate 3 is the second functional component 2, which is physically-chemically connected to the substrate 3 only at the two locations 10, 10 '. The second functional component 2 consists of a responsive, polar polymer component as a spacer layer. The first functional component 1, namely a hydrophilic component, is physically chemically fixed on the responsive polymer component. First and second functional components 1, 2 form a responsive functional layer 5 or a finishing layer, eg a soil release functional layer. layer.

The responsive functional layer 5 is water-repellent at a low moisture content, which is indicated by the water molecule 4 'and by the arrow 6'. Any dirt 11 or dirt particles remain on the hydrophobic surface of the functional layer 5 adhere.

Due to the water absorption of the responsive polymer and the preferably weakly alkaline pH value, swelling or stretching of the spacer polymer 2 'occurs. As a result, the distance between the first functional component 1 'or the hydrophobic chains fixed thereon opens. As a result, the access of water is made possible, as indicated by the water molecules 4 and the arrow 6. Thus, the cleaning effect of the functional layer 5 'and thus of the substrate 3 is made possible by any soiling 11, which is indicated by an arrow 12. The external stimulus is the moisture content of the functional layer 5, 5 ', which is reversibly switched or triggered by the washing process or the drying. This is again indicated by the double arrow 7.

The 'Soil release' function consists of two opposing functions. On the one hand, this is the dirt-repelling function and, on the other hand, the best possible washability of once soiled surfaces. The principle for the realization of the two functions is the use of a hydrophobic membrane-forming polymer in combination with a hydrophilic-dominated responsive polymer. The use of specially modified cellulose derivatives as a spacer polymer, this is present at low humidity in geknäter, more or less unswollen form. In the presence of water, for example during the washing process, a water access can be detected by existing defects in the barrier layer, which has a significant swelling of the spacer layer and thus an opening of the membrane layer result. As a trigger for triggering the responsive effect is used in this case, the increased water content of the spacer layer.

The spacer layer is not necessarily a responsive polymer layer; Thus, the at least one first functional component may also be formed as a spacer layer, for example as a lipophilic functional component.

As a barrier layer forming polymers are preferably fluorocarbon resins with C ₄ - C ₁₂ chains and as responsive polymers polyelectrolytes such as carboxylated poly- saccharides and / or acrylic acid derivatives applied. The amounts used of the barrier layer forming compounds is 0.1 - 3.0%, preferably 0.2 - 1.5% and that of the responsive polymer 0.05 - 5.0%, preferably 0.1 - 2.0% of the active ingredient, based on the dry weight of the textile material to be finished.

The responsive nature of a corresponding spacer polymer can also be used to achieve high oil and gasoline repellency of e.g. Protective clothing can be used. Of particular importance is the high oil and gasoline rejection in protective suits for the police, fire and the military, as in appropriate operations the risk of fire is the biggest threat. While in the unswollen spacer polymer once penetrated oil or gasoline can distribute freely, the swollen spacer polymer forms a second, for oil and gasoline impermeable barrier layer. The swelling of the responsive spacer layer already takes place through human perspiration, with which in this case the relative humidity of the body-near climate is the stimulus for the formation of the desired function. This behavior can be repeated as often as desired after drying the protective suit.

In addition to the barrier-forming and the responsive polymer component, a functional layer according to the invention contains further ingredients and thus forms a multifunctional composite.

Crosslinkers: The crosslinkers used are formaldehyde resins, in particular melamine and ethyleneurea derivatives, such as, for example, Knittex FEL (Huntsman), free and blocked isocyanates, e.g. Phobol XAN (Huntsman), aziridine compounds, e.g. XAMA 7 (flevo chemistry) and multifunctional glycidyl compounds, e.g. Isobond GE 100 (Isochem) used. Depending on the molecular weight and the reaction group content of the crosslinker, the mass quantities vary in the range of 0.05-1.5%, preferably 0.1-0.5%, of the active substance, based on the dry weight of the textile material to be finished.

Catalysts: The catalysts should be selected specifically for the reaction system. In the case of formaldehyde resins but also in the use of glycidyl compounds, metal salts and preferably carboxylic acids are used. Typical catalysts for formaldehyde resins are magnesium chloride, aluminum chlorohydrate, citric acid acid and tartaric acid. The quantities used for metal salts in the liquor are 1 to 25 g / l, preferably 5 to 15 g / l. The acid concentrations to be set in the liquors are in the range of 0.1-10 g / l, preferably 0.5-4 g / l.

When using isocyanates but also of glycidyl compounds, amines, preferably tertiary amines such as e.g. 1, 4-diazabicyclo (2.2.2) octane (DABCO), triethanolamine, 1, 2-dimethylimidazole and benzyldimethylamine (BDMA) for use. The amounts used are 0.5-15 g / l, preferably 2-10 g / l.

With the measures described above, a new generation of finishing processes is realized, which, according to the underlying bionic concept, leads to improved moisture and temperature control through body-worn textiles.

Example 1: Soil release functional layer.

This example relates to the preparation of a soil release function on textiles, with a responsive-acting functional component, characterized by a repellency of hydrophilic and hydrophobic substances and by a simultaneously present good washability of any residual dirt.

For the production of dirt-repellent shirts, a yarn-dyed blended fabric with a grammage of 120 g, consisting of 70% polyester and 30% cotton, is applied to a soil release liquor formulation. It is a responsive functional layer which on the one hand repels water and oil and on the other hand can be cleaned as part of a washing process. The stimulus for switching the respective function (reject or mobilize) is the moisture content of the functional layer. While up to a moisture content of about 8%, based on the dry weight of the finishing layer, this has a high water, oil and soil repellency occurs when further increasing the water content (typically in the washing machine), a strong reduction of the repellent character. With the reduction of water, oil and soil repellency increasingly dominated by the hydrophilic nature of the functional layer, whereby the dirt removal is much easier. The subsequent drying of the garment returns to its original state, with high water, oil and dirt repellency. The production of the functional layer takes place by the application of a fleet containing all functional components. This is applied to the fabric by means of an impregnation process with a pick-up of 65%. By the subsequent drying of the fabric at about 120 ⁰ C and condensation at 150 ⁰ C, the functional layer is fixed wash-resistant on the fabric. The liquor formulation is listed in Table 1.

Tab. 1 Fleet formulation

The equipped according to the method described tissues exhibit a very good water, oil and dirt repellency, characterized by the contact angle with water and heptane (Tab. 2) and by the evaluation of soil removal after a washing operation at 40 ⁰ C (Tab. 3 ).

Tab. 2 Characterization of water and oil repellency

Tab. 3 Evaluation of the dirt removal

The rating scale includes grades 1-5. Grade 1 corresponds to an invisible cleaning effect and Grade 5 indicates complete removability. Grade 4 is synonymous with barely visible residues (dirt removal> 95%). Based on the values in Tables 2 and 3, according to the invention, the very good water, oil and soil repellency in the dry fabric state and in the wet state of the fabric, the good cleaning ability of the fabric by the responsive functional behavior and the washing resistance of the functional layer.

Example 2: Combination of soil release with an antimicrobial function. This example relates to the preparation of a multifunctional responsive functional layer which combines an antimicrobial action with a hydrophilic or hydrophobic function, wherein the antimicrobial function can be switched on and off by an external stimulus.

In order to meet the high functional standard of workwear in the healthcare sector (hospitals, medical practices, etc.), the corresponding textile material has to be equipped with a combined soil release / antimicrobial function. It is a polyester fabric with a grammage of 160 g. The production of the functional layer is carried out in two stages. In the first application process the responsive and antimicrobial functional composite is applied (Tab. 4) and in the second step the membrane layer is applied. The application of the responsive / antimicrobial layer takes place by means of a padding process (Table 5). The resulting pick up is 45%, based on the dry weight of the Tissue. The drying process after the padding is conducted so that the resulting residual moisture on the fabric after this process step is 20-25%.

In the second step, the membrane layer is also applied with an impregnation process. The pick-up of the fleet containing the membrane composite is 30%. The subsequent drying is carried out at 120 ⁰ C, followed by the condensation process, with a temperature setting of 150 ⁰ C.

Tab. 4 Fleet formulation of the first application step (responsive and antimicrobial).

Tab. 5 liquor formulation of the second application step (membrane formulation)

Tab. 6 Characterization of water and oil repellency

Tab. 7 Evaluation of soil removal

The described equipment shows a wash-resistant, high water, oil and soil repellency due to its responsive behavior in the dry state of the fabric and the excellent leachability of soils when wet, as well as the desired antimicrobial function after fifty washes at 40 ^° C. Especially present in this equipment Good cleaning is usually not given in hydrophobicized with fluorocarbon resins tissues. The antimicrobial activity localized in the polar, responsive polymer unfolds with increasing moisture content. In the water-free or water-poor state of the functional layer, a bacterial attack is hardly possible anyway. The layer characterization is carried out by determining the contact angles with water / alcohol solutions in the unwashed state and after 50 washes (Table 6) as well as by a soiling test with various substances (Table 7). Example 3: Moisture transport and temperature regulating equipment. This example relates to a responsive, equipment-based functional layer on textiles, which layer intrinsically comprises both moisture wicking and thermal regulation. Today's demands on modern sports underwear include not only the pleasant feel, which is essentially determined by the moisture transport, but also the antimicrobial function. An additional desirable function is the heat regulation that is realized today on the fiber material and the Gewirkkonstruktion and possibly with the use of Phase-Change Materials (PCM). According to the invention, the heat-regulating effect is achieved by the use of a responsive composite in this example of equipment. A knitted fabric consisting of 80% polyester, 15% cotton and 5% elastane fiber material is impregnated in one stage with a liquor formulation containing the functional components (Table 8). By applying a responsive composite whose water-storing function is regulated by the temperature, a permanent heat regulation results, in contrast to phase-change materials.

The Flottenappiikation carried out by means of a foulard passage with subsequent crushing, drying of the fabric and condensation for washing permanent fixation of the functional layer on the textile. The fleet order is 72%. The drying is carried out at 110-120 ⁰ C and the condensation at 150 to 160 ⁰ C. The criteria for the evaluation of the functions are the contact angle with water, the antimicrobial effect and the water storage by the responsive composite with the associated water release. The film characterization is performed (Tab. 9) in the unwashed state and after 10 washes, which were carried out at 40 ⁰ C. The liquor formulation is listed below. Tab. 8 Fleet formulation

Tab. 9 Characterization of the functional layer in the unwashed state and after 10 washes.

(1) Test Method: Japanese Industrial Standard JIS L 1902

The values in Table 9 clearly show the decreasing water storage capacity of the repulsive functional layer with increasing temperature and the associated increasing evaporation of water, which extracts heat from the system. According to the invention, this is due to the responsive behavior of the functional layer. This is a direct consequence of the dehydration of the responsive polymer occurring at elevated body temperature.

The bacterial test shows that a permanently high antimicrobial function is present and thus an odor is not given even with strong perspiration. The contact angle with water is over 90 °, which excludes the formation of a wet layer on the body side of the textile, but the water transport through the gas phase is unhindered. The combination of the three functions (moisture transport, thermoregulation, antimicrobial effect) gives the wearer an extremely pleasant wearing experience, even with changing wearing conditions. Example 4: Body temperature regulating equipment of sportswear. This example describes a responsive finishing layer on textiles, especially for sportswear. It regulates body temperature based on water sorption and desorption. With the water desorption from the functional layer, the evaporation rate is increased, as a result of which heat is removed from the body. The external stimuli for the responsive behavior of the functional layer are the temperature and the electrolyte content of the water released by the body (sweat). While under normal load the sweat emitted by the body is primarily transported as water vapor and partially sorbed by the finishing layer, a mixed phase of welding fluid and water vapor occurs during athletic activity. Both the elevated temperature (about 30 ^° C.) and the electrolyte content of the welding fluid lead to contraction and curling of the responsive polymer with the associated 'release' of the sorbed water.

The polymers used for this purpose are, on the one hand, block or random polymers based on polyethylene oxide, which additionally have anionic end groups and, on the other hand, product mixtures, one of the products being nonionic and the other being ionogenic (anionic or cationic) in nature.

A fabric consisting of 92% polyester and 8% elastane is impregnated with a liquor containing the functional polymers (Table 10). The presence of the functional polymer (62% non-ionic, 38% anionic based on the total polymer composition) in the finishing layer leads to the control of the body temperature, with a cooling effect due to the increased water release from about 28 ^° C. The fleet application and the completion of the equipment is done with conventional technology (impregnation, drying and condense). Fleet application is 48% based on the dry weight of the fabric.

The drying is carried out at 100 - 12O ⁰ C and the fixing of the finish layer on the textile substrate at 150 - 160 ⁰ C.

The characterization of the functional layer takes place by detecting the water sorption at different temperature and different electrolyte content of the water. The Fiotten formulation and test results are listed in Tables 10 and 11.

Tab. 10 Fleet formulation

_Flotten component j Function! Company I Conc. G / l

Respond I: Responsive Polymer j HeiQ 75

Phobol XAN | Crosslinker ERBA 8

Fumexol WDN wetting agent ^: ERBA 1

Prodotto 175; Fluorocarbon resin HeiQ 10 JEssjgsäure ^' pH-adjustment Fluka 1

Tab. 11 Characterization results of the functional layer

Water sorption ⁽¹⁾ Washed unwashed 5x Washed 40 ⁰ C ⁰ C q H ₂ O / g DM ^(2> g H ₂ O / g TS < ² >

Deionized water 25 11.70 7.30 Deionized water 40: 0.63 1.12

Saline 1% 25, 13.41 9.12 Saline 1% 40! 0.44 0.95

(1) Water sorption was determined by the percolation method (O. Marte, U. Meyer, New Test Methods for Evaluating Hydrophobic and Superhydrophobic Finishes, Melliand Textile Reports 10/2006)

(2) TS: = dry matter of the finish layer

The test results listed in Table 11 show the high water absorption of the finishing layer at 25 ⁰ C and relative to 25 ⁰ C significantly lower water absorption at 40 ⁰ C. This effect (release of the previously sorbed water), in combination with the evaporation of water, is for the cooling effect of the described equipment on sportswear. A comparison of the sorption values with pure water and those with a physiological saline solution show that the water sorption and release can be increased by electrolytes and thus the cooling effect can be increased. The examples listed are varied and in no way conclusive. For example, achieving greater oil repellency compared to today's fluorocarbon resin-based, water and oil repellent finishes can be achieved through the use of a system responsive component that is also coupled with antimicrobial equipment. Furthermore, the rejection of liquid and / or contaminants present as an aerosol with simultaneous absorption of gaseous substances penetrated into the substrate and their Wiederauswaschbarkeit, based on the responsive effect of the overall system.

Or the production of a multifunctional, responsive functional layer which combines an antistatic effect with a hydrophilic or hydrophobic function, wherein the antistatic function can be switched on and off by an external stimulus.

Uses find the inventive responsive functional layers in working and protective clothing, such. in the hospital, fire department, police, military, forestry and food technology.

Furthermore, for sportswear, e.g. Outdoor clothing as jackets, trousers, headgear, and breathable garments such as shirts, trousers and trainers. Further, as underwear, e.g. Thermal underwear with an additional antimicrobial effect.

Further uses are cloths, tablecloths, tarpaulins, foils, bedding or use as a water collector.

Claims

claims

1. Multifunctional responsive functional layer on a substrate, a solid surface, in particular textiles, paper and plastic materials, characterized in that it comprises at least a first and at least one second functional components (1, 2), of which at least one second functional component (2) the chemically Functional and constitutional prerequisite for a responsive behavior or a responsive property and thus reversibly switchable by an external stimulus, that the at least two functional components (1, 2) differ in their intrinsically predetermined properties, that in the functional layer (5 , 5 ¹ ) present functional components (1, 2) behave cooperatively with respect to their properties in the functional layer and that at least one of the functional components (1, 2) is physically-chemically bonded to the substrate (3).

2. Functional layer according to claim 1, characterized in that the responsive property of the functional layer (5) is predetermined only by the combination of at least one first and second functional components (1, 2).

3. Functional layer according to claim 1 or 2, characterized in that at least one of the first functional components (1) and one of the second functional components (2) is designed as a spacer layer.

4. Functional layer according to one of claims 1 - 3, characterized in that the at least two functional components (1, 2) are present side by side on the substrate (3) and that the removal of water creates a miscibility gap, the formation of water-transporting polymer bridges leads.

5. Functional layer according to one of claims 1 - 4, characterized in that it by mechanical forces in the range of 10 ^"7 Newton (N) up to several Newtons (N), by electromagnetic radiation of different spectral ranges and their strength is switchable.

6. Functional layer according to one of claims 1 - 4, characterized in that it is switchable by physical and / or chemical, layer extrinsic factors such as temperature, pH, electrical charge, moisture, the ionic strength of an electrolyte solution or polymer surface.

7. Functional layer according to one of claims 1-6, characterized in that the external stimulus is stress, temperature, oil and chemical contact.

8. functional layer according to one of claims 1-7, characterized in that the second functional component (2) with the responsive property as a spacer layer on the substrate (3) is physically-chemically connected, that at the second functional component (2) the first functional component (1) is physically-chemically fixed as a hydrophobic barrier layer, whereby the functional layer (5) forms a water reservoir between the substrate (3) and the first functional component (1).

9. Functional layer according to one of claims 1-7, characterized in that the at least one second functional component (2) is a responsive polymer from the group of polyethylene oxide and polypropylene oxide derivatives and their copolymers or from the group of ethoxylated and propoxylated polysaccharides which is polyacrylamides or polyacrylates, which is polyelectrolytes, in particular ionic polysaccharides, acrylamides or acrylates.

10. Functional layer according to claim 9, characterized in that the amount used of the responsive polymer is 0.05-5.0%, preferably 0.1-2.0% of the active substance, based on the dry weight of the textile material to be finished.

11. functional layer according to one of claims 1-10, characterized in that by the incorporation of nano- and / or microparticles in the functional layer (5) this intrinsically intricate a lotus effect or a petal effect layer, wherein the moisture or the corresponding water content of the functional layer (5) the trigger for Circuit of the respective function or property forms.

12. Functional layer according to one of claims 1-11, characterized in that the switchable function is moisture transport, heat transfer, soil release, hydrophobicity, oleophobicity or a combination thereof.

13. Functional layer according to one of claims 1-12, characterized in that the second functional component (2) has an antistatic effect or an antimicrobial effect.

14. Use of the functional layer according to one of claims 1 - 13 for work and protective clothing.

15. Use of the functional layer according to one of claims 1 - 13 for sportswear, outdoor clothing and underwear.

16. Use of the functional layer according to one of claims 1 - 13 as a water collector.

17. A method for producing a multifunctional responsive functional layer according to any one of claims 1-13, characterized in that the at least two functional components (1, 2) are presented in a single liquor and applied to the substrate (3), that the applied substrate in a drying unit is performed, where the formation of the responsive functional layer (5) takes place, that this is physically-chemically fixed on the substrate and that thereby a responsive functional layer (5) is produced in a one-step process.

18. A method for producing a multifunctional responsive functional layer according to one of claims 1 - 13, characterized in that the at least one second functional component (2) is applied to the substrate (2) on two sides and forms a responsive spacer layer, that thereafter the first functional component ( 1) is applied on two sides, that the two-stage acted substrate is fed into a drying unit, where the formation of the responsive functional layer (5) and this is fixed physically-chemically on the substrate and that thereby a responsive functional layer (5) on both sides of the substrate (3) is produced in a two-stage process.

19. A method for producing a multifunctional responsive functional layer according to any one of claims 1-13, characterized in that the at least one second functional component (2) on the substrate (3) is applied on two sides and forms a responsive spacer layer, that thereafter the first functional component ( 1) is applied only on one side, that the two-stage acted substrate is fed into a drying unit, where the formation of the responsive functional layer (5) takes place and this physico-chemically fixed on the substrate and thereby characterized a responsive functional layer (5) on only one Side of the substrate (3) is generated in a two-stage process.

20. The method according to any one of claims 17 - 19, characterized in that the functional components (1, 2) crosslinker and / or catalysts are added, whereby a multifunction composite is formed.